CN115991481A - Compound lanthanum strontium chloroborate and lanthanum barium chloroborate, nonlinear optical crystal thereof and preparation method and application thereof - Google Patents

Compound lanthanum strontium chloroborate and lanthanum barium chloroborate, nonlinear optical crystal thereof and preparation method and application thereof Download PDF

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CN115991481A
CN115991481A CN202111219639.5A CN202111219639A CN115991481A CN 115991481 A CN115991481 A CN 115991481A CN 202111219639 A CN202111219639 A CN 202111219639A CN 115991481 A CN115991481 A CN 115991481A
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lanthanum
barium
strontium
chloroborate
pbo
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吴红萍
袁斌倩
俞洪伟
胡章贵
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Tianjin University of Technology
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Abstract

The invention relates to a compound strontium lanthanum chloroborate and barium lanthanum chloroborate, and a nonlinear optical crystal of the strontium lanthanum chloroborate and the barium lanthanum chloroborate, a preparation method and application thereof, wherein the chemical formulas of the compound and the crystal are A 3 La 4 B 3 O 13 Cl, wherein A=Sr, ba, the space group is P6 3 Belongs to a hexagonal system, and has unit cell parameters of
Figure DDA0003312096560000011
Figure DDA0003312096560000012
Z=2. The compound strontium lanthanum chloroborate and barium lanthanum chloroborate are synthesized by adopting a solid phase reaction method, the nonlinear optical crystals of the strontium lanthanum chloroborate and the barium lanthanum chloroborate are grown by adopting a high-temperature melt method, and the material can be applied to manufacturing a second harmonic generator, an upper-lower frequency converter, an optical parametric oscillator and the like.

Description

Compound lanthanum strontium chloroborate and lanthanum barium chloroborate, nonlinear optical crystal thereof and preparation method and application thereof
Technical Field
The invention relates to a compound with a chemical formula A 3 La 4 B 3 O 13 The compound of Cl (A=Sr, ba) is chlorborate lanthanum strontium chloroborate and chlorborate barium lanthanum chloroborate nonlinear optical crystal, the preparation method of the crystal and nonlinear optical device made of the crystal.
Background
Nonlinear optical crystals are one of important photoelectric information functional materials and are an important material basis for optoelectronic technology, particularly laser technology. The nonlinear optical crystal material can be used for converting laser frequency and expanding laser wavelength, and is used for adjusting the intensity and phase of laser so as to realize holographic storage of laser signals. Therefore, the nonlinear optical crystal is an indispensable key material in the advanced technology and the modern military technology, and the information technology is put in a development priority position in each country and is brought into advanced technology development planning as an important strategic measure for high importance and support.
The requirements for the second-order nonlinear optical crystal mainly comprise a non-central symmetrical structure, proper double refractive index, wide transmission range in the ultraviolet region, high laser damage threshold, excellent physical and chemical properties and the like. Borate crystals have important application values in the fields of semiconductor lithography, laser micromachining and photochemical synthesis, and the performances of the borate crystals are widely focused. The band gap is larger, the laser damage threshold is higher, the physical and chemical properties are stable, the strong nonlinear optical effect is favorable to be obtained, the novel ultraviolet nonlinear optical crystal is ideal, alkaline earth cations and rare earth elements (Sr or Ba and La) are introduced into borate, no electron transition of d-d and f-f exists, and the novel ultraviolet nonlinear optical crystal is ideal for ultraviolet region transmission. Cl with large electronegativity - The transmission range can be widened, and the cut-off edge can be blue-shifted to the ultraviolet region or even the deep ultraviolet region. Thus, it contains Cl - The synthesis of alkaline earth rare earth borates will beThe frequency multiplication effect is calculated and applied to an effective means of ultraviolet and deep ultraviolet nonlinear optical materials.
Disclosure of Invention
The invention aims to provide two compounds of strontium lanthanum chloroborate and barium lanthanum chloroborate, two kinds of nonlinear optical crystals of strontium lanthanum chloroborate and nonlinear optical crystals of barium lanthanum chloroborate, and a chemical formula A 3 La 4 B 3 O 13 Cl, wherein a=sr, ba.
The invention also aims at providing a preparation method for synthesizing the compound strontium lanthanum chloroborate and barium lanthanum chloroborate by adopting a solid phase reaction method and growing the nonlinear optical crystal of the strontium lanthanum chloroborate and the barium lanthanum chloroborate by adopting a high-temperature melt method or a pulling method.
It is a further object of the present invention to provide strontium lanthanum chloroborate and barium lanthanum chloroborate nonlinear optical devices and the use of strontium lanthanum chloroborate and barium lanthanum chloroborate nonlinear optical devices for the preparation of frequency doubling generators, up or down frequency converters or optical parametric oscillators.
