CN111020702A - Rubidium barium bismuth phosphate and cesium barium bismuth phosphate compound, and preparation method and application of nonlinear optical crystal thereof - Google Patents

Rubidium barium bismuth phosphate and cesium barium bismuth phosphate compound, and preparation method and application of nonlinear optical crystal thereof Download PDF

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CN111020702A
CN111020702A CN201911149224.8A CN201911149224A CN111020702A CN 111020702 A CN111020702 A CN 111020702A CN 201911149224 A CN201911149224 A CN 201911149224A CN 111020702 A CN111020702 A CN 111020702A
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陈兆慧
齐鲁
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Xinjiang University
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    • C30—CRYSTAL GROWTH
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    • 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
    • C30B29/14—Phosphates
    • 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
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    • 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
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    • 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
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Abstract

The invention provides two compounds of rubidium (cesium) barium bismuth phosphate, a preparation method and application of two compounds of nonlinear optical crystals, wherein the chemical formulas of the two compounds are M3BaBi(P2O7)2(M = Rb, Cs) by a high temperature solid phase method. The chemical formula of the nonlinear optical crystal of the two compounds is M3BaBi(P2O7)2(M = Rb, Cs), wherein Rb is3BaBi(P2O7)2Belonging to monoclinic system, the space group isP21Cell parameter ofa=8.9377(3) Å，b=9.8247(4) Å，c=9.1683(3) Å，β=106.7460(10)°；Cs3BaBi(P2O7)2Belonging to the orthorhombic system, the space group beingP212121Cell parameter ofa=9.4656(3) Å，b=9.9015(3) Å，c=17.6265(6) Å, the frequency doubling effect of the two phosphate nonlinear optical crystals is about KH respectively2PO4(KDP) is 0.3 and 1.5 times of the KDP, the cut-off edges are 270 and 275 nm respectively, and crystals are grown by a high-temperature melt method and a hydrothermal method. The two crystals have good chemical stability and can be used as ultraviolet-visible nonlinear optical crystals to be applied to all-solid-state lasers.

Description

Rubidium barium bismuth phosphate and cesium barium bismuth phosphate compound, and preparation method and application of nonlinear optical crystal thereof
Technical Field
The invention relates to two compounds of rubidium barium bismuth phosphate and cesium barium bismuth phosphate, and a preparation method and application of nonlinear optical crystals of the two compounds.
Background
Nonlinear optical (NLO) crystal materials are used as key functional materials of many advanced scientific technologies, and are widely applied to various fields such as laser frequency conversion, information communication, optical information processing, laser ranging, medical treatment, laser countermeasure and the like, along with the development of the society and the continuous expansion of application fields, the requirements on nonlinear optical crystal materials are higher and higher, new nonlinear optical crystals with more excellent performance and suitable for different wavelength ranges are continuously explored, and the NLO crystal materials are one of important tasks and challenges faced by modern scientific research workers. In the laser technology, the laser band obtained by directly using the laser crystal is very limited, and there is a blank band from the deep ultraviolet band to the infrared band. An important function of the nonlinear optical crystal material is frequency conversion, so that the laser can output laser wavelength with new frequency, the tunable range of the laser is expanded, the laser can be widely applied, and the nonlinear optical crystal material has important application value in the technical field of laser.
In recent years, phosphates are a new system for exploring nonlinear optical crystal materials due to their structural diversity, wide transmission range and stable physicochemical properties. 2013, the Guilin researcher team of Fujian substance Structure institute of Chinese academy of sciences reports two novel deep ultraviolet NLO phosphates Ba for the first time3P3O10X (X = Cl, Br), pull open the screen of the phosphate NLO crystal material study. In 2016, LiCs were successfully synthesized by the Panshier group of the Xinjiang Hospital institute2PO4The frequency doubling of the nonlinear optical crystal material reaches 2.6 times KDP, the cut-off edge reaches the deep ultraviolet region of 176 nm, and the crystal is a deep ultraviolet nonlinear optical material with application prospect through performance evaluation. Further, RbBa2(PO3)5、LiRb2PO4、Ba5P6O20、Ba2NaClP2O7And a series of phosphate NLO crystal materials with excellent performance are reported successively. Nevertheless, phosphate NLO crystal materials still have their respective disadvantages, such as frequency doubling effect and low birefringence, which are the most important problems faced by phosphates. Therefore, a new design concept is adopted, and the exploration and synthesis of a novel ultraviolet phosphate NLO crystal material with excellent comprehensive performance is still necessary at present.
Disclosure of Invention
The invention aims to provide two compounds of rubidium barium bismuth phosphate and cesium barium bismuth phosphate and a synthesis method thereof, and is characterized in that the chemical formulas of the two compounds are M3BaBi(P2O7)2(M = Rb, Cs) with molecular weights of 950.61 and 1092.93, respectively, were synthesized by high temperature solid phase method.
Another object of the present invention is to provide two phosphate nonlinear optical crystals, wherein the crystal has a chemical formula: m3BaBi(P2O7)2(M = Rb, Cs), wherein Rb is3BaBi(P2O7)2Belonging to monoclinic system, the space group isP21Cell parameter ofa= 8.9377(3) Å，b= 9.8247(4) Å，c= 9.1683(3) Å，β= 106.7460(10) ° unit cell volume 770.93(5) Å3；Cs3BaBi(P2O7)2Belonging to the orthorhombic system, the space group beingP2 12121Cell parameter ofa=9.4656(3) Å，b= 9.9015(3) Å，c=17.6265(6) Å, unit cell volume 1652.02(9) Å3。
It is a further object of the present invention to provide two phosphates M3BaBi(P2O7)2The preparation method of the (M = Rb, Cs) nonlinear optical crystal adopts a high-temperature melt method and a hydrothermal method to grow the crystal.
It is a further object of the present invention to provide two phosphates M3BaBi(P2O7)2Use of a nonlinear optical device made of (M = Rb, Cs) nonlinear optical crystal for the preparation of a frequency doubler generator, an upper or lower frequency converter or an optical parametric oscillator.
The two compounds of the invention are rubidium barium bismuth phosphate and cesium barium bismuth phosphate, and the chemical formulas of the two compounds are M3BaBi(P2O7)2(M = Rb, Cs), and the preparation method of the two compounds rubidium-barium-bismuth phosphate and cesium-barium-bismuth phosphate is synthesized by a high-temperature solid-phase method, and the specific operation is carried out according to the following steps:
uniformly mixing Rb or Cs containing compound, Ba containing compound, Bi containing compound and P containing compound according to the stoichiometric ratio of Rb (Cs) to Ba to Bi to P = 3:1: 4, putting the mixture into a platinum crucible, putting the platinum crucible into a muffle furnace, heating the mixture to the temperature of 450 ℃ and 700 ℃, and keeping the temperature for 20-120 hours to obtain a compound M3BaBi(P2O7)2(M = Rb, Cs), wherein the Rb containing compound is RbF, RbCl, RbBr, RbI, Rb2CO3、RbNO3(ii) a The compound containing Cs is CsF, CsCl, CsBr, CsI, Cs2CO3、CsNO3(ii) a The compound containing Ba is BaCO3、BaO、Ba(NO3)2、Ba(CH3COO)2、BaF2、BaCl2、BaBr2、BaI2(ii) a The bismuth-containing compound is Bi (NO)3)3·5H2O、Bi2O3、Bi(CH3COO)3、Bi(OH)3、(BiO)CO3、BiCl3、BiI3(ii) a The phosphorus-containing compound being NH4H2PO4、(NH4)2HPO4、H3PO4Or P2O5。
Two phosphates M according to the invention3BaBi(P2O7)2The preparation method of the (M = Rb, Cs) nonlinear optical crystal adopts a high-temperature melt method or a hydrothermal method to grow the crystal, and the specific operation steps are as follows:
the high-temperature melt method is used for growing M3BaBi(P2O7)2The specific operation of the (M = Rb, Cs) nonlinear optical crystal is carried out according to the following steps:
a. uniformly mixing Rb or Cs containing compound, Ba containing compound, Bi containing compound and P containing compound according to the stoichiometric ratio of Rb (Cs) to Ba to Bi to P = 3:1: 4, putting the mixture into a platinum crucible, putting the platinum crucible into a muffle furnace, heating the mixture to the temperature of 450 ℃ and 700 ℃, and keeping the temperature for 20-120 hours to obtain a compound M3BaBi(P2O7)2(M = Rb, Cs) polycrystalline powder, wherein the Rb containing compound is RbF, RbCl, RbBr, RbI, Rb2CO3、RbNO3(ii) a The Cs-containing compound is CsF、CsCl、CsBr、CsI、Cs2CO3、CsNO3(ii) a The compound containing Ba is BaCO3、BaO、Ba(NO3)2、Ba(CH3COO)2、BaF2、BaCl2、BaBr2、BaI2(ii) a The bismuth-containing compound is Bi (NO)3)3·5H2O、Bi2O3、Bi(CH3COO)3、Bi(OH)3、(BiO)CO3、BiCl3、BiI3(ii) a The phosphorus-containing compound being NH4H2PO4、(NH4)2HPO4、H3PO4Or P2O5；
b. B, mixing the compound M obtained in the step a3BaBi(P2O7)2(M = Rb, Cs) polycrystalline powder and fluxing agent are uniformly mixed and put into a platinum crucible according to the mol ratio of 1: 0.1-6, the mixture is heated to 650-880 ℃ in a muffle furnace and is kept at the constant temperature for 20-120 hours to obtain mixed melt, and the fluxing agent is RbF, CsF and Bi2O3，NH4H2PO4Or BaF2；
c. Preparing seed crystals: b, placing the mixed melt obtained in the step b in a single crystal furnace, heating to 900 ℃ until the melt is uniform and transparent, then slowly cooling to 500 ℃ at the speed of 1-2 ℃/h, and rapidly cooling to room temperature at the speed of 5-50 ℃/h to obtain M3BaBi(P2O7)2(M = Rb, Cs) seed crystal;
d. growing a crystal: c, fixing the seed crystal obtained in the step c on a seed crystal rod, fixing the seed crystal on the seed crystal rod in any direction, discharging the seed crystal from the top of the crystal growth furnace, preheating the seed crystal for 5-60 min, and discharging the seed crystal to M3BaBi(P2O7)2(M = Rb, Cs) and fluxing agent, the mixture is melted back, the temperature is kept for 5-60 min, the temperature is slowly reduced at the speed of 0.1-3 ℃/day, the seed rod is rotated at the speed of 2-50rpm to grow crystals, after the single crystals grow to the required size, the crystals are lifted from the liquid level and cooled to the room temperature at the speed of 1-100 ℃/h, and then the crystals are taken out from the hearth, thus obtaining the M3BaBi(P2O7)2(M = Rb, Cs) nonlinear optical crystal;
the hydrothermal method is used for growing M3BaBi(P2O7)2The specific operation of the (M = Rb, Cs) nonlinear optical crystal is carried out according to the following steps:
a. uniformly mixing Rb or Cs containing compound, Ba containing compound, Bi containing compound and P containing compound according to the stoichiometric ratio of Rb (Cs) to Ba to Bi to P = 3:1: 4, putting the mixture into a platinum crucible, putting the platinum crucible into a muffle furnace, heating the mixture to the temperature of 450 ℃ and 700 ℃, and keeping the temperature for 20-120 hours to obtain a compound M3BaBi(P2O7)2(M = Rb, Cs) polycrystalline powder, wherein the Rb containing compound is RbF, RbCl, RbBr, RbI, Rb2CO3、RbNO3(ii) a The compound containing Cs is CsF, CsCl, CsBr, CsI, Cs2CO3、CsNO3(ii) a The compound containing Ba is BaCO3、BaO、Ba(NO3)2、Ba(CH3COO)2、BaF2、BaCl2、BaBr2、BaI2(ii) a The bismuth-containing compound is Bi (NO)3)3·5H2O、Bi2O3、Bi(CH3COO)3、Bi(OH)3、(BiO)CO3、BiCl3、BiI3(ii) a The phosphorus-containing compound being NH4H2PO4、(NH4)2HPO4、H3PO4Or P2O5；
b. B, mixing the compound M obtained in the step a3BaBi(P2O7)2Dissolving (M = Rb, Cs) polycrystalline powder in deionized water, subjecting the incompletely dissolved mixture to ultrasonic treatment at 50-90 deg.C to thoroughly mix and dissolve, and dissolving with H3PO4Adjusting the pH value to 3-5;
c. b, transferring the mixed solution obtained in the step b into a clean and pollution-free lining of a high-pressure reaction kettle with the volume of 23 mL, and screwing and sealing the reaction kettle;
d. placing the high-pressure reaction kettle in a constant temperature box, heating to 180 ℃ and 220 ℃, keeping the temperature for 7-15 days, and then cooling to room temperature at a cooling rate of 1-20 ℃/day, namelyTo obtain M3BaBi(P2O7)2(M = Rb, Cs) nonlinear optical crystal.