The technical scheme of the invention is as follows:
the chemical formulas of the strontium lanthanum chloroborate and the barium lanthanum chloroborate compounds provided by the invention are A 3 La 4 B 3 O 13 Cl, wherein a=sr, ba, which employs a solid phase reaction method to prepare strontium lanthanum chloroborate and barium lanthanum chloroborate compounds according to the following chemical reaction formula:
1)5ACO 3 +6H 3 BO 3 +1ACl 2 +4La 2 O 3 →2A 3 La 4 B 3 O 13 Cl+5CO 2 ↑+9H 2 o ≡, wherein a=sr, ba
2)3ACO 3 +3H 3 BO 3 +2La 2 O 3 +1NH 4 Cl→A 3 La 4 B 3 O 13 Cl+1NH 3 ↑+3CO 2 ↑+5H 2 O ≡, wherein a=sr, ba
3)5A(OH) 2 +1SrCl 2 +6H 3 BO 3 +4La 2 O 3 →2A 3 La 4 B 3 O 13 Cl+14H 2 O ≡, where a=sr,Ba
4)3AO+3H 3 BO 3 +2La 2 O 3 +1NH 4 Cl→A 3 La 4 B 3 O 13 Cl+5H 2 O↑+NH 3 ∈, where a=sr, ba
5)3A(OH) 2 +1NH 4 Cl+3H 3 BO 3 +2La 2 O 3 →A 3 La 4 B 3 O 13 Cl+8H 2 O ≡+1NH3 ≡, where A=Sr, ba
6)5AO+6H 3 BO 3 +4La 2 O 3 +1ACl 2 →2A 3 La 4 B 3 O 13 Cl+9H 2 O ≡, wherein a=sr, ba
7)5ACO 3 +6H 3 BO 3 +1ACl 2 +8La(NO 3 ) 3 ·6H 2 O→2A 3 La 4 B 3 O 13 Cl+24NO 2 ↑+57H 2 O↑+5CO 2 ↑+6O 2 ∈, where a=sr, ba
8)3ACO 3 +3H 3 BO 3 +4La(NO 3 ) 3 ·6H 2 O+1NH 4 Cl→A 3 La 4 B 3 O 13 Cl+1NH 3 ↑+3CO 2 ↑+12NO 2 ↑+29H 2 O↑+3O 2 ∈, where a=sr, ba
9)1A(OH) 2 +2ACO 3 +1NH 4 Cl+2La 2 O 3 +3H 3 BO 3 →A 3 La 4 B 3 O 13 Cl+1NH 3 ↑+6H 2 O↑+2CO 2 ∈, where a=sr, ba
10)2A(OH) 2 +1ACO 3 +1NH 4 Cl+2La 2 O 3 +3H 3 BO 3 →A 3 La 4 B 3 O 13 Cl+1NH 3 ↑+7H 2 O↑+1CO 2 ∈, where a=sr, ba
11)1A(OH) 2 +2ACO 3 +1NH 4 Cl+4La(NO3) 3 ·6H 2 O+3H 3 BO 3 →A 3 La 4 B 3 O 13 Cl+1NH 3 ↑+30H 2 O↑+2CO 2 ↑+15O 2 ∈, where a=sr, ba
12)2A(OH) 2 +1ACO 3 +1NH 4 Cl+4La(NO 3 ) 3 ·6H 2 O+3H 3 BO 3 →A 3 La 4 B 3 O 13 Cl+1NH 3 ↑+31H 2 O↑+1CO 2 ↑+15O 2 ∈, where a=sr, ba
13)10ASO 4 +12H 3 BO 3 ++2ACl2+8La 2 O 3 →4A 3 La 4 B 3 O 13 Cl+10SO 2 ↑+18H 2 O↑+5O 2 ∈, where a=sr, ba
14)6ASO 4 +6H 3 BO 3 +4La 2 O 3 +2NH 4 Cl→2A 3 La 4 B 3 O 13 Cl+2NH 3 ↑+6SO 2 ↑+10H 2 O↑+3O 2 ∈, where a=sr, ba
15)5ANO 3 +6H 3 BO 3 +1ACl2+4La 2 O 3 →2A 3 La 4 B 3 O 13 Cl+5CO 2 ↑+9H 2 O ≡, wherein a=sr, ba
16)3ANO 3 +3H 3 BO 3 +2La 2 O 3 +1NH 4 Cl→A 3 La 4 B 3 O 13 Cl+1NH 3 ↑+3NO 2 ↑+5H 2 O ≡, wherein a=sr, ba
17)1A(OH) 2 +2ANO 3 +1NH 4 Cl+2La 2 O 3 +3H 3 BO 3 →A 3 La 4 B 3 O 13 Cl+1NH 3 ↑+6H 2 O↑+2NO 2 ∈, where a=sr, ba
18)2A(OH) 2 +1ANO 3 +1NH 4 Cl+2La 2 O 3 +3H 3 BO 3 →A 3 La 4 B 3 O 13 Cl+1NH 3 ↑+7H 2 O↑+1NO 2 ∈, where a=sr, ba
The invention provides two kinds of nonlinear optical crystals of strontium lanthanum chloroborate and barium lanthanum chloroborate, which is characterized in that the chemical formula of the crystal is A 3 La 4 B 3 O 13 Cl, wherein A=Sr, ba has a molecular weight of 1094.36-1243.48, does not have a symmetry center, belongs to a hexagonal system and has a space group of P6 3 The unit cell parameters are
Figure BDA0003312096540000031
Figure BDA0003312096540000032
The preparation method of the strontium lanthanum chloroborate and barium lanthanum chloroborate nonlinear optical crystal is characterized in that the strontium lanthanum chloroborate and barium lanthanum chloroborate nonlinear optical crystal is grown by adopting a high-temperature melt method or a pulling method, and the specific operation is as follows:
a. uniformly mixing strontium lanthanum chloroborate and barium lanthanum chloroborate compound single-phase polycrystalline powder with a fluxing agent, heating the single-phase polycrystalline powder to 650-1000 ℃ at a heating rate of 1-30 ℃/h, keeping the temperature for 5-80 hours to obtain mixed melt, and cooling the mixed melt to 500-800 ℃, wherein the molar ratio of the compound single-phase polycrystalline powder to the fluxing agent is 1:0.5-25;
or directly heating the strontium (barium) containing compound, lanthanum containing compound, boron containing compound and chlorine containing compound or barium containing compound, lanthanum containing compound, boron containing compound and chlorine containing compound and fluxing agent mixture to 650-1000 ℃ at a heating rate of 1-30 ℃/h, keeping the temperature for 5-80 hours to obtain mixed solution, and cooling to 500-800 ℃, wherein the molar ratio of the strontium (barium) containing compound, lanthanum containing compound, boron containing compound and chlorine containing compound to fluxing agent is 2.5-3.3:3.5-4.2:2.5-0.7-1.3:0.1-30;
the fluxing agent being essentially a single fluxing agent, e.g. SrCO 3 (BaCO 3 )、(SrCl 2 )BaCl 2 、SrO(BaO)、H 3 BO 3 、PbO、NaCl、Na 2 CO 3 、LiCl、Li 2 CO 3 、KCl、K 2 CO 3 、LiBO 2 Etc. and other complex fluxing agents, such as SrCO 3 (BaCO 3 )-SrCl 2 、SrCO 3 (BaCO 3 )-SrO(BaO)、SrCO 3 (BaCO 3 )-H 3 BO 3 、SrCO 3 (BaCO 3 )-NaCl、SrCO 3 (BaCO 3 )-KCl、SrCO 3 (BaCO 3 )-PbO、SrCO 3 (BaCO 3 )-LiCl、SrCl 2 (BaCl 2 )-SrO(BaO)、SrCl 2 (BaCl 2 )-PbO、SrCl 2 (BaCl 2 )-NaCl、SrCl 2 (BaCl 2 )-Na 2 CO 3 、SrCl 2 (BaCl 2 )-LiCl、SrCl 2 (BaCl 2 )-KCl、SrCl 2 (BaCl 2 )-K 2 CO 3 、SrO(BaO)-H 3 BO 3 、SrO(BaO)-PbO、SrO(BaO)-NaCl、SrO(BaO)-Na 2 CO 3 、SrO(BaO)-LiCl、SrO(BaO)-Li 2 CO 3 、SrO(BaO)-KCl、SrO(BaO)-K 2 CO 3 、SrO(BaO)-LiBO 2 、H 3 BO 3 -PbO、H 3 BO 3 -Na 2 CO 3 、H 3 BO 3 -Li 2 CO 3 、H 3 BO 3 -KCl、H 3 BO 3 -K 2 CO 3 、H 3 BO 3 -LiBO 2 、SrCO 3 (BaCO 3 )-NaCl-H 3 BO 3 、SrCO 3 (BaCO 3 )-SrO-H 3 BO 3 、SrCO 3 (BaCO 3 )-LiCl-H 3 BO 3 、SrCO 3 (BaCO 3 )-KCl-H 3 BO 3 、SrCl 2 (BaCl 2 )-SrO(BaO)-H 3 BO 3 、SrCl 2 (BaCl 2 )-NaCl-H 3 BO 3 、SrCl 2 (BaCl 2 )-LiCl-H 3 BO 3 、SrO(BaO)-SrCl 2 (BaCl 2 )-H 3 BO 3 、SrO(BaO)-NaCl-H 3 BO 3 、H 3 BO 3 -PbO-SrCl 2 (BaCl 2 )、NaCl-PbO-H 3 BO 3 、KCl-PbO-H 3 BO 3 、Li 2 CO 3 -PbO-H 3 BO 3 、LiBO 2 -PbO-H 3 BO 3 、H 3 BO 3 -KCl-NaCl、H 3 BO 3 -K 2 CO 3 -Na 2 CO 3 、H 3 BO 3 -K 2 CO 3 -NaCl、H 3 BO 3 -KCl-Na 2 CO 3 、H 3 BO 3 -KCl-Na 2 CO 3 -SrCl 2 (BaCl 2 )、H 3 BO 3 -K 2 CO 3 -NaCl-SrCl 2 (BaCl 2 )、H 3 BO 3 -PbO-NaCl-SrCl 2 (BaCl 2 )、H 3 BO 3 -LiCl-NaCl-SrCl 2 (BaCl 2 )、H 3 BO 3 -K 2 CO 3 -LiCl-SrCl 2 (BaCl 2 ) Etc.