Said M3BaBi(P2O7)2Use of a (M = Rb, Cs) nonlinear optical crystal for producing 2-fold harmonic light output from a primary-frequency light of 1064 nm wavelength output from a Nd: YAG all-solid-state laser.
Said M3BaBi(P2O7)2Use of a (M = Rb, Cs) nonlinear optical crystal in the preparation of a light source producing uv multiplied light output below 280 nm.
Said M3BaBi(P2O7)2Use of a (M = Rb, Cs) nonlinear optical crystal for the preparation of a frequency doubling generator, an upper or lower frequency converter or an optical parametric oscillator.
Compound M of the present invention3BaBi(P2O7)2The preparation method and the application of the (M = Rb, Cs) nonlinear optical crystal are characterized in that a container used in the preparation process is a platinum crucible, a conical flask and a beaker, and the inner lining is a polytetrafluoroethylene inner lining or a stainless steel inner lining hydrothermal kettle provided with a platinum sleeve. When the container is a conical bottle or a beaker, the container is cleaned by acid, rinsed by deionized water and dried.
Compound M of the present invention3BaBi(P2O7)2The preparation method and the application of the (M = Rb, Cs) nonlinear optical crystal, wherein a resistance furnace used in the preparation process is a muffle furnace or a drying oven.
With the compound M of the invention3BaBi(P2O7)2Preparation method and application of (M = Rb, Cs) nonlinear optical crystal, and large-size M obtained by preparation method3BaBi(P2O7)2(M = Rb, Cs) nonlinear optical crystal, according to the crystallographic data of the crystal, the crystal blank is oriented, the crystal is cut according to the required angle, thickness and section size, the light-passing surface of the crystal is polished, and the crystal can be used as a nonlinear optical device3BaBi(P2O7)2(M = Rb, Cs) nonlinear optical crystal having a light transmitting waveReach ultraviolet region, stable physical and chemical performance, difficult deliquescence, easy processing and preservation and the like.
Drawings
FIGS. 1 and 2 show the X-ray diffraction patterns of powders of rubidium barium bismuth phosphate (cesium barium bismuth phosphate) according to the present invention;
FIGS. 3 and 4 are structural diagrams of rubidium barium bismuth phosphate (cesium barium bismuth phosphate) crystals according to the present invention;
fig. 5 is a schematic diagram of the working principle of the nonlinear optical device manufactured by the present invention, wherein 1 is a laser, 2 is an all-focusing lens, 3 is a rubidium barium bismuth phosphate (cesium barium bismuth phosphate) nonlinear optical crystal, 4 is a beam splitter prism, 5 is a filter, and ω is a frequency of refracted light equal to or 2 times of an incident light frequency.
Detailed Description
The present invention is further described below with reference to examples. It should be noted that the following examples are not intended to limit the scope of the present invention, and any modifications made on the basis of the present invention do not depart from the spirit of the present invention. The raw materials or equipment used in the present invention are commercially available unless otherwise specified.
For Rb3BaBi(P2O7)2In terms of:
example 1:
preparation of the compound:
according to the chemical reaction formula 3Rb2CO3+ Bi2O3+ 2BaCO3+ 8NH4H2PO4→ 2Rb3BaBi(P2O7)2+ 5CO2+ 8NH3+ 12H2O, synthesizing compound Rb by adopting a high-temperature solid-phase method3BaBi(P2O7)2：
a. Will Rb2CO3，Bi2O3，BaCO3，NH4H2PO4Putting the mixture into an agate mortar according to the mol ratio of 3:1:2:8, mixing and finely grinding the mixture to fully and uniformly mix the mixture;
b. placing the uniformly mixed powder in the step a into platinum with the diameter of 2 cmCalcining in a muffle furnace at 300 deg.C to completely volatilize gas, heating to 650 deg.C, maintaining for 100 hr, taking out, grinding to obtain completely sintered Rb3BaBi(P2O7)2Compound polycrystalline powder, X-ray analysis of the product, X-ray spectrum and Rb3BaBi(P2O7)2The X-ray spectra obtained for the single crystal structures were consistent.
Example 2:
preparation of the compound:
according to the chemical reaction formula 3Rb2CO3+ Bi2O3+ 2BaO + 8NH4H2PO4→ 2Rb3BaBi(P2O7)2+ 3CO2+8NH3+ 12H2O, synthesizing compound Rb by adopting a high-temperature solid-phase method3BaBi(P2O7)2：
a. Will Rb2CO3，Bi2O3，BaO，NH4H2PO4Putting the mixture into an agate mortar according to the mol ratio of 3:1:2:8, mixing and finely grinding the mixture to fully and uniformly mix the mixture;
b. b, placing the uniformly mixed powder in the step a into a platinum crucible with the diameter of 2 cm, calcining in a muffle furnace, heating to 300 ℃, keeping the temperature to ensure that the gas is completely volatilized, heating to 620 ℃, keeping the temperature for 85 hours, taking out, grinding to obtain completely sintered Rb3BaBi(P2O7)2Compound polycrystalline powder, X-ray analysis of the product, X-ray spectrum and Rb3BaBi(P2O7)2The X-ray spectra obtained for the single crystal structures were consistent.
Example 3:
preparation of the compound:
according to the chemical reaction formula 6RbF + Bi2O3+ 2BaF2+ 8NH4H2PO4→ 2Rb3BaBi(P2O7)2+ 8NH3+7H2O + 5F2+ 5H2The compound Rb is synthesized by adopting a high-temperature solid-phase method3BaBi(P2O7)2：
a. Mixing RbF and Bi2O3，BaF，NH4H2PO4Putting the mixture into an agate mortar according to the mol ratio of 6:1:2:8, mixing and finely grinding the mixture to fully and uniformly mix the mixture;
b. b, placing the uniformly mixed powder in the step a into a platinum crucible with the diameter of 2 cm, calcining in a muffle furnace, heating to 300 ℃, keeping the temperature to ensure that the gas is completely volatilized, heating to 580 ℃, keeping the temperature for 90 hours, taking out, grinding to obtain completely sintered Rb3BaBi(P2O7)2Compound polycrystalline powder, X-ray analysis of the product, X-ray spectrum and Rb3BaBi(P2O7)2The X-ray spectra obtained for the single crystal structures were consistent.
Example 4:
preparation of the compound:
according to the chemical reaction formula 3RbNO3+ BiCl3+ Ba(NO3)2+ 4(NH4)2HPO4→ Rb3BaBi(P2O7)2+8NH3+ 1/2O2+ 5NO2+ 6H2O + 3/2Cl2The compound Rb is synthesized by adopting a high-temperature solid-phase method3BaBi(P2O7)2：
a. Converting RbNO3，BiCl3，Ba(NO3)2，(NH4)2HPO4Putting the mixture into an agate mortar according to the mol ratio of 3:1:1:4, mixing and finely grinding the mixture to fully and uniformly mix the mixture;
b. b, placing the uniformly mixed powder in the step a into a platinum crucible with the diameter of 2 cm, calcining in a muffle furnace, heating to 300 ℃, keeping the temperature to ensure that the gas is completely volatilized, heating to 600 ℃, keeping the temperature for 110 hours, taking out, grinding to obtain completely sintered Rb3BaBi(P2O7)2Compound polycrystalline powder, X-ray analysis of the product, X-ray spectrum and Rb3BaBi(P2O7)2The X-ray spectra obtained for the single crystal structures were consistent.
Example 5:
preparation of the compound:
according to the chemical reaction formula 3Rb2CO3+ 2Bi(NO3)3·5H2O + 2BaCO3+ 4P2O5→ 2Rb3BaBi(P2O7)2+5CO2+ 6NO2+ 10H2O + 3/2O2The compound Rb is synthesized by adopting a high-temperature solid-phase method3BaBi(P2O7)2：
a. Will Rb2CO3，Bi(NO3)3·5H2O，BaCO3，P2O5Putting the mixture into an agate mortar according to the mol ratio of 3:2:2:4, mixing and finely grinding the mixture to fully and uniformly mix the mixture;
b. b, placing the uniformly mixed powder in the step a into a platinum crucible with the diameter of 2 cm, calcining in a muffle furnace, heating to 300 ℃, keeping the temperature to ensure that the gas is completely volatilized, heating to 700 ℃, keeping the temperature for 80 hours, taking out, grinding to obtain completely sintered Rb3BaBi(P2O7)2Compound polycrystalline powder, X-ray analysis of the product, X-ray spectrum and Rb3BaBi(P2O7)2The X-ray spectra obtained for the single crystal structures were consistent.
Example 6:
preparation of the compound:
according to the chemical reaction formula of 6RbCl + Bi2O3+ 2BaCO3+ 8NH4H2PO4→ 2Rb3BaBi(P2O7)2+ 2CO2+8NH3+ 3Cl2+ 3H2+ 9H2O, synthesizing compound Rb by adopting a high-temperature solid-phase method3BaBi(P2O7)2：
a. Mixing RbCl and Bi2O，BaCO3，NH4H2PO4According to a molar ratio of 6:1:2:8, putting the mixture into an agate mortar for mixing and finely grinding the mixture to ensure that the mixture is fully and uniformly mixed;
b. b, placing the uniformly mixed powder in the step a into a platinum crucible with the diameter of 2 cm, calcining in a muffle furnace, heating to 300 ℃, keeping the temperature to ensure that the gas is completely volatilized, heating to 620 ℃, keeping the temperature for 95 hours, taking out, grinding to obtain completely sintered Rb3BaBi(P2O7)2Compound polycrystalline powder, X-ray analysis of the product, X-ray spectrum and Rb3BaBi(P2O7)2The X-ray spectra obtained for the single crystal structures were consistent.
Example 7:
preparation of the compound:
according to the chemical reaction formula 6RbBr + Bi2O3+ 2BaO + 8NH4H2PO4→ 2Rb3BaBi(P2O7)2+ 8NH3+9H2O + 3Br2+ 3H2The compound Rb is synthesized by adopting a high-temperature solid-phase method3BaBi(P2O7)2：
a. Mixing RbBr and Bi2O3，BaO，NH4H2PO4Putting the mixture into an agate mortar according to the mol ratio of 6:1:2:8, mixing and finely grinding the mixture to fully and uniformly mix the mixture;
b. b, placing the uniformly mixed powder in the step a into a platinum crucible with the diameter of 2 cm, calcining in a muffle furnace, raising the temperature to 300 ℃, keeping the temperature to ensure that the gas is completely volatilized, raising the temperature to 630 ℃, keeping the temperature for 87 hours, taking out, grinding to obtain completely sintered Rb3BaBi(P2O7)2Compound polycrystalline powder, X-ray analysis of the product, X-ray spectrum and Rb3BaBi(P2O7)2The X-ray spectra obtained for the single crystal structures were consistent.
Example 8:
preparation of the compound:
according to the chemical reaction formula 3Rb2CO3+ Bi2O3+ 2BaCl2+ 8NH4H2PO4→ 2Rb3BaBi(P2O7)2+ 3CO2+ 8NH3+ 2Cl2+ 2H2+ 10H2O, synthesizing compound Rb by adopting a high-temperature solid-phase method3BaBi(P2O7)2：
a. Will Rb2CO3，Bi2O3，BaCl2，NH4H2PO4Putting the mixture into an agate mortar according to the mol ratio of 3:1:2:8, mixing and finely grinding the mixture to fully and uniformly mix the mixture;
b. b, placing the uniformly mixed powder in the step a into a platinum crucible with the diameter of 2 cm, calcining in a muffle furnace, heating to 300 ℃, keeping the temperature to ensure that the gas is completely volatilized, heating to 660 ℃, keeping the temperature for 120 hours, taking out, grinding to obtain completely sintered Rb3BaBi(P2O7)2Compound polycrystalline powder, X-ray analysis of the product, X-ray spectrum and Rb3BaBi(P2O7)2The X-ray spectra obtained for the single crystal structures were consistent.
Example 9:
preparation of the compound:
according to the chemical reaction formula 3RbI + Bi (OH)3+ BaCO3+ 2P2O5→ Rb3BaBi(P2O7)2+ 3/2I2+ CO2+ 3/2H2The compound Rb is synthesized by adopting a high-temperature solid-phase method3BaBi(P2O7)2：
a. Mixing RbI, Bi (OH)3，BaCO3，P2O5Putting the mixture into an agate mortar according to the mol ratio of 3:1:1:2, mixing and finely grinding the mixture to fully and uniformly mix the mixture;
b. b, placing the uniformly mixed powder in the step a into a platinum crucible with the diameter of 2 cm, calcining in a muffle furnace, heating to 300 ℃, keeping the temperature to ensure that the gas is completely volatilized, heating to 680 ℃, keeping the temperature for 75 hours, taking out, grinding to obtain completely sintered Rb3BaBi(P2O7)2Compound polycrystalline powder, X-ray analysis of the product, X-ray spectrum and Rb3BaBi(P2O7)2The X-ray spectra obtained for the single crystal structures were consistent.
Example 10:
preparation of the compound:
according to the chemical reaction formula 3Rb2CO3+ Bi2O3+ 2BaBr2+ 8NH4H2PO4→ 2Rb3BaBi(P2O7)2+ 3CO2+ 8NH3+ 2Br2+ 2H2+ 10H2O, synthesizing compound Rb by adopting a high-temperature solid-phase method3BaBi(P2O7)2：
a. Will Rb2CO3，Bi2O3，BaBr2，NH4H2PO4Putting the mixture into an agate mortar according to the mol ratio of 3:1:2:8, mixing and finely grinding the mixture to fully and uniformly mix the mixture;
b. b, placing the uniformly mixed powder in the step a into a platinum crucible with the diameter of 2 cm, calcining in a muffle furnace, heating to 300 ℃, keeping the temperature to ensure that the gas is completely volatilized, heating to 550 ℃, keeping the temperature for 105 hours, taking out, grinding to obtain completely sintered Rb3BaBi(P2O7)2Compound polycrystalline powder, X-ray analysis of the product, X-ray spectrum and Rb3BaBi(P2O7)2The X-ray spectra obtained for the single crystal structures were consistent.
Example 11:
preparation of the compound:
according to the chemical reaction formula 3Rb2CO3+ 2Bi(CH3COO)3+ 2Ba(CH3COO)2+ 8NH4H2PO4→ 2Rb3BaBi(P2O7)2+ 8NH3+ 3CO2+ 10CH3COOH + 7H2O, synthesizing compound Rb by adopting a high-temperature solid-phase method3BaBi(P2O7)2：
a. Will Rb2CO3，Bi(CH3COO)3，Ba(CH3COO)2，NH4H2PO4Putting the mixture into an agate mortar according to the mol ratio of 3:2:2:8, mixing, and finely grinding to fully and uniformly mix the mixture;
b. b, placing the uniformly mixed powder in the step a into a platinum crucible with the diameter of 2 cm, calcining in a muffle furnace, raising the temperature to 300 ℃, keeping the temperature to ensure that the gas is completely volatilized, raising the temperature to 650 ℃, keeping the temperature for 56 hours, taking out, grinding to obtain completely sintered Rb3BaBi(P2O7)2Compound polycrystalline powder, X-ray analysis of the product, X-ray spectrum and Rb3BaBi(P2O7)2The X-ray spectra obtained for the single crystal structures were consistent.
Example 12:
preparation of the compound:
according to the chemical reaction formula 3Rb2CO3+ 2(BiO)CO3+ 2BaI2+ 8NH4H2PO4→ 2Rb3BaBi(P2O7)2+8NH3+ 5CO2+ 2I2+ H2+ 11H2O, synthesizing compound Rb by adopting a high-temperature solid-phase method3BaBi(P2O7)2：
a. Will Rb2CO3，(BiO)CO3，BaI2，NH4H2PO4Putting the mixture into an agate mortar according to the mol ratio of 3:2:2:8, mixing, and finely grinding to fully and uniformly mix the mixture;
b. b, placing the uniformly mixed powder in the step a into a platinum crucible with the diameter of 2 cm, calcining in a muffle furnace, heating to 300 ℃, keeping the temperature to ensure that the gas is completely volatilized, heating to 680 ℃, keeping the temperature for 110 hours, taking out, grinding to obtain completely sintered Rb3BaBi(P2O7)2Compound polycrystalline powder, X-ray analysis of the product, X-ray spectrum and Rb3BaBi(P2O7)2The X-ray spectra obtained for the single crystal structures were consistent.
Example 13:
preparation of the compound:
according to the chemical reaction formula 3Rb2CO3+ 2BiI3+ 2BaCO3+ 8NH4H2PO4→ 2Rb3BaBi(P2O7)2+ 8NH3+ 5CO2+ 3I2+ 3H2+ 6H2O, synthesizing compound Rb by adopting a high-temperature solid-phase method3BaBi(P2O7)2：
a. Will Rb2CO3，BiI3，BaCO3，NH4H2PO4Putting the mixture into an agate mortar according to the mol ratio of 3:2:2:8, mixing, and finely grinding to fully and uniformly mix the mixture;
b. b, placing the uniformly mixed powder in the step a into a platinum crucible with the diameter of 2 cm, calcining in a muffle furnace, heating to 300 ℃, keeping the temperature to ensure that the gas is completely volatilized, heating to 620 ℃, keeping the temperature for 85 hours, taking out, grinding to obtain completely sintered Rb3BaBi(P2O7)2Compound polycrystalline powder, X-ray analysis of the product, X-ray spectrum and Rb3BaBi(P2O7)2The X-ray spectra obtained for the single crystal structures were consistent.
Example 14:
high temperature melt method for Rb growth3BaBi(P2O7)2Nonlinear optical crystal:
a. compound Rb prepared according to example 13BaBi(P2O7)2Uniformly mixing the polycrystalline powder and a fluxing agent RbF according to the mol ratio of 1: 0.1, putting the mixture into a platinum crucible, heating the mixture to 850 ℃ in a muffle furnace, and keeping the temperature for 100 hours to obtain a mixed solution;
b. preparing seed crystals: cooling the mixed melt obtained in the step a, transferring the cooled mixed melt into a single crystal growth furnace, heating to 900 ℃ until the melt is uniform and transparent, keeping the temperature for 40 hours, then slowly reducing the temperature to 500 ℃ at the speed of 1 ℃/hour, and then, at the temperature of 10 DEG CThe/h rate is rapidly reduced to room temperature, and single crystal powder is finally obtained, and transparent crystals are selected from the single crystal powder. To obtain Rb3BaBi(P2O7)2Seed crystal;
c. growing a crystal: b, fixing the seed crystal obtained in the step b on a seed crystal rod, fixing the seed crystal on the seed crystal rod in any direction, discharging the seed crystal from the top of the crystal growth furnace, preheating the seed crystal for 15 min, and discharging the seed crystal to Rb3BaBi(P2O7)2Melting back the mixture of the crystal and the fluxing agent, keeping the temperature for 60 min, slowly cooling at the speed of 0.1 ℃/day, rotating the seed rod at the speed of 2 rpm to grow crystals, lifting the crystals away from the liquid surface after the single crystals grow to the required size, cooling to the room temperature at the speed of 100 ℃/h, and taking the crystals out of the furnace to obtain Rb3BaBi(P2O7)2A nonlinear optical crystal.
Example 15:
high temperature melt method for Rb growth3BaBi(P2O7)2Nonlinear optical crystal:
a. compound Rb prepared according to example 23BaBi(P2O7)2Polycrystalline powder and flux Bi2O3Uniformly mixing the components according to the molar ratio of 1: 0.5, putting the mixture into a platinum crucible, heating the mixture to 880 ℃ in a muffle furnace, and keeping the temperature for 120 hours to obtain a mixed melt;
b. preparing seed crystals: and (b) cooling the mixed melt obtained in the step (a), transferring the cooled mixed melt into a single crystal growth furnace, heating to 900 ℃ until the melt is uniform and transparent, keeping the temperature for 40 h, slowly cooling to 500 ℃ at the speed of 1.5 ℃/h, and quickly cooling to room temperature at the speed of 20 ℃/h to finally obtain single crystal powder, and picking out transparent crystals from the single crystal powder. To obtain Rb3BaBi(P2O7)2Seed crystal;
c. growing a crystal: b, fixing the seed crystal obtained in the step b on a seed crystal rod, fixing the seed crystal on the seed crystal rod in any direction, discharging the seed crystal from the top of the crystal growth furnace, preheating the seed crystal for 20 min, and discharging the seed crystal to Rb3BaBi(P2O7)2Melting back the mixture in the mixed solution of the fluxing agent,keeping the temperature for 50 min, slowly cooling at a speed of 1 ℃/day, rotating the seed rod at a speed of 2 rpm to grow crystals, lifting the crystals out of the liquid surface after the single crystals grow to the required size, cooling to room temperature at a speed of 80 ℃/h, and taking out the crystals from the hearth to obtain Rb3BaBi(P2O7)2A nonlinear optical crystal.