The preparation method of the strontium lanthanum chloroborate and barium lanthanum chloroborate nonlinear optical crystal is characterized in that the strontium lanthanum chloroborate and barium lanthanum chloroborate single-phase polycrystalline powder is prepared by adopting a solid phase synthesis method, and the preparation method comprises the following steps: mixing a strontium (barium) compound, a lanthanum compound, a boron compound and a chlorine compound, preparing the strontium (barium) chloride borate and the barium lanthanum chloride borate by adopting a solid phase reaction method, taking out and grinding the components, calcining the components in the muffle furnace, heating the components to 600-1000 ℃, keeping the temperature for 72 hours, cooling the components to the room temperature, and taking out and grinding the components to prepare the single-phase polycrystalline powder of the strontium (barium) chloride borate and the barium chloride borate.
b. Preparing seed crystals of strontium lanthanum chloroborate and barium lanthanum chloroborate nonlinear optical crystals: slowly cooling the mixed solution obtained in the step a to room temperature at a speed of 3-10 ℃/h, and spontaneously crystallizing to obtain seed crystals of the strontium lanthanum chloroborate and barium lanthanum chloroborate nonlinear optical crystal;
c. c, placing the crucible containing the mixed solution prepared in the step a into a crystal growth furnace, fixing the seed crystal obtained in the step b on a seed rod, preheating the seed crystal for 5-60 minutes from the top of the crystal growth furnace, lowering the seed crystal to be in contact with the liquid surface of the mixed solution or the mixed solution for remelting, keeping the temperature for 5-60 minutes, and reducing the temperature to a saturation temperature at a speed of 1-60 ℃/h;
d. and then slowly cooling at the speed of 0.1-5 ℃/day, rotating a seed rod at the speed of 0-60rpm to perform crystal growth, lifting the crystal off the surface of the mixed molten liquid after the single crystal grows to a required size, cooling to room temperature at the speed of 1-80 ℃/h, and taking the crystal out of a hearth to obtain the strontium lanthanum chloroborate and barium lanthanum chloroborate nonlinear optical crystal.
The fluxing agent SrCO 3 (BaCO 3 )-SrCl 2 (BaCl 3 ) SrCO in the system 3 (BaCO 3 ) With SrCl 2 (BaCl 3 ) The molar ratio of (2) is 1-3:2-5; srCO 3 (BaCO 3 ) SrCO in a SrO (BaO) system 3 (BaCO 3 ) The molar ratio of the catalyst to SrO (BaO) is 1-3:3-6; srCO 3 (BaCO 3 )-H 3 BO 3 SrCO in the system 3 (BaCO 3 ) And H is 3 BO 3 The molar ratio is 1-5:3-7; srCO 3 (BaCO 3 ) SrCO in NaCl system 3 (BaCO 3 ) The molar ratio of the sodium chloride to NaCl is 1-5:2-8; srCO 3 (BaCO 3 ) SrCO in KCl system 3 (BaCO 3 ) The molar ratio of the catalyst to KCl is 1-8:2-5; srCO 3 (BaCO 3 ) SrCO in PbO systems 3 The mol ratio of the catalyst to PbO is 1-10:3-6; srCO 3 SrCO in LiCl System 3 (BaCO 3 ) The molar ratio of the catalyst to LiCl is 1-7:1-6; srCl 2 (BaCl 2 ) SrCl in PbO system 2 (BaCl 2 ) The mol ratio of the catalyst to PbO is 1-7:1-6; srCl 2 (BaCl 2 ) SrCl in NaCl system 2 (BaCl 2 ) The molar ratio of the sodium chloride to NaCl is 1-8:2-5; srCl 2 (BaCl 2 )-Na 2 CO 3 SrCl in the system 2 (BaCl 2 ) With Na and Na 2 CO 3 The molar ratio is 1-10:3-6; srCl 2 (BaCl 2 ) SrCl in LiCl system 2 (BaCl 2 ) The molar ratio of the catalyst to LiCl is 1-7:5-6; h 3 BO 3 H in PbO System 3 BO 3 The mol ratio of the catalyst to PbO is 1-7:2-6; h 3 BO 3 -Na 2 CO 3 H in the system 3 BO 3 With Na and Na 2 CO 3 The molar ratio is 1-6:1-5; h 3 BO 3 -Li 2 CO 3 H in the system 3 BO 3 With Li 2 CO 3 The molar ratio is 1-6:2-6; h 3 BO 3 H in KCl System 3 BO 3 The molar ratio of the catalyst to KCl is 1-6:4-6; h 3 BO 3 -K 2 CO 3 H in the system 3 BO 3 And K is equal to 2 CO 3 The molar ratio is 1-6:2-6; h 3 BO 3 -LiBO 2 H in the system 3 BO 3 And LiBO 2 The molar ratio is 1-5:4-6; srO (BaO) Na 2 CO 3 SrO (BaO) and Na in the system 2 CO 3 The molar ratio is 1-4:2-6; na in SrO (BaO) -KCl system 2 CO 3 With Na and Na 2 CO 3 The molar ratio is 1-6:1-5; sr (Ba) CO 3 -NaCl-H 3 BO 3 Sr (Ba) CO in