Example 16:
high temperature melt method for Rb growth3BaBi(P2O7)2Nonlinear optical crystal:
a. compound Rb prepared according to example 33BaBi(P2O7)2Uniformly mixing the polycrystalline powder and a fluxing agent BaF according to the mol ratio of 1: 0.3, putting the mixture into a platinum crucible, heating the mixture to 880 ℃ in a muffle furnace, and keeping the temperature for 90 hours to obtain a mixed melt;
b. preparing seed crystals: and (b) cooling the mixed melt obtained in the step (a), transferring the cooled mixed melt into a single crystal growth furnace, heating to 900 ℃ until the melt is uniform and transparent, keeping the temperature for 40 h, slowly cooling to 500 ℃ at the speed of 2 ℃/h, and quickly cooling to room temperature at the speed of 30 ℃/h to finally obtain single crystal powder, and picking out transparent crystals from the single crystal powder. To obtain Rb3BaBi(P2O7)2Seed crystal;
c. growing a crystal: b, fixing the seed crystal obtained in the step b on a seed crystal rod, fixing the seed crystal on the seed crystal rod in any direction, discharging the seed crystal from the top of the crystal growth furnace, preheating the seed crystal for 40 min, and discharging the seed crystal to Rb3BaBi(P2O7)2Melting back the mixture of the crystal and the fluxing agent, keeping the temperature for 20 min, slowly cooling at the speed of 0.5 ℃/day, rotating the seed rod at the rotating speed of 4 rpm to grow crystals, lifting the crystals away from the liquid surface after the single crystals grow to the required size, cooling to room temperature at the speed of 90 ℃/h, and taking the crystals out of the furnace to obtain Rb3BaBi(P2O7)2A nonlinear optical crystal.
Example 17:
high temperature melt method for Rb growth3BaBi(P2O7)2Nonlinear optical crystal：
a. Compound Rb prepared according to example 43BaBi(P2O7)2Polycrystalline powder and flux NH4H2PO4Uniformly mixing the components according to the molar ratio of 1:1, putting the mixture into a platinum crucible, heating the mixture to 850 ℃ in a muffle furnace, and keeping the temperature for 110 hours to obtain a mixed melt;
b. preparing seed crystals: and (b) cooling the mixed melt obtained in the step (a), transferring the cooled mixed melt into a single crystal growth furnace, heating to 900 ℃ until the melt is uniform and transparent, keeping the temperature for 40 h, slowly cooling to 500 ℃ at the speed of 1 ℃/h, and quickly cooling to room temperature at the speed of 50 ℃/h to finally obtain single crystal powder, and picking out transparent crystals from the single crystal powder. To obtain Rb3BaBi(P2O7)2Seed crystal;
c. growing a crystal: b, fixing the seed crystal obtained in the step b on a seed crystal rod, fixing the seed crystal on the seed crystal rod in any direction, discharging the seed crystal from the top of the crystal growth furnace, preheating the seed crystal for 30 min, and discharging the seed crystal to Rb3BaBi(P2O7)2Melting back the mixture of the crystal and the fluxing agent, keeping the temperature for 35 min, slowly cooling at the speed of 0.3 ℃/day, rotating the seed rod at the speed of 5 rpm to grow crystals, lifting the crystals away from the liquid surface after the single crystals grow to the required size, cooling to room temperature at the speed of 50 ℃/h, and taking the crystals out of the furnace to obtain Rb3BaBi(P2O7)2A nonlinear optical crystal.
Example 18:
high temperature melt method for Rb growth3BaBi(P2O7)2Nonlinear optical crystal:
a. compound Rb prepared according to example 53BaBi(P2O7)2Uniformly mixing the polycrystalline powder and a fluxing agent RbF according to the mol ratio of 1:2, putting the mixture into a platinum crucible, heating the mixture to 870 ℃ in a muffle furnace, and keeping the temperature for 80 hours to obtain a mixed melt;
b. preparing seed crystals: cooling the mixed melt obtained in the step a, transferring the cooled mixed melt into a single crystal growth furnace, heating to 900 ℃ until the melt is uniform and transparent, keeping the temperature for 40 hours, and then keeping the temperatureSlowly reducing the temperature to 500 ℃ at the speed of 1 ℃/h, and then rapidly reducing the temperature to room temperature at the speed of 20 ℃/h to finally obtain single crystal powder, and picking out transparent crystals from the single crystal powder. To obtain Rb3BaBi(P2O7)2Seed crystal;
c. growing a crystal: b, fixing the seed crystal obtained in the step b on a seed crystal rod, fixing the seed crystal on the seed crystal rod in any direction, discharging the seed crystal from the top of the crystal growth furnace, preheating the seed crystal for 60 min, and discharging the seed crystal to Rb3BaBi(P2O7)2Melting back the mixture of the crystal and the fluxing agent, keeping the temperature for 10 min, slowly cooling at the speed of 2 ℃/day, rotating the seed rod at the speed of 2 rpm to grow crystals, lifting the crystals away from the liquid surface after the single crystals grow to the required size, cooling to room temperature at the speed of 60 ℃/h, and taking out the crystals from the hearth to obtain Rb3BaBi(P2O7)2A nonlinear optical crystal.
Example 19:
high temperature melt method for Rb growth3BaBi(P2O7)2Nonlinear optical crystal:
a. compound Rb prepared according to example 63BaBi(P2O7)2Polycrystalline powder and flux Bi2O3Uniformly mixing the components according to the molar ratio of 1:4, putting the mixture into a platinum crucible, heating the mixture to 850 ℃ in a muffle furnace, and keeping the temperature for 70 hours to obtain a mixed melt;
b. preparing seed crystals: and (b) cooling the mixed melt obtained in the step (a), transferring the cooled mixed melt into a single crystal growth furnace, heating to 900 ℃ until the melt is uniform and transparent, keeping the temperature for 40 h, slowly cooling to 500 ℃ at the speed of 2 ℃/h, and quickly cooling to room temperature at the speed of 5 ℃/h to finally obtain single crystal powder, and picking out transparent crystals from the single crystal powder. To obtain Rb3BaBi(P2O7)2Seed crystal;
c. growing a crystal: b, fixing the seed crystal obtained in the step b on a seed crystal rod, fixing the seed crystal on the seed crystal rod in any direction, discharging the seed crystal from the top of the crystal growth furnace, preheating the seed crystal for 10 min, and discharging the seed crystal to Rb3BaBi(P2O7)2Melting back the mixture of the crystal and the fluxing agent, keeping the temperature for 60 min, slowly cooling at the speed of 3 ℃/day, rotating the seed rod at the speed of 2 rpm to grow crystals, lifting the crystals away from the liquid surface after the single crystals grow to the required size, cooling to room temperature at the speed of 70 ℃/h, and taking out the crystals from the hearth to obtain Rb3BaBi(P2O7)2A nonlinear optical crystal.
Example 20:
high temperature melt method for Rb growth3BaBi(P2O7)2Nonlinear optical crystal:
a. compound Rb prepared according to example 73BaBi(P2O7)2Polycrystalline powder and flux NH4H2PO4Uniformly mixing the components according to the molar ratio of 1: 5, putting the mixture into a platinum crucible, heating the mixture to 860 ℃ in a muffle furnace, and keeping the temperature for 85 hours to obtain mixed melt;
b. preparing seed crystals: and (b) cooling the mixed melt obtained in the step (a), transferring the cooled mixed melt into a single crystal growth furnace, heating to 900 ℃ until the melt is uniform and transparent, keeping the temperature for 40 h, slowly cooling to 500 ℃ at the speed of 1.5 ℃/h, and quickly cooling to room temperature at the speed of 10 ℃/h to finally obtain single crystal powder, and picking out transparent crystals from the single crystal powder. To obtain Rb3BaBi(P2O7)2Seed crystal;
c. growing a crystal: b, fixing the seed crystal obtained in the step b on a seed crystal rod, fixing the seed crystal on the seed crystal rod in any direction, discharging the seed crystal from the top of the crystal growth furnace, preheating the seed crystal for 12 min, and discharging the seed crystal to Rb3BaBi(P2O7)2Melting back the mixture of the crystal and the fluxing agent, keeping the temperature for 40 min, slowly cooling at the speed of 0.2 ℃/day, rotating the seed rod at the speed of 3 rpm to grow crystals, lifting the crystals away from the liquid surface after the single crystals grow to the required size, cooling to room temperature at the speed of 50 ℃/h, and taking out the crystals from the hearth to obtain Rb3BaBi(P2O7)2A nonlinear optical crystal.
Example 21:
high temperature melt processGrowing Rb3BaBi(P2O7)2Nonlinear optical crystal:
a. compound Rb prepared according to example 83BaBi(P2O7)2Uniformly mixing the polycrystalline powder and a fluxing agent RbF according to the mol ratio of 1: 3, putting the mixture into a platinum crucible, heating the mixture to 880 ℃ in a muffle furnace, and keeping the temperature for 100 hours to obtain a mixed melt;
b. preparing seed crystals: and (b) cooling the mixed melt obtained in the step (a), transferring the cooled mixed melt into a single crystal growth furnace, heating to 900 ℃ until the melt is uniform and transparent, keeping the temperature for 40 h, slowly cooling to 500 ℃ at the speed of 1 ℃/h, and quickly cooling to room temperature at the speed of 50 ℃/h to finally obtain single crystal powder, and picking out transparent crystals from the single crystal powder. To obtain Rb3BaBi(P2O7)2Seed crystal;
c. growing a crystal: b, fixing the seed crystal obtained in the step b on a seed crystal rod, fixing the seed crystal on the seed crystal rod in any direction, discharging the seed crystal from the top of the crystal growth furnace, preheating the seed crystal for 35 min, and discharging the seed crystal to Rb3BaBi(P2O7)2Melting back the mixture of the crystal and the fluxing agent, keeping the temperature for 25 min, slowly cooling at the speed of 0.1 ℃/day, rotating the seed rod at the speed of 2 rpm to grow crystals, lifting the crystals away from the liquid surface after the single crystals grow to the required size, cooling to the room temperature at the speed of 100 ℃/h, and taking the crystals out of the furnace to obtain Rb3BaBi(P2O7)2A nonlinear optical crystal.