the system 3 NaCl and H 3 BO 3 The molar ratio is 1-5:2-6:3-8; sr (Ba) CO 3 -SrO-H 3 BO 3 SrCO in the system 3 (BaCO 3 ) SrO (BaO) and H 3 BO 3 The molar ratio is 0.5-5:1-6:3-8; srCO 3 (BaCO 3 )-LiCl-H 3 BO 3 SrCO in the system 3 (BaCO 3 ) LiCl and H 3 BO 3 The molar ratio is 1-5:0.5-6:2.9-8; srCl 2 (BaCl 2 )-LiCl-H 3 BO 3 SrCl in the system 2 (BaCl 2 ) LiCl and H 3 BO 3 The molar ratio is 1-6:1-7:3-8; srO (BaO) -SrCl 2 -H 3 BO 3 Sr (Ba) O, srCl in System 2 (BaCl 2 ) And H is 3 BO 3 The molar ratio is 1-3:1-4:3-10; srO (BaO) -NaCl-H 3 BO 3 SrO (BaO), naCl and H in the system 3 BO 3 The molar ratio is 1-5:1-9:3-12; h 3 BO 3 -PbO-SrCl 2 (BaCl 2 ) H in the system 3 BO 3 PbO and SrCl 2 (BaCl 2 ) The molar ratio is 2-5:1-6:3-8; naCl-PbO-H 3 BO 3 NaCl, pbO and H in the system 3 BO 3 The molar ratio is 2-9:1-7:1-10; KCl-PbO-H 3 BO 3 KCl, pbO and H in the system 3 BO 3 The molar ratio is 2-5:1-6:2-8; li (Li) 2 CO 3 -PbO-H 3 BO 3 Li in the system 2 CO 3 PbO and H 3 BO 3 The molar ratio is 2-5:1-10:2-11; liBO 2 -PbO-H 3 BO 3 LiBO in System 2 PbO and H 3 BO 3 The molar ratio is 0.5-5:1.5-10:2-10; h 3 BO 3 H in KCl-NaCl System 3 BO 3 The molar ratio of KCl to NaCl is 2-5:1-10:2-9; h 3 BO 3 -KCl-Na 2 CO 3 -SrCl 2 (BaCl 2 ) H in the system 3 BO 3 、KCl、Na 2 CO 3 With SrCl 2 (BaCl 2 ) The molar ratio is 1-21:1-10:2-8:1-8; h 3 BO 3 -K 2 CO 3 -NaCl-SrCl 2 (BaCl 2 ) H in the system 3 BO 3 、K 2 CO 3 NaCl and SrCl 2 (BaCl 2 ) The molar ratio is 1-21:1-10:2-8:1-8; h 3 BO 3 -PbO-NaCl-SrCl 2 (BaCl 2 ) H in the system 3 BO 3 、K 2 CO 3 NaCl and SrCl 2 (BaCl 2 ) The molar ratio is 1-20:1-10:2-8:1-8; h 3 BO 3 -LiCl-NaCl-SrCl 2 (BaCl 2 ) H in the system 3 BO 3 、K 2 CO 3 NaCl and SrCl 2 (BaCl 2 ) The molar ratio is 1-21:1-10:3-8:1-8; h 3 BO 3 -K 2 CO 3 -LiCl-SrCl 2 (BaCl 2 ) H in the system 3 BO 3 、K 2 CO 3 NaCl and SrCl 2 (BaCl 2 ) The molar ratio is 1-21:2-10:2-9:1-7; h 3 BO 3 -KCl-NaCl-SrCl 2 (BaCl 2 ) H in the system 3 BO 3 KCl, naCl and SrCl 2 (BaCl 2 ) Friction wheelThe molar ratio is 1-18:1-9:2-10:1-9.
The invention provides two kinds of nonlinear optical crystals of strontium lanthanum chloroborate and barium lanthanum chloroborate, which is characterized in that the chemical formula of the crystal is A 3 La 4 B 3 O 13 Cl, wherein A=Sr, ba has a molecular weight of 1094.36-1243.48, does not have a symmetry center, belongs to a hexagonal system and has a space group of P6 3 Compound A 3 La 4 B 3 O 13 Cl, wherein a=sr, ba has a unit cell parameter of
Figure BDA0003312096540000071
Figure BDA0003312096540000072
Since, in the process of growing the strontium lanthanum chloroborate and barium lanthanum chloroborate nonlinear optical crystal, srCO, for example, is used 3 (BaCO 3 )、SrCl 2 (BaCl 2 )、Sr(OH) 2 (BaOH 2 )、SrO(BaO)、H 3 BO 3 、B 2 O 3 Self-fluxing agents, other fluxing agents, e.g. NaCl, liCl, KCl, na 2 CO 3 、Li 2 CO 3 、K 2 CO 3 Etc. and for example SrCl 2 (BaCl 2 )-Sr(Ba)(OH) 2 、SrCl 2 (BaCl 2 )-SrO(BaO)、SrCl 2 (BaCl 2 )-H 3 BO 3 、SrCl 2 (BaCl 2 )-B 2 O 3 、Sr(OH) 2 (BaOH 2 )-SrO(BaO)、Sr(OH) 2 (BaOH 2 )-H 3 BO 3 、Sr(OH) 2 (BaOH 2 )-B 2 O 3 、SrO(BaO)-H 3 BO 3 、SrCO 3 (BaCO 3 )-SrCl 2 、SrCO 3 (BaCO 3 )-SrO(BaO)、SrCO 3 (BaCO 3 )-H 3 BO 3 、SrCO 3 (BaCO 3 )-NaCl、SrCO 3 (BaCO 3 )-KCl、SrCO 3 (BaCO 3 )-PbO、SrCO 3 (BaCO 3 )-LiCl、SrCl 2 (BaCl 2 )-Sr(Ba)O、SrCl 2 (BaCl 2 )-PbO、SrCl 2 (BaCl 2 )-NaCl、SrCl 2 (BaCl 2 )-Na 2 CO 3 、SrCl 2 (BaCl 2 )-LiCl、SrCl 2 (BaCl 2 )-KCl、SrCl 2 (BaCl 2 )-K 2 CO 3 、SrO(BaO)-H 3 BO 3 、SrO(BaO)-PbO、SrO(BaO)-NaCl、SrO(BaO)-Na 2 CO 3 、SrO(BaO)-LiCl、SrO(BaO)-Li 2 CO 3 、SrO(BaO)-KCl、SrO(BaO)-K 2 CO 3 、SrO(BaO)-LiBO 2 、H 3 BO 3 -PbO、H 3 BO 3 -Na 2 CO 3 、H 3 BO 3 -Li 2 CO 3 、H 3 BO 3 -KCl、H 3 BO 3 -K 2 CO 3 、H 3 BO 3 -LiBO 2 、SrCO 3 (BaCO 3 )-NaCl-H 3 BO 3 、SrCO 3 (BaCO 3 )-Sr(Ba)O-H 3 BO 3 、SrCO 3 (BaCO 3 )-LiCl-H 3 BO 3 、SrCO 3 (BaCO 3 )-KCl-H 3 BO 3 、SrCl 2 (BaCl 2 )-SrO(BaO)-H 3 BO 3 、SrCl 2 (BaCl 2 )-NaCl-H 3 BO 3 、SrCl 2 (BaCl 2 )-LiCl-H 3 BO 3 、SrO(BaO)-SrCl 2 -H 3 BO 3 、SrO(BaO)-NaCl-H 3 BO 3 、H 3 BO 3 -PbO-SrCl 2 (BaCl 2 )、NaCl-PbO-H 3 BO 3 、KCl-PbO-H 3 BO 3 、Li 2 CO 3 -PbO-H 3 BO 3 、LiBO 2 -PbO-H 3 BO 3 、H 3 BO 3 -KCl-NaCl、H 3 BO 3 -K 2 CO 3 -Na 2 CO 3 、H 3 BO 3 -K 2 CO 3 -NaCl、H 3 BO 3 -KCl-Na 2 CO 3 、H 3 BO 3 -KCl-Na 2 CO 3 -SrCl 