Example 22:
hydrothermal method for growing Rb3BaBi(P2O7)2Nonlinear optical crystal:
compound Rb prepared according to example 93BaBi(P2O7)2Dissolving the polycrystalline powder in deionized water, treating incompletely dissolved mixture with ultrasonic wave at 60 deg.C to make it fully mixed and dissolved, and dissolving with H3PO4Adjusting the pH value to 4;
transferring the obtained mixed solution into a clean pollution-free lining of a high-pressure reaction kettle with the volume of 23 mL, and screwing and sealing the reaction kettle;
placing the high-pressure reaction kettle in a constant temperature box, heating to 200 ℃, keeping the temperature for 14 days, and then cooling to room temperature at a cooling rate of 5 ℃/day to obtain Rb with the thickness of 3 mm multiplied by 2 mm3BaBi(P2O7)2A nonlinear optical crystal.
Example 23:
hydrothermal method for growing Rb3BaBi(P2O7)2Nonlinear optical crystal:
compound Rb prepared according to example 103BaBi(P2O7)2Dissolving the polycrystalline powder in deionized water, treating incompletely dissolved mixture with ultrasonic wave at 60 deg.C to make it fully mixed and dissolved, and dissolving with H3PO4Adjusting the pH value to 4;
transferring the obtained mixed solution into a clean pollution-free lining of a high-pressure reaction kettle with the volume of 23 mL, and screwing and sealing the reaction kettle;
placing the high-pressure reaction kettle in a constant temperature box, heating to 200 ℃, keeping the temperature for 10 days, and then cooling to room temperature at a cooling rate of 10 ℃/day to obtain Rb with the thickness of 3 mm multiplied by 2 mm multiplied by 1 mm3BaBi(P2O7)2A nonlinear optical crystal.
Example 24:
hydrothermal method for growing Rb3BaBi(P2O7)2Nonlinear optical crystal:
compound Rb prepared according to example 113BaBi(P2O7)2Dissolving the polycrystalline powder in deionized water, treating incompletely dissolved mixture with ultrasonic wave at 60 deg.C to make it fully mixed and dissolved, and dissolving with H3PO4Adjusting the pH value to 5;
transferring the obtained mixed solution into a clean pollution-free lining of a high-pressure reaction kettle with the volume of 23 mL, and screwing and sealing the reaction kettle;
placing the high-pressure reaction kettle in a constant temperature box, heating to 200 ℃, keeping the temperature for 12 days, and then reducing the temperature to 10 ℃/dayAt room temperature, obtaining 2 mm multiplied by 1 mm Rb3BaBi(P2O7)2A nonlinear optical crystal.
Example 25:
hydrothermal method for growing Rb3BaBi(P2O7)2Nonlinear optical crystal:
compound Rb prepared according to example 133BaBi(P2O7)2Dissolving the polycrystalline powder in deionized water, treating incompletely dissolved mixture with ultrasonic wave at 60 deg.C to make it fully mixed and dissolved, and dissolving with H3PO4Adjusting the pH value to 4;
transferring the obtained mixed solution into a clean pollution-free lining of a high-pressure reaction kettle with the volume of 23 mL, and screwing and sealing the reaction kettle;
placing the high-pressure reaction kettle in a constant temperature box, heating to 200 ℃, keeping the temperature for 14 days, and then cooling to room temperature at a cooling rate of 5 ℃/day to obtain Rb with the thickness of 3 mm multiplied by 1 mm multiplied by 2 mm3BaBi(P2O7)2A nonlinear optical crystal.
For Cs3BaBi(P2O7)2In terms of:
example 1:
preparation of the compound:
according to the chemical reaction formula 3Cs2CO3+ Bi2O3+ 2BaCO3+ 8NH4H2PO4→ 2Cs3BaBi(P2O7)2+ 5CO2+ 8NH3+ 12H2O, synthesizing the compound Cs by adopting a high-temperature solid-phase method3BaBi(P2O7)2：
a. Mixing Cs2CO3，Bi2O3，BaCO3，NH4H2PO4Putting the mixture into an agate mortar according to the mol ratio of 3:1:2:8, mixing and finely grinding the mixture to fully and uniformly mix the mixture;
b. b, placing the uniformly mixed powder in the step a into a platinum crucible with the diameter of 2 cm, calcining in a muffle furnace, and heatingRaising the temperature to 300 ℃, keeping the temperature to ensure that the gas is completely volatilized, then raising the temperature to 650 ℃, keeping the temperature for 100 hours, taking out and grinding to obtain fully sintered Cs3BaBi(P2O7)2Compound polycrystal powder, X-ray analysis of the product to obtain X-ray spectrum and Cs3BaBi(P2O7)2The X-ray spectra obtained for the single crystal structures were consistent.
Example 2:
preparation of the compound:
according to the chemical reaction formula 3Cs2CO3+ Bi2O3+ 2BaO + 8NH4H2PO4→ 2Cs3BaBi(P2O7)2+ 3CO2+8NH3+ 12H2O, synthesizing the compound Cs by adopting a high-temperature solid-phase method3BaBi(P2O7)2：
a. Mixing Cs2CO3，Bi2O3，BaO，NH4H2PO4Putting the mixture into an agate mortar according to the mol ratio of 3:1:2:8, mixing and finely grinding the mixture to fully and uniformly mix the mixture;
b. b, placing the uniformly mixed powder in the step a into a platinum crucible with the diameter of 2 cm, calcining in a muffle furnace, heating to 300 ℃, keeping the temperature to ensure that the gas is completely volatilized, heating to 620 ℃, keeping the temperature for 85 hours, taking out, grinding to obtain fully sintered Cs3BaBi(P2O7)2Compound polycrystal powder, X-ray analysis of the product to obtain X-ray spectrum and Cs3BaBi(P2O7)2The X-ray spectra obtained for the single crystal structures were consistent.
Example 3:
preparation of the compound:
according to the chemical reaction formula 6CsF + Bi2O3+ 2BaF2+ 8NH4H2PO4→ 2Cs3BaBi(P2O7)2+ 8NH3+7H2O + 5F2+ 5H2Synthesized by high-temperature solid-phase methodSubstance Cs3BaBi(P2O7)2：
a. Mixing CsF and Bi2O3，BaF，NH4H2PO4Putting the mixture into an agate mortar according to the mol ratio of 6:1:2:8, mixing and finely grinding the mixture to fully and uniformly mix the mixture;
b. b, placing the uniformly mixed powder in the step a into a platinum crucible with the diameter of 2 cm, calcining in a muffle furnace, heating to 300 ℃, keeping the temperature to ensure that the gas is completely volatilized, heating to 580 ℃, keeping the temperature for 90 hours, taking out, grinding to obtain the Cs completely sintered3BaBi(P2O7)2Compound polycrystal powder, X-ray analysis of the product to obtain X-ray spectrum and Cs3BaBi(P2O7)2The X-ray spectra obtained for the single crystal structures were consistent.
Example 4:
preparation of the compound:
according to the chemical reaction formula 3CsNO3+ BiCl3+ Ba(NO3)2+ 4(NH4)2HPO4→ Cs3BaBi(P2O7)2+8NH3+ 1/2O2+ 5NO2+ 6H2O + 3/2Cl2Synthesizing the compound Cs by adopting a high-temperature solid-phase method3BaBi(P2O7)2：
a. CsNO is added3，BiCl3，Ba(NO3)2，(NH4)2HPO4Putting the mixture into an agate mortar according to the mol ratio of 3:1:1:4, mixing and finely grinding the mixture to fully and uniformly mix the mixture;
b. b, placing the uniformly mixed powder in the step a into a platinum crucible with the diameter of 2 cm, calcining in a muffle furnace, heating to 300 ℃, keeping the temperature to ensure that the gas is completely volatilized, heating to 600 ℃, keeping the temperature for 110 hours, taking out, grinding to obtain fully sintered Cs3BaBi(P2O7)2Compound polycrystal powder, X-ray analysis of the product to obtain X-ray spectrum and Cs3BaBi(P2O7)2The X-ray spectra obtained for the single crystal structures were consistent.
Example 5:
preparation of the compound:
according to the chemical reaction formula 3Cs2CO3+ 2Bi(NO3)3·5H2O + 2BaCO3+ 4P2O5→ 2Cs3BaBi(P2O7)2+5CO2+ 6NO2+ 10H2O + 3/2O2Synthesizing the compound Cs by adopting a high-temperature solid-phase method3BaBi(P2O7)2：
a. Mixing Cs2CO3，Bi(NO3)3·5H2O，BaCO3，P2O5Putting the mixture into an agate mortar according to the mol ratio of 3:2:2:4, mixing and finely grinding the mixture to fully and uniformly mix the mixture;
b. b, placing the uniformly mixed powder in the step a into a platinum crucible with the diameter of 2 cm, calcining in a muffle furnace, heating to 300 ℃, keeping the temperature to ensure that the gas is completely volatilized, heating to 700 ℃, keeping the temperature for 80 hours, taking out, grinding to obtain the completely sintered Cs3BaBi(P2O7)2Compound polycrystal powder, X-ray analysis of the product to obtain X-ray spectrum and Cs3BaBi(P2O7)2The X-ray spectra obtained for the single crystal structures were consistent.
Example 6:
preparation of the compound:
according to the chemical reaction formula 6CsCl + Bi2O3+ 2BaCO3+ 8NH4H2PO4→ 2Cs3BaBi(P2O7)2+ 2CO2+8NH3+ 3Cl2+ 3H2+ 9H2O, synthesizing the compound Cs by adopting a high-temperature solid-phase method3BaBi(P2O7)2：
a. CsCl, Bi2O，BaCO3，NH4H2PO4Putting the mixture into an agate mortar according to the mol ratio of 6:1:2:8, mixing and finely grinding the mixture,mixing them uniformly;
b. b, placing the uniformly mixed powder in the step a into a platinum crucible with the diameter of 2 cm, calcining in a muffle furnace, heating to 300 ℃, keeping the temperature to ensure that the gas is completely volatilized, heating to 620 ℃, keeping the temperature for 95 hours, taking out, grinding to obtain the completely sintered Cs3BaBi(P2O7)2Compound polycrystal powder, X-ray analysis of the product to obtain X-ray spectrum and Cs3BaBi(P2O7)2The X-ray spectra obtained for the single crystal structures were consistent.
Example 7:
preparation of the compound:
according to the chemical reaction formula 6CsBr + Bi2O3+ 2BaO + 8NH4H2PO4→ 2Cs3BaBi(P2O7)2+ 8NH3+9H2O + 3Br2+ 3H2Synthesizing the compound Cs by adopting a high-temperature solid-phase method3BaBi(P2O7)2：
a. Mixing CsBr, Bi2O3，BaO，NH4H2PO4Putting the mixture into an agate mortar according to the mol ratio of 6:1:2:8, mixing and finely grinding the mixture to fully and uniformly mix the mixture;
b. b, placing the uniformly mixed powder in the step a into a platinum crucible with the diameter of 2 cm, calcining in a muffle furnace, raising the temperature to 300 ℃, keeping the temperature to ensure that the gas is completely volatilized, raising the temperature to 630 ℃, keeping the temperature for 87 hours, taking out, grinding to obtain fully sintered Cs3BaBi(P2O7)2Compound polycrystal powder, X-ray analysis of the product to obtain X-ray spectrum and Cs3BaBi(P2O7)2The X-ray spectra obtained for the single crystal structures were consistent.