2 (BaCl 2 )、H 3 BO 3 -K 2 CO 3 -NaCl-SrCl 2 (BaCl 2 )、H 3 BO 3 -PbO-NaCl-SrCl 2 (BaCl 2 )、H 3 BO 3 -LiCl-NaCl-SrCl 2 (BaCl 2 ) Or other composite fluxing agents, the product purity is high, the crystals are easy to grow and transparent without wrapping, and the method has the advantages of high growth speed, low cost, easy obtainment of crystals with larger size and the like; the nonlinear optical crystal is used for preparing a frequency multiplication generator, an upper frequency converter, a lower frequency converter or an optical parametric oscillator. The obtained crystal has the advantages of wider light transmission wave band, higher hardness, good mechanical property, difficult fragmentation and deliquescence, easy processing and storage, and the like. The strontium lanthanum chloroborate and barium lanthanum chloroborate nonlinear optical crystal obtained by the method can be made into nonlinear optical devices for laser frequency conversion.
Drawings
FIG. 1 shows Sr of the present invention 3 La 4 B 3 O 13 X-ray diffraction pattern of Cl powder.
FIG. 2 is a schematic diagram of a nonlinear optical device according to the present invention, wherein 1 is a laser, 2 is an emitted beam, and 3 is A 3 La 4 B 3 O 13 Cl, wherein a=sr, a nonlinear optical crystal of Ba, 4 is an outgoing light beam, and 5 is a filter.
Detailed Description
The invention is described in detail below with reference to the attached drawings and examples:
example 1:
according to the reaction formula: 5ACO 3 +6H 3 BO 3 +1ACl 2 +4La 2 O 3 →2A 3 La 4 B 3 O 13 Cl+5CO 2 ↑+9H 2 O ≡, synthesis A 3 La 4 B 3 O 13 Cl (a=sr, ba) compound, wherein a=sr, ba:
SrCO 3 (BaCO 3 )、H 3 BO 3 、SrCl 2 (BaCl 2 )、La 2 O 3 Weighing according to a molar ratio of 5:6:1:4, placing into a mortar, mixing, grinding, then placing into an open corundum crucible with phi of 100mm multiplied by 100mm, placing into a muffle furnace, slowly heating to 300 ℃, keeping the temperature constant for 24 hours, cooling to room temperature, taking out, grinding for the second time, placing into the muffle furnace, heating to 950 ℃, keeping the temperature constant for 24 hours, cooling to room temperature, taking out, grinding for the third time, placing into the muffle furnace, keeping the temperature constant for 48 hours at 950 ℃, taking out, grinding to obtain single-phase polycrystalline powder of strontium lanthanum chloroborate and barium lanthanum chloroborate compound, carrying out X-ray analysis on the product, and obtaining an X-ray spectrogram and strontium lanthanum chloroborate and barium lanthanum chloroborate A 3 La 4 B 3 O 13 X-ray spectra obtained for Cl (a=sr, ba) single crystal structure are consistent;
the obtained strontium lanthanum chloroborate and barium lanthanum chloroborate A 3 La 4 B 3 O 13 Single-phase polycrystalline powder of Cl (a=sr, ba) compound and flux H 3 BO 3 KCl-NaCl in molar ratio A 3 La 4 B 3 O 13 Cl(A＝Sr，Ba):H 3 BO 3 -KCl-nacl=1:3, wherein H 3 BO 3 Mixing KCl and NaCl in the molar ratio of 6:3:5, loading into an open platinum crucible with phi 80mm multiplied by 80mm, heating to 900 ℃ at the temperature rising rate of 30 ℃/h, keeping the temperature for 15 hours to obtain mixed melt, and cooling to 880 ℃;
slowly cooling to room temperature at the speed of 0.5 ℃/h, and obtaining strontium lanthanum chloroborate and barium lanthanum chloroborate seed crystals through spontaneous crystallization;
growing crystals in a compound melt: a to be obtained 3 La 4 B 3 O 13 A Cl (A=Sr, ba) seed crystal is fixed on a seed rod and is seeded from the top of a crystal growth furnace, the seed crystal is preheated on the surface of the mixed melt for 10 minutes and is immersed into the liquid level, the seed crystal is remelted in the mixed melt, the temperature is kept for 30 minutes, and the temperature is quickly reduced to the saturation temperature of 865 ℃;
then cooling at a rate of 2 ℃/day, rotating the seed rod at a rotation speed of 10rpm, separating the crystal from the liquid surface after the crystal growth is completed, and cooling to room temperature at a rate of 10 ℃/hour to obtain A with a size of 56mm×40mm×30mm 3 La 4 B 3 O 13 Cl (a=sr, ba) crystal.
The raw material strontium carbonate (barium carbonate) in the reaction formula can be replaced by other strontium (barium) containing salts such as strontium chloride (barium chloride) or strontium nitrate (barium nitrate) or strontium oxalate (barium oxalate) or strontium sulfate (barium sulfate), or strontium oxide (barium oxide) or strontium hydroxide (barium hydroxide), the lanthanum oxide can be replaced by lanthanum carbonate or lanthanum nitrate or lanthanum chloride or lanthanum oxalate or lanthanum sulfate, and the boric acid can be replaced by boron oxide.
Example 2:
according to the reaction formula: 3ACO 3 +3H 3 BO 3 +2La 2 O 3 +1NH 4 Cl→A 3 La 4 B 3 O 13 Cl+NH3↑+4NO 2 ↑+3CO 2 ↑+5H 2 O ≡synthesis A 3 La 4 B 3 O 13 Cl compound, wherein a=sr, ba:
SrCO 3 (BaCO 3 )、H 3 BO 3 、La 2 O 3 、NH 4 Cl is directly weighed according to the mol ratio of 3:3:2:1, and the weighed raw materials and fluxing agent H are mixed 3 BO 3 PbO is mixed according to a mol ratio of 1:4, wherein H is as follows 3 BO 3 The molar ratio of the alloy to PbO is 3:5, the alloy is put into an open platinum crucible with phi 80mm multiplied by 80mm, the temperature is raised to 650 ℃, the temperature is kept for 60 hours, mixed melt is obtained, and the temperature is lowered to 600 ℃ after cooling;
slowly cooling to room temperature at a speed of 1.5 ℃/h, and obtaining strontium lanthanum chloroborate and barium lanthanum chloroborate seed crystals through spontaneous crystallization;
will obtain A 3 La 4 B 3 O 13 Cl, wherein A=Sr, the Ba seed crystal is fixed on a seed rod and is seeded from the top of a crystal growth furnace, the seed crystal is preheated on the surface of the mixed melt for 10 minutes and immersed under the liquid level, the seed crystal is remelted in the mixed melt, the temperature is kept for 30 minutes, and the temperature is quickly reduced to 620 ℃ in saturation;
slowly cooling at a rate of 1 deg.C/day without rotating seed rod, and lifting the crystal off the surface of the molten liquid at a temperature of 2 deg.C after the crystal grows to a desired sizeCooling to room temperature at a speed of 0 ℃/h, and taking out the crystal from the hearth to obtain the A with the size of 36mm multiplied by 22mm multiplied by 15mm 3 La 4 B 3 O 13 Cl crystal, wherein a=sr, ba.
The raw material strontium carbonate (barium carbonate) in the reaction formula can be replaced by other strontium (barium) containing salts such as strontium chloride (barium chloride) or strontium nitrate (barium nitrate) or strontium oxalate (barium oxalate) or strontium sulfate (barium sulfate) or strontium oxide (barium oxide) or strontium hydroxide (barium hydroxide), lanthanum oxide can be replaced by lanthanum carbonate or lanthanum nitrate or lanthanum chloride or lanthanum oxalate or lanthanum sulfate and other lanthanum containing salts or lanthanum hydroxide, and boric acid can be replaced by boron oxide.
Example 3:
according to the reaction formula: 5A (OH) 2 +1SrCl 2 +6H 3 BO 3 +4La 2 O 3 →2A 3 La 4 B 3 O 13 Cl+14H 2 O ≡synthesis A 3 La 4 B 3 O 13 Cl compound, wherein a=sr, ba:
sr (OH) 2 (Ba(OH) 2 )、SrCl 2 (BaCl 2 )、H 3 BO 3 、La 2 O 3 Directly weighing raw materials according to a molar ratio of 5:1:6:4, and mixing the weighed raw materials with a fluxing agent SrCl 2 (BaCl 2 )-H 3 BO 3 Mixing according to a molar ratio of 1:3, wherein SrCl 2 (BaCl 2 ) And H is 3 BO 3 Placing the mixture into an open platinum crucible with the mol ratio of phi 80mm multiplied by 80mm, heating to 1000 ℃, keeping the temperature for 60 hours to obtain mixed melt, and then cooling to 880 ℃;
slowly cooling to room temperature at the speed of 3.5 ℃/h, and obtaining strontium lanthanum chloroborate and barium lanthanum chloroborate seed crystals through spontaneous crystallization;
a to be obtained 3 La 4 B 3 O 13 Cl, wherein A=Sr, the Ba seed crystal is fixed on a seed rod and is seeded from the top of a crystal growth furnace, the seed crystal is preheated on the surface of the mixed melt for 15 minutes and immersed under the liquid level, the seed crystal is remelted in the mixed melt, the temperature is kept for 30 minutes, and the temperature is quickly reduced to the saturation temperature of 867 ℃;
slowly cooling at 3 deg.C/day, rotating the seed crystal crucible at 5rpm, lifting the crystal from the surface of molten liquid after the crystal grows to the required size, cooling to room temperature at 1 deg.C/h, and taking out the crystal from the hearth to obtain the product A with the size of 25mm×24mm×10mm 3 La 4 B 3 O 13 Cl crystal, wherein a=sr, ba.
The raw material strontium hydroxide (barium hydroxide) in the reaction formula can be replaced by other strontium (barium) containing salts such as strontium chloride (barium strontium chloride) or strontium nitrate (barium nitrate) or strontium oxalate (barium oxalate) or strontium sulfate (barium sulfate), or strontium oxide (barium oxide) or strontium hydroxide (barium hydroxide), lanthanum oxide can be replaced by lanthanum carbonate or lanthanum nitrate or lanthanum chloride or lanthanum oxalate or lanthanum sulfate, and boric acid can be replaced by boron oxide.
Example 4:
according to the reaction formula: 3AO+3H 3 BO 3 +2La 2 O 3 +1NH 4 Cl↑→A 3 La 4 B 3 O 13 Cl+5H 2 O↑+NH 3 Synthesis of ≡A 3 La 4 B 3 O 13 Cl compound, wherein a=sr, ba:
SrO (BaO), H 3 BO 3 、La 2 O 3 、NH 4 Cl is directly weighed according to the mol ratio of 3:3:2:1, and the weighed raw materials and fluxing agent PbO-H are mixed 3 BO 3 Mixing according to a molar ratio of 1:3, wherein PbO and H 3 BO 3 Placing the mixture into an open platinum crucible with the mol ratio of phi 80mm multiplied by 80mm, heating to the temperature of 890 ℃, keeping the temperature for 80 hours to obtain mixed melt, and then cooling to the temperature of 875 ℃;
slowly cooling to room temperature at a speed of 5 ℃/h, and obtaining strontium lanthanum chloroborate and barium lanthanum chloroborate seed crystals through spontaneous crystallization;
a to be obtained 3 La 4 B 3 O 13 Cl, wherein A=Sr, ba seed crystal is fixed on seed rod from top of crystal growth furnace to seed crystal under the top of crystal growth furnace, preheating seed crystal on surface of mixed molten liquid for 20 min, immersing under liquid surface, making seed crystal melt back in mixed molten liquid, holding temperature for 5 min, quickly reducingThe temperature reaches to the saturation temperature of 860 ℃;
then slowly cooling at a speed of 3 ℃/day, rotating a seed rod at a speed of 15rpm, separating the crystal from the surface of the molten liquid after the crystal grows to a required size, cooling to room temperature at a speed of 15 ℃/h, and taking the crystal out of a hearth to obtain the A with the size of 35mm multiplied by 25mm multiplied by 20mm 3 La 4 B 3 O 13 Cl crystal, wherein a=sr, ba.