Example 8:
preparation of the compound:
according to the chemical reaction formula 3Cs2CO3+ Bi2O3+ 2BaCl2+ 8NH4H2PO4→ 2Cs3BaBi(P2O7)2+ 3CO2+ 8NH3+ 2Cl2+ 2H2+ 10H2O, synthesizing the compound Cs by adopting a high-temperature solid-phase method3BaBi(P2O7)2：
a. Mixing Cs2CO3，Bi2O3，BaCl2，NH4H2PO4Putting the mixture into an agate mortar according to the mol ratio of 3:1:2:8, mixing and finely grinding the mixture to fully and uniformly mix the mixture;
b. b, placing the uniformly mixed powder in the step a into a platinum crucible with the diameter of 2 cm, calcining in a muffle furnace, heating to 300 ℃, keeping the temperature constant to ensure that the gas is completely volatilized, heating to 660 ℃, keeping the temperature constant for 120 hours, taking out, grinding to obtain fully sintered Cs3BaBi(P2O7)2Compound polycrystal powder, X-ray analysis of the product to obtain X-ray spectrum and Cs3BaBi(P2O7)2The X-ray spectra obtained for the single crystal structures were consistent.
Example 9:
preparation of the compound:
according to the chemical reaction formula 3CsI + Bi (OH)3+ BaCO3+ 2P2O5→ Cs3BaBi(P2O7)2+ 3/2I2+ CO2+ 3/2H2Synthesizing the compound Cs by adopting a high-temperature solid-phase method3BaBi(P2O7)2：
a. Mixing CsI, Bi (OH)3，BaCO3，P2O5Putting the mixture into an agate mortar according to the mol ratio of 3:1:1:2, mixing and finely grinding the mixture to fully and uniformly mix the mixture;
b. b, placing the uniformly mixed powder in the step a into a platinum crucible with the diameter of 2 cm, calcining in a muffle furnace, heating to 300 ℃, keeping the temperature to ensure that the gas is completely volatilized, heating to 680 ℃, keeping the temperature for 75 hours, taking out, grinding to obtain fully sintered Cs3BaBi(P2O7)2Polycrystalline powder of the compound, process for producing the samePerforming X-ray analysis to obtain X-ray spectrogram and Cs3BaBi(P2O7)2The X-ray spectra obtained for the single crystal structures were consistent.
Example 10:
preparation of the compound:
according to the chemical reaction formula 3Cs2CO3+ Bi2O3+ 2BaBr2+ 8NH4H2PO4→ 2Cs3BaBi(P2O7)2+ 3CO2+ 8NH3+ 2Br2+ 2H2+ 10H2O, synthesizing the compound Cs by adopting a high-temperature solid-phase method3BaBi(P2O7)2：
a. Mixing Cs2CO3，Bi2O3，BaBr2，NH4H2PO4Putting the mixture into an agate mortar according to the mol ratio of 3:1:2:8, mixing and finely grinding the mixture to fully and uniformly mix the mixture;
b. b, placing the uniformly mixed powder in the step a into a platinum crucible with the diameter of 2 cm, calcining in a muffle furnace, raising the temperature to 300 ℃, keeping the temperature constant to ensure that the gas is completely volatilized, raising the temperature to 550 ℃, keeping the temperature constant for 105 hours, taking out, grinding to obtain the Cs completely sintered3BaBi(P2O7)2Compound polycrystal powder, X-ray analysis of the product to obtain X-ray spectrum and Cs3BaBi(P2O7)2The X-ray spectra obtained for the single crystal structures were consistent.
Example 11:
preparation of the compound:
according to the chemical reaction formula 3Cs2CO3+ 2Bi(CH3COO)3+ 2Ba(CH3COO)2+ 8NH4H2PO4→ 2Cs3BaBi(P2O7)2+ 8NH3+ 3CO2+ 10CH3COOH + 7H2O, synthesizing the compound Cs by adopting a high-temperature solid-phase method3BaBi(P2O7)2：
a. Mixing Cs2CO3，Bi(CH3COO)3，Ba(CH3COO)2，NH4H2PO4Putting the mixture into an agate mortar according to the mol ratio of 3:2:2:8, mixing, and finely grinding to fully and uniformly mix the mixture;
b. b, placing the uniformly mixed powder in the step a into a platinum crucible with the diameter of 2 cm, calcining in a muffle furnace, raising the temperature to 300 ℃, keeping the temperature to ensure that the gas is completely volatilized, raising the temperature to 650 ℃, keeping the temperature for 56 hours, taking out, grinding to obtain fully sintered Cs3BaBi(P2O7)2Compound polycrystal powder, X-ray analysis of the product to obtain X-ray spectrum and Cs3BaBi(P2O7)2The X-ray spectra obtained for the single crystal structures were consistent.
Example 12:
preparation of the compound:
according to the chemical reaction formula 3Cs2CO3+ 2(BiO)CO3+ 2BaI2+ 8NH4H2PO4→ 2Cs3BaBi(P2O7)2+8NH3+ 5CO2+ 2I2+ H2+ 11H2O, synthesizing the compound Cs by adopting a high-temperature solid-phase method3BaBi(P2O7)2：
a. Will be Cs2CO3，(BiO)CO3，BaI2，NH4H2PO4Putting the mixture into an agate mortar according to the mol ratio of 3:2:2:8, mixing, and finely grinding to fully and uniformly mix the mixture;
b. b, placing the uniformly mixed powder in the step a into a platinum crucible with the diameter of 2 cm, calcining in a muffle furnace, heating to 300 ℃, keeping the temperature to ensure that the gas is completely volatilized, heating to 680 ℃, keeping the temperature for 110 hours, taking out, grinding to obtain fully sintered Cs3BaBi(P2O7)2Compound polycrystal powder, X-ray analysis of the product to obtain X-ray spectrum and Cs3BaBi(P2O7)2The X-ray spectra obtained for the single crystal structures were consistent.
Example 13:
preparation of the compound:
according to the chemical reaction formula 3Cs2CO3+ 2BiI3+ 2BaCO3+ 8NH4H2PO4→ 2Cs3BaBi(P2O7)2+ 8NH3+ 5CO2+ 3I2+ 3H2+ 6H2O, synthesizing the compound Cs by adopting a high-temperature solid-phase method3BaBi(P2O7)2：
a. Will be Cs2CO3，BiI3，BaCO3，NH4H2PO4Putting the mixture into an agate mortar according to the mol ratio of 3:2:2:8, mixing, and finely grinding to fully and uniformly mix the mixture;
b. b, placing the uniformly mixed powder in the step a into a platinum crucible with the diameter of 2 cm, calcining in a muffle furnace, heating to 300 ℃, keeping the temperature to ensure that the gas is completely volatilized, heating to 620 ℃, keeping the temperature for 85 hours, taking out, grinding to obtain fully sintered Cs3BaBi(P2O7)2Compound polycrystal powder, X-ray analysis of the product to obtain X-ray spectrum and Cs3BaBi(P2O7)2The X-ray spectra obtained for the single crystal structures were consistent.
Example 14:
high temperature melt method for growing Cs3BaBi(P2O7)2Nonlinear optical crystal:
a. compound Cs prepared according to example 13BaBi(P2O7)2Uniformly mixing the polycrystalline powder and a fluxing agent CsF according to the molar ratio of 1: 0.1, putting the mixture into a platinum crucible, heating the mixture to 850 ℃ in a muffle furnace, and keeping the temperature for 100 hours to obtain a mixed melt;
b. preparing seed crystals: cooling the mixed melt obtained in the step a, transferring the cooled mixed melt into a single crystal growth furnace, heating to 900 ℃ until the melt is uniform and transparent, keeping the temperature for 40 h, then slowly cooling to 500 ℃ at the speed of 1 ℃/h, and rapidly cooling to room temperature at the speed of 10 ℃/h to finally obtain the single crystalPowder, from which clear crystals were sorted out. To obtain Cs3BaBi(P2O7)2Seed crystal;
c. growing a crystal: b, fixing the seed crystal obtained in the step b on a seed crystal rod, fixing the seed crystal on the seed crystal rod in any direction, discharging the seed crystal from the top of the crystal growth furnace, preheating the seed crystal for 15 min, and discharging the seed crystal to Cs3BaBi(P2O7)2Melting back the mixture of the crystal and the fluxing agent, keeping the temperature for 60 min, slowly cooling at the speed of 0.1 ℃/day, rotating the seed rod at the speed of 2 rpm to grow crystals, lifting the crystals away from the liquid surface after the single crystals grow to the required size, cooling to room temperature at the speed of 100 ℃/h, and taking the crystals out of the furnace to obtain Cs3BaBi(P2O7)2A nonlinear optical crystal.
Example 15:
high temperature melt method for growing Cs3BaBi(P2O7)2Nonlinear optical crystal:
a. compound Cs prepared according to example 23BaBi(P2O7)2Polycrystalline powder and flux Bi2O3Uniformly mixing the components according to the molar ratio of 1: 0.5, putting the mixture into a platinum crucible, heating the mixture to 880 ℃ in a muffle furnace, and keeping the temperature for 120 hours to obtain a mixed melt;
b. preparing seed crystals: and (b) cooling the mixed melt obtained in the step (a), transferring the cooled mixed melt into a single crystal growth furnace, heating to 900 ℃ until the melt is uniform and transparent, keeping the temperature for 40 h, slowly cooling to 500 ℃ at the speed of 1.5 ℃/h, and quickly cooling to room temperature at the speed of 20 ℃/h to finally obtain single crystal powder, and picking out transparent crystals from the single crystal powder. To obtain Cs3BaBi(P2O7)2Seed crystal;
c. growing a crystal: b, fixing the seed crystal obtained in the step b on a seed crystal rod, fixing the seed crystal on the seed crystal rod in any direction, discharging the seed crystal from the top of the crystal growth furnace, preheating the seed crystal for 20 min, and discharging the seed crystal to Cs3BaBi(P2O7)2Melting back in the mixed solution of the fluxing agent, keeping the temperature for 50 min, slowly cooling at the speed of 1 ℃/day,rotating the seed rod at the rotating speed of 2 rpm to grow crystals, lifting the crystals away from the liquid surface after the single crystals grow to the required size, reducing the temperature to room temperature at the speed of 80 ℃/h, and taking the crystals out of the hearth to obtain Cs3BaBi(P2O7)2A nonlinear optical crystal.