The raw material barium oxide (strontium oxide) in the reaction formula can be replaced by other strontium (barium) containing salts such as strontium chloride (barium chloride) or strontium nitrate (barium nitrate) or strontium oxalate (barium strontium oxalate) or strontium sulfate (barium strontium sulfate) or strontium oxide (barium strontium oxide) or strontium hydroxide (barium strontium hydroxide), the lanthanum oxide can be replaced by other lanthanum containing salts such as lanthanum carbonate or lanthanum nitrate or lanthanum chloride or lanthanum oxalate or lanthanum sulfate, and the boric acid can be replaced by boron oxide.
Example 5
According to the reaction formula: 3A (OH) 2 +1NH 4 Cl+3H 3 BO 3 +2La 2 O 3 →A 3 La 4 B 3 O 13 Cl，+8H 2 O↑+1NH 3 Synthesis of ≡A 3 La 4 B 3 O 13 Cl compound, wherein a=sr, ba:
sr (OH) 2 (Ba(OH) 2 )、NH 4 Cl、H 3 BO 3 、La 2 O 3 Directly weighing raw materials according to a molar ratio of 3:1:3:2, and mixing the weighed raw materials with a fluxing agent H 3 BO 3 -KCl-Na 2 CO 3 Mixing according to a molar ratio of 1:2, wherein H 3 BO 3 KCl and Na 2 CO 3 Placing the mixture into an open platinum crucible with the diameter of 80mm multiplied by 80mm according to the molar ratio of 5:1:3, heating to the temperature of 850 ℃, keeping the temperature for 80 hours to obtain mixed melt, and then cooling to the temperature of 830 ℃;
slowly cooling to room temperature at a speed of 10 ℃/h, and obtaining strontium lanthanum chloroborate and barium lanthanum chloroborate seed crystals through spontaneous crystallization;
a to be obtained 3 La 4 B 3 O 13 Cl, wherein a=sr, ba seed crystal is fixed on seed rodPreheating seed crystals on the surface of the mixed molten liquid for 25 minutes, partially immersing the seed crystals under the liquid surface, carrying out remelting on the seed crystals in the mixed molten liquid, keeping the temperature for 25 minutes, and rapidly cooling to the saturation temperature of 820 ℃;
then cooling at a speed of 5 ℃/day, rotating the seed rod at a speed of 30rpm, lifting the crystal from the surface of the molten liquid after the crystal grows to a required size, cooling to room temperature at a speed of 35 ℃/h, and taking the crystal out of a hearth to obtain the A with the size of 22mm multiplied by 32mm multiplied by 20mm 3 La 4 B 3 O 13 Cl crystal, wherein a=sr, ba.
The raw material strontium hydroxide (barium hydroxide) in the reaction formula can be replaced by other strontium (barium) containing salts such as strontium chloride (barium chloride) or strontium nitrate (barium nitrate) or strontium oxalate (barium oxalate) or strontium sulfate (barium sulfate), or strontium oxide (barium oxide) or strontium hydroxide (barium hydroxide), lanthanum oxide can be replaced by lanthanum carbonate or lanthanum nitrate or lanthanum chloride or lanthanum oxalate or lanthanum sulfate, and boric acid can be replaced by boron oxide.
Example 6
According to the reaction formula: 5AO+6H 3 BO 3 +4La 2 O 3 +1SrCl 2 →2A 3 La 4 B 3 O 13 Cl+9H 2 O ≡synthesis A 3 La 4 B 3 O 13 Cl compound, wherein a=sr, ba:
SrO (BaO), H 3 BO 3 、La 2 O 3 、SrCl 2 (BaCl 2 ) Directly weighing raw materials according to a molar ratio of 5:6:4:1, and mixing the weighed raw materials with a fluxing agent H 3 BO 3 -KCl is compounded in a molar ratio of 1:4, wherein H 3 BO 3 Putting the mixture into an open platinum crucible with the mol ratio of KCl of 3:2 and phi of 80mm multiplied by 80mm, heating to 900 ℃, keeping the temperature for 5 hours to obtain mixed melt, and then cooling to 880 ℃;
slowly cooling to room temperature at the speed of 4.0 ℃/h, and obtaining strontium lanthanum chloroborate and barium lanthanum chloroborate seed crystals through spontaneous crystallization;
a to be obtained 3 La 4 B 3 O 13 Cl, which isWherein a=sr, fixing the Ba seed crystal on the seed rod from the top of the crystal growth furnace to the seed crystal under the top of the crystal growth furnace, preheating the seed crystal on the surface of the mixed melt for 20 minutes, immersing the seed crystal under the liquid surface, melting the seed crystal in the mixed melt, keeping the temperature for 25 minutes, and rapidly cooling to the saturation temperature of 865 ℃;
then cooling at a rate of 3 ℃/day, rotating a seed rod at a rotating speed of 50rpm, separating the crystal from the surface of the molten liquid after the crystal grows to a required size, cooling to room temperature at a rate of 70 ℃/h, and taking the crystal out of a hearth to obtain the A with the size of 22mm multiplied by 21mm multiplied by 16mm 3 La 4 B 3 O 13 Cl crystal, wherein a=sr, ba.
The raw material strontium oxide (barium oxide) in the reaction formula can be replaced by other strontium (barium) containing salts such as strontium chloride (strontium barium chloride) or strontium nitrate (strontium barium nitrate) or strontium oxalate (barium oxalate) or strontium sulfate (barium sulfate) or strontium oxide (strontium barium oxide) or strontium hydroxide (barium hydroxide), the lanthanum oxide can be replaced by other lanthanum containing salts such as lanthanum carbonate or lanthanum nitrate or lanthanum chloride or lanthanum oxalate or lanthanum sulfate, and the boric acid can be replaced by boron oxide.