Example 16:
high temperature melt method for growing Cs3BaBi(P2O7)2Nonlinear optical crystal:
a. compound Cs prepared according to example 33BaBi(P2O7)2Uniformly mixing the polycrystalline powder and a fluxing agent BaF according to the mol ratio of 1: 0.3, putting the mixture into a platinum crucible, heating the mixture to 880 ℃ in a muffle furnace, and keeping the temperature for 90 hours to obtain a mixed melt;
b. preparing seed crystals: and (b) cooling the mixed melt obtained in the step (a), transferring the cooled mixed melt into a single crystal growth furnace, heating to 900 ℃ until the melt is uniform and transparent, keeping the temperature for 40 h, slowly cooling to 500 ℃ at the speed of 2 ℃/h, and quickly cooling to room temperature at the speed of 30 ℃/h to finally obtain single crystal powder, and picking out transparent crystals from the single crystal powder. To obtain Cs3BaBi(P2O7)2Seed crystal;
c. growing a crystal: b, fixing the seed crystal obtained in the step b on a seed crystal rod, fixing the seed crystal on the seed crystal rod in any direction, discharging the seed crystal from the top of the crystal growth furnace, preheating the seed crystal for 40 min, and discharging the seed crystal to Cs3BaBi(P2O7)2Melting back the mixture of the crystal and the fluxing agent, keeping the temperature for 20 min, slowly cooling at the speed of 0.5 ℃/day, rotating the seed rod at the rotating speed of 4 rpm to grow crystals, lifting the crystals away from the liquid surface after the single crystals grow to the required size, cooling to room temperature at the speed of 90 ℃/h, and taking the crystals out of the furnace to obtain Cs3BaBi(P2O7)2A nonlinear optical crystal.
Example 17:
high temperature melt method for growing Cs3BaBi(P2O7)2Nonlinear optical crystal:
a. according toCompound Cs prepared in example 43BaBi(P2O7)2Polycrystalline powder and flux NH4H2PO4Uniformly mixing the components according to the molar ratio of 1:1, putting the mixture into a platinum crucible, heating the mixture to 850 ℃ in a muffle furnace, and keeping the temperature for 110 hours to obtain a mixed melt;
b. preparing seed crystals: and (b) cooling the mixed melt obtained in the step (a), transferring the cooled mixed melt into a single crystal growth furnace, heating to 900 ℃ until the melt is uniform and transparent, keeping the temperature for 40 h, slowly cooling to 500 ℃ at the speed of 1 ℃/h, and quickly cooling to room temperature at the speed of 50 ℃/h to finally obtain single crystal powder, and picking out transparent crystals from the single crystal powder. To obtain Cs3BaBi(P2O7)2Seed crystal;
c. growing a crystal: b, fixing the seed crystal obtained in the step b on a seed crystal rod, fixing the seed crystal on the seed crystal rod in any direction, discharging the seed crystal from the top of the crystal growth furnace, preheating the seed crystal for 30 min, and discharging the seed crystal to Cs3BaBi(P2O7)2Melting back the mixture of the crystal and the fluxing agent, keeping the temperature for 35 min, slowly cooling at the speed of 0.3 ℃/day, rotating the seed rod at the speed of 5 rpm to grow crystals, lifting the crystals away from the liquid surface after the single crystals grow to the required size, cooling to room temperature at the speed of 50 ℃/h, and taking the crystals out of the furnace to obtain Cs3BaBi(P2O7)2A nonlinear optical crystal.
Example 18:
high temperature melt method for growing Cs3BaBi(P2O7)2Nonlinear optical crystal:
a. compound Cs prepared according to example 53BaBi(P2O7)2Uniformly mixing the polycrystalline powder and a fluxing agent CsF according to the molar ratio of 1:2, putting the mixture into a platinum crucible, heating the mixture to 870 ℃ in a muffle furnace, and keeping the temperature for 80 hours to obtain a mixed melt;
b. preparing seed crystals: cooling the mixed melt obtained in the step a, transferring the cooled mixed melt into a single crystal growth furnace, heating to 900 ℃ until the melt is uniform and transparent, keeping the temperature for 40 hours, then slowly reducing the temperature to 500 ℃ at the speed of 1 ℃/h, and then slowly reducing the temperature by 2 DEG CThe temperature is rapidly reduced to the room temperature at the speed of 0 ℃/h, and single crystal powder is finally obtained, and transparent crystals are selected from the single crystal powder. To obtain Cs3BaBi(P2O7)2Seed crystal;
c. growing a crystal: b, fixing the seed crystal obtained in the step b on a seed crystal rod, fixing the seed crystal on the seed crystal rod in any direction, discharging the seed crystal from the top of the crystal growth furnace, preheating the seed crystal for 60 min, and discharging the seed crystal to Cs3BaBi(P2O7)2Melting back the mixture of the crystal and the fluxing agent, keeping the temperature for 10 min, slowly cooling at the speed of 2 ℃/day, rotating the seed rod at the speed of 2 rpm to grow crystals, lifting the crystals away from the liquid surface after the single crystals grow to the required size, cooling to room temperature at the speed of 60 ℃/h, and taking out the crystals from the hearth to obtain the Cs3BaBi(P2O7)2A nonlinear optical crystal.
Example 19:
high temperature melt method for growing Cs3BaBi(P2O7)2Nonlinear optical crystal:
a. compound Cs prepared according to example 63BaBi(P2O7)2Polycrystalline powder and flux Bi2O3Uniformly mixing the components according to the molar ratio of 1:4, putting the mixture into a platinum crucible, heating the mixture to 850 ℃ in a muffle furnace, and keeping the temperature for 70 hours to obtain a mixed melt;
b. preparing seed crystals: and (b) cooling the mixed melt obtained in the step (a), transferring the cooled mixed melt into a single crystal growth furnace, heating to 900 ℃ until the melt is uniform and transparent, keeping the temperature for 40 h, slowly cooling to 500 ℃ at the speed of 2 ℃/h, and quickly cooling to room temperature at the speed of 5 ℃/h to finally obtain single crystal powder, and picking out transparent crystals from the single crystal powder. To obtain Cs3BaBi(P2O7)2Seed crystal;
c. growing a crystal: b, fixing the seed crystal obtained in the step b on a seed crystal rod, fixing the seed crystal on the seed crystal rod in any direction, discharging the seed crystal from the top of the crystal growth furnace, preheating the seed crystal for 10 min, and discharging the seed crystal to Cs3BaBi(P2O7)2Is melted back in the mixed solution of the fluxing agentHeating for 60 min, slowly cooling at a speed of 3 ℃/day, rotating the seed rod at a speed of 2 rpm to grow crystals, lifting the crystals out of the liquid surface after the single crystals grow to the required size, cooling to room temperature at a speed of 70 ℃/h, and taking out the crystals from the hearth to obtain Cs3BaBi(P2O7)2A nonlinear optical crystal.
Example 20:
high temperature melt method for growing Cs3BaBi(P2O7)2Nonlinear optical crystal:
a. compound Cs prepared according to example 73BaBi(P2O7)2Polycrystalline powder and flux NH4H2PO4Uniformly mixing the components according to the molar ratio of 1: 5, putting the mixture into a platinum crucible, heating the mixture to 860 ℃ in a muffle furnace, and keeping the temperature for 85 hours to obtain mixed melt;
b. preparing seed crystals: and (b) cooling the mixed melt obtained in the step (a), transferring the cooled mixed melt into a single crystal growth furnace, heating to 900 ℃ until the melt is uniform and transparent, keeping the temperature for 40 h, slowly cooling to 500 ℃ at the speed of 1.5 ℃/h, and quickly cooling to room temperature at the speed of 10 ℃/h to finally obtain single crystal powder, and picking out transparent crystals from the single crystal powder. To obtain Cs3BaBi(P2O7)2Seed crystal;
c. growing a crystal: b, fixing the seed crystal obtained in the step b on a seed crystal rod, fixing the seed crystal on the seed crystal rod in any direction, discharging the seed crystal from the top of the crystal growth furnace, preheating the seed crystal for 12 min, and discharging the seed crystal to Cs3BaBi(P2O7)2Melting back the mixture of the crystal and the fluxing agent, keeping the temperature for 40 min, slowly cooling at the speed of 0.2 ℃/day, rotating the seed rod at the rotating speed of 3 rpm to grow crystals, lifting the crystals away from the liquid surface after the single crystals grow to the required size, cooling to room temperature at the speed of 50 ℃/h, and taking the crystals out of the furnace to obtain Cs3BaBi(P2O7)2A nonlinear optical crystal.
Example 21:
high temperature melt method for growing Cs3BaBi(P2O7)2Nonlinear optical crystal:
a. compound Cs prepared according to example 83BaBi(P2O7)2Uniformly mixing the polycrystalline powder and a fluxing agent CsF according to the molar ratio of 1: 3, putting the mixture into a platinum crucible, heating the mixture to 880 ℃ in a muffle furnace, and keeping the temperature for 100 hours to obtain a mixed melt;
b. preparing seed crystals: and (b) cooling the mixed melt obtained in the step (a), transferring the cooled mixed melt into a single crystal growth furnace, heating to 900 ℃ until the melt is uniform and transparent, keeping the temperature for 40 h, slowly cooling to 500 ℃ at the speed of 1 ℃/h, and quickly cooling to room temperature at the speed of 50 ℃/h to finally obtain single crystal powder, and picking out transparent crystals from the single crystal powder. To obtain Cs3BaBi(P2O7)2Seed crystal;
c. growing a crystal: b, fixing the seed crystal obtained in the step b on a seed crystal rod, fixing the seed crystal on the seed crystal rod in any direction, discharging the seed crystal from the top of the crystal growth furnace, preheating the seed crystal for 35 min, and discharging the seed crystal to Cs3BaBi(P2O7)2Melting back the mixture of the crystal and the fluxing agent, keeping the temperature for 25 min, slowly cooling at the speed of 0.1 ℃/day, rotating the seed rod at the speed of 2 rpm to grow crystals, lifting the crystals away from the liquid surface after the single crystals grow to the required size, cooling to room temperature at the speed of 100 ℃/h, and taking out the crystals from the hearth to obtain the Cs3BaBi(P2O7)2A nonlinear optical crystal.
Example 22:
hydrothermal growth of Cs3BaBi(P2O7)2Nonlinear optical crystal:
compound Cs prepared according to example 93BaBi(P2O7)2Dissolving the polycrystalline powder in deionized water, treating incompletely dissolved mixture with ultrasonic wave at 60 deg.C to make it fully mixed and dissolved, and dissolving with H3PO4Adjusting the pH value to 4;
transferring the obtained mixed solution into a clean pollution-free lining of a high-pressure reaction kettle with the volume of 23 mL, and screwing and sealing the reaction kettle;
placing the high-pressure reaction kettle in a constant temperature box, heating to 200 ℃, keeping the temperature for 14 days, and then cooling to room temperature at a cooling rate of 5 ℃/day to obtain Cs with the size of 5 mm multiplied by 4 mm multiplied by 2 mm3BaBi(P2O7)2A nonlinear optical crystal.
Example 23:
hydrothermal growth of Cs3BaBi(P2O7)2Nonlinear optical crystal:
compound Cs prepared according to example 103BaBi(P2O7)2Dissolving the polycrystalline powder in deionized water, treating incompletely dissolved mixture with ultrasonic wave at 60 deg.C to make it fully mixed and dissolved, and dissolving with H3PO4Adjusting the pH value to 4;
transferring the obtained mixed solution into a clean pollution-free lining of a high-pressure reaction kettle with the volume of 23 mL, and screwing and sealing the reaction kettle;
placing the high-pressure reaction kettle in a constant temperature box, heating to 200 ℃, keeping the temperature for 10 days, and then cooling to room temperature at a cooling rate of 10 ℃/day to obtain Cs with the size of 3 mm multiplied by 2 mm3BaBi(P2O7)2A nonlinear optical crystal.
Example 24:
hydrothermal growth of Cs3BaBi(P2O7)2Nonlinear optical crystal:
compound Cs prepared according to example 113BaBi(P2O7)2Dissolving the polycrystalline powder in deionized water, treating incompletely dissolved mixture with ultrasonic wave at 60 deg.C to make it fully mixed and dissolved, and dissolving with H3PO4Adjusting the pH value to 5;
transferring the obtained mixed solution into a clean pollution-free lining of a high-pressure reaction kettle with the volume of 23 mL, and screwing and sealing the reaction kettle;
placing the high-pressure reaction kettle in a constant temperature box, heating to 200 ℃, keeping the temperature for 12 days, and then cooling to room temperature at a cooling rate of 10 ℃/day to obtain Cs with the size of 2 mm multiplied by 2 mm3BaBi(P2O7)2A nonlinear optical crystal.
Example 25:
hydrothermal growth of Cs3BaBi(P2O7)2Nonlinear optical crystal:
compound Cs prepared according to example 133BaBi(P2O7)2Dissolving the polycrystalline powder in deionized water, treating incompletely dissolved mixture with ultrasonic wave at 60 deg.C to make it fully mixed and dissolved, and dissolving with H3PO4Adjusting the pH value to 4;
transferring the obtained mixed solution into a clean pollution-free lining of a high-pressure reaction kettle with the volume of 23 mL, and screwing and sealing the reaction kettle;
placing the high-pressure reaction kettle in a constant temperature box, heating to 200 ℃, keeping the temperature for 14 days, and then cooling to room temperature at a cooling rate of 5 ℃/day to obtain Cs with the size of 5 mm multiplied by 3 mm multiplied by 2 mm3BaBi(P2O7)2A nonlinear optical crystal.
The compounds obtained in examples 1-13, arranged at the position 3 as shown in FIG. 5, were observed to give a significant 532 nm double-frequency green output for Rb at room temperature using a 1064 nm output from a YAG laser at QNd as the light source3BaBi(P2O7)2The output intensity is about 0.3 times of KDP under the same condition; for Cs3BaBi(P2O7)2The output intensity is about 1.5 times of that of the KDP of the same condition.

Claims (6)

1. Two compounds of rubidium barium bismuth phosphate and cesium barium bismuth phosphate are characterized in that the chemical formulas of the two compounds are M3BaBi(P2O7)2(M = Rb, Cs) with molecular weights of 950.61 and 1092.93, respectively.
2. A method for preparing two compounds of rubidium-barium-bismuth phosphate and cesium-barium-bismuth phosphate according to claim 1, which is characterized by adopting a high-temperature solid-phase method for synthesis, and the specific operation is carried out according to the following steps:
the high-temperature solid phase method is used for preparing compounds of rubidium barium bismuth phosphate and cesium barium bismuth phosphate:
uniformly mixing Rb or Cs containing compound, Ba containing compound, Bi containing compound and P containing compound according to the stoichiometric ratio of Rb (Cs) to Ba to Bi to P = 3:1: 4, putting the mixture into a platinum crucible, putting the platinum crucible into a muffle furnace, heating the mixture to the temperature of 450 ℃ and 700 ℃, and keeping the temperature for 20-120 hours to obtain a compound M3BaBi(P2O7)2(M = Rb, Cs), wherein the Rb containing compound is RbF, RbCl, RbBr, RbI, Rb2CO3、RbNO3(ii) a The compound containing Cs is CsF, CsCl, CsBr, CsI, Cs2CO3、CsNO3(ii) a The compound containing Ba is BaCO3、BaO、Ba(NO3)2、Ba(CH3COO)2、BaF2、BaCl2、BaBr2、BaI2(ii) a The bismuth-containing compound is Bi (NO)3)3·5H2O、Bi2O3、Bi(CH3COO)3、Bi(OH)3、(BiO)CO3、BiCl3、BiI3(ii) a The phosphorus-containing compound being NH4H2PO4、(NH4)2HPO4、H3PO4Or P2O5。
3. The two phosphate nonlinear optical crystals of rubidium barium bismuth phosphate and cesium barium bismuth phosphate are characterized in that the two crystals have the chemical formulas: m3BaBi(P2O7)2(M = Rb, Cs), wherein Rb is3BaBi(P2O7)2Belonging to monoclinic system, the space group isP21Cell parameter ofa= 8.9377(3) Å，b= 9.8247(4) Å，c= 9.1683(3) Å，β= 106.7460(10) ° unit cell volume 770.93(5) Å3；Cs3BaBi(P2O7)2Belonging to the orthorhombic system, the space group beingP212121Cell parameter ofa=9.4656(3) Å，b= 9.9015(3) Å，c=17.6265(6) Å, unit cell volume 1652.02(9) Å3。
4. A method for preparing the nonlinear optical crystal of two phosphates according to claim 3, wherein the crystal is grown by a high temperature melt method and a hydrothermal method;
the high-temperature melt method is used for growing M3BaBi(P2O7)2The specific operation of the (M = Rb, Cs) nonlinear optical crystal is carried out according to the following steps:
a. uniformly mixing Rb or Cs containing compound, Ba containing compound, Bi containing compound and P containing compound according to the stoichiometric ratio of Rb (Cs) to Ba to Bi to P = 3:1: 4, putting the mixture into a platinum crucible, putting the platinum crucible into a muffle furnace, heating the mixture to the temperature of 450 ℃ and 700 ℃, and keeping the temperature for 20-120 hours to obtain a compound M3BaBi(P2O7)2(M = Rb, Cs) polycrystalline powder, wherein the Rb containing compound is RbF, RbCl, RbBr, RbI, Rb2CO3、RbNO3(ii) a The compound containing Cs is CsF, CsCl, CsBr, CsI, Cs2CO3、CsNO3(ii) a The compound containing Ba is BaCO3、BaO、Ba(NO3)2、Ba(CH3COO)2、BaF2、BaCl2、BaBr2、BaI2(ii) a The bismuth-containing compound is Bi (NO)3)3·5H2O、Bi2O3、Bi(CH3COO)3、Bi(OH)3、(BiO)CO3、BiCl3、BiI3(ii) a The phosphorus-containing compound being NH4H2PO4、(NH4)2HPO4、H3PO4Or P2O5；
b. B, mixing the compound M obtained in the step a3BaBi(P2O7)2(M = Rb, Cs) polycrystalline powder and fluxing agent are uniformly mixed and put into a platinum crucible according to the mol ratio of 1: 0.1-6, the mixture is heated to 650-880 ℃ in a muffle furnace and is kept at the constant temperature for 20-120 hours to obtain mixed melt, and the fluxing agent is RbF, CsF and Bi2O3，NH4H2PO4Or BaF2；
c. Preparing seed crystals: will step withB, placing the mixed melt obtained in the step b in a single crystal furnace, heating to 900 ℃ until the melt is uniform and transparent, then slowly cooling to 500 ℃ at the speed of 1-2 ℃/h, and then rapidly cooling to room temperature at the speed of 5-50 ℃/h to obtain M3BaBi(P2O7)2(M = Rb, Cs) seed crystal;
d. growing a crystal: c, fixing the seed crystal obtained in the step c on a seed crystal rod, fixing the seed crystal on the seed crystal rod in any direction, discharging the seed crystal from the top of the crystal growth furnace, preheating the seed crystal for 5-60 min, and discharging the seed crystal to M3BaBi(P2O7)2(M = Rb, Cs) and fluxing agent, the mixture is melted back, the temperature is kept for 5-60 min, the temperature is slowly reduced at the speed of 0.1-3 ℃/day, the seed rod is rotated at the speed of 2-50rpm to grow crystals, after the single crystals grow to the required size, the crystals are lifted from the liquid level and cooled to the room temperature at the speed of 1-100 ℃/h, and then the crystals are taken out from the hearth, thus obtaining the M3BaBi(P2O7)2(M = Rb, Cs) nonlinear optical crystal;
the hydrothermal method is used for growing M3BaBi(P2O7)2The specific operation of the (M = Rb, Cs) nonlinear optical crystal is carried out according to the following steps:
a. uniformly mixing Rb or Cs containing compound, Ba containing compound, Bi containing compound and P containing compound according to the stoichiometric ratio of Rb (Cs) to Ba to Bi to P = 3:1: 4, putting the mixture into a platinum crucible, putting the platinum crucible into a muffle furnace, heating the mixture to the temperature of 450 ℃ and 700 ℃, and keeping the temperature for 20-120 hours to obtain a compound M3BaBi(P2O7)2(M = Rb, Cs) polycrystalline powder, wherein the Rb containing compound is RbF, RbCl, RbBr, RbI, Rb2CO3、RbNO3(ii) a The compound containing Cs is CsF, CsCl, CsBr, CsI, Cs2CO3、CsNO3(ii) a The compound containing Ba is BaCO3、BaO、Ba(NO3)2、Ba(CH3COO)2、BaF2、BaCl2、BaBr2、BaI2(ii) a The bismuth-containing compound is Bi (NO)3)3·5H2O、Bi2O3、Bi(CH3COO)3、Bi(OH)3、(BiO)CO3、BiCl3、BiI3(ii) a The phosphorus-containing compound being NH4H2PO4、(NH4)2HPO4、H3PO4Or P2O5；
b. B, mixing the compound M obtained in the step a3BaBi(P2O7)2Dissolving (M = Rb, Cs) polycrystalline powder in deionized water, subjecting the incompletely dissolved mixture to ultrasonic treatment at 50-90 deg.C to thoroughly mix and dissolve, and dissolving with H3PO4Adjusting the pH value to 3-5;
c. b, transferring the mixed solution obtained in the step b into a clean and pollution-free lining of a high-pressure reaction kettle with the volume of 23 mL, and screwing and sealing the reaction kettle;
d. placing the high-pressure reaction kettle in a constant temperature box, heating to 180 ℃ and 220 ℃, keeping the temperature for 7-15 days, and then cooling to room temperature at the cooling rate of 1-20 ℃/day to obtain M3BaBi(P2O7)2(M = Rb, Cs) nonlinear optical crystal.
5. M according to claim 33BaBi(P2O7)2Use of a (M = Rb, Cs) nonlinear optical crystal for producing 2-fold harmonic light output from a primary-frequency light of 1064 nm wavelength output from a Nd: YAG all-solid-state laser.
6. The method according to claim 3, characterized in that the two phosphate nonlinear optical crystals obtained by the method are used for the preparation of a frequency doubler generator, an upper or lower frequency converter or an optical parametric oscillator.
CN201911149224.8A 2019-11-21 2019-11-21 Rubidium barium bismuth phosphate and cesium barium bismuth phosphate compound, and preparation method and application of nonlinear optical crystal thereof Pending CN111020702A (en)

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Application publication date: 20200417