Example 7
According to the reaction formula: 5ACO 3 +6H 3 BO 3 +1SrCl 2 (BaCl 2 )+8La(NO 3 ) 3 ·6H 2 O→2A 3 La 4 B 3 O 13 Cl+24NO 2 ↑+57H 2 O↑+5CO 2 ↑+6O 2 Synthesis of ≡A 3 La 4 B 3 O 13 Cl compound, wherein a=sr, ba:
SrCO 3 (BaCO 3 )、H 3 BO 3 、SrCl 2 (BaCl 2 )、La(NO 3 ) 3 ·6H 2 O is put into a mortar according to the mol ratio of 5:6:1:8, mixed and finely ground, then is put into an open corundum crucible with phi of 100mm multiplied by 100mm, is tightly pressed, is put into a muffle furnace, is slowly heated to the temperature of 400 ℃ and is kept at the constant temperature for 4 hours, is taken out of the crucible after cooling, is loose at the moment, is taken out of the crucible, is ground again uniformly, is put into the crucible, is kept at the constant temperature of 950 ℃ for 48 hours in the muffle furnace, and is taken out of the crucibleTaking out, putting into a mortar, mashing and grinding to obtain A 3 La 4 B 3 O 13 Cl (a=sr, ba) compound, and subjecting the product to X-ray analysis, the obtained X-ray spectrum being combined with lanthanum strontium chloroborate and barium lanthanum chloroborate a 3 La 4 B 3 O 13 X-ray spectra obtained for Cl (a=sr, ba) single crystal structure are consistent;
to be synthesized A 3 La 4 B 3 O 13 Cl (a=sr, ba) compound and flux H 3 BO 3 -PbO-SrCl 2 (BaCl 2 ) Mixing according to a molar ratio of 1:4, wherein H 3 BO 3 PbO and SrCl 2 (BaCl 2 ) The molar ratio is 5:1:1, the mixture is put into an open platinum crucible with phi 80mm multiplied by 80mm, the temperature is raised to 900 ℃, the mixture is kept at the constant temperature for 50 hours to obtain mixed melt, and then the mixture is lowered to 880 ℃;
slowly cooling to room temperature at the speed of 4.0 ℃/h, and obtaining strontium lanthanum chloroborate and barium lanthanum chloroborate seed crystals through spontaneous crystallization;
a to be obtained 3 La 4 B 3 O 13 Cl, wherein A=Sr, the Ba seed crystal is fixed on a seed rod and is seeded from the top of a crystal growth furnace, the seed crystal is preheated on the surface of the mixed melt for 20 minutes and immersed under the liquid level, the seed crystal is remelted in the mixed melt, the temperature is kept constant for 25 minutes, and the temperature is reduced to 850 ℃ of saturation temperature;
then cooling at a speed of 2 ℃/day, rotating the seed rod at a speed of 28rpm, separating the crystal from the surface of the molten liquid after the crystal grows to a required size, cooling to room temperature at a speed of 25 ℃/h, and taking the crystal out of a hearth to obtain the A with the size of 30mm multiplied by 22mm multiplied by 15mm 3 La 4 B 3 O 13 Cl crystal, wherein a=sr, ba.
The raw material strontium carbonate (barium carbonate) in the reaction formula can be replaced by other strontium (barium) containing salts such as strontium chloride (barium chloride) or strontium nitrate (barium strontium nitrate) or strontium oxalate (barium strontium oxalate) or strontium sulfate (barium strontium sulfate) or strontium oxide (barium strontium oxide) or strontium hydroxide (barium strontium hydroxide), the lanthanum oxide can be replaced by other lanthanum containing salts such as lanthanum carbonate or lanthanum nitrate or lanthanum chloride or lanthanum oxalate or lanthanum sulfate, and the boric acid can be replaced by boron oxide.
Example 8
According to the reaction formula: 3SrCO 3 (BaCO 3 )+3H 3 BO 3 +4La(NO 3 ) 3 ·6H 2 O+1NH 4 Cl→A 3 La 4 B 3 O 13 Cl+1NH 3 ↑+3CO 2 ↑+12NO 2 ↑+29H 2 O↑+3O 2 Synthesis of A3La4B3O13Cl compound, wherein a=sr, ba:
by mixing Sr (Ba) CO 3 、H 3 BO 3 、La(NO 3 ) 3 ·6H 2 O、NH 4 Cl、O 2 Putting the raw materials and a fluxing agent H into a mortar according to a molar ratio of 3:3:4:1:1 3 BO 3 -PbO-NaCl-SrCl2 (BaCl 2) is mixed according to the mol ratio of 1:1, wherein H 3 BO 3 PbO, naCl and SrCl 2 (BaCl 2 ) The molar ratio is 5:3:4:1, the mixture is put into an open platinum crucible with phi of 80mm multiplied by 80mm, the temperature is raised to 890 ℃, the temperature is kept for 80 hours, mixed melt is obtained, and then the temperature is lowered to 865 ℃;
slowly cooling to room temperature at a speed of 10 ℃/h, and obtaining strontium lanthanum chloroborate and barium lanthanum chloroborate seed crystals through spontaneous crystallization;
a to be obtained 3 La 4 B 3 O 13 Cl, wherein A=Sr, the Ba seed crystal is fixed on a seed rod and is seeded from the top of a crystal growth furnace, the seed crystal is preheated on the surface of the mixed melt for 25 minutes, and is partially immersed under the liquid surface, so that the seed crystal is remelted in the mixed melt, kept at a constant temperature for 25 minutes, and rapidly cooled to a saturation temperature of 840 ℃;
then cooling at a speed of 5 ℃/day, rotating the seed rod at a speed of 30rpm, lifting the crystal from the surface of the molten liquid after the crystal grows to a required size, cooling to room temperature at a speed of 35 ℃/h, and taking the crystal out of a hearth to obtain the A with the size of 22mm multiplied by 32mm multiplied by 20mm 3 La 4 B 3 O 13 Cl crystal, wherein a=sr, ba.
The raw material strontium carbonate (barium) in the reaction formula can be replaced by other strontium (barium) containing salts such as strontium chloride (barium) or strontium nitrate (barium) or strontium oxalate (barium) or strontium sulfate (barium), or strontium oxide (barium) or strontium hydroxide (barium), lanthanum oxide can be replaced by other lanthanum containing salts such as lanthanum carbonate or lanthanum nitrate or lanthanum chloride or lanthanum oxalate or lanthanum sulfate, or lanthanum hydroxide, and boric acid can be replaced by boron oxide.
Example 9
Any of the A obtained in examples 1 to 8 3 La 4 B 3 O 13 Cl (A=Sr, ba) crystal is processed into a frequency doubling device with the size of 5mm multiplied by 6mm according to the matching direction, the frequency doubling device is arranged at a position of 3 according to the figure 2, a Q-switched Nd-YAG laser is used as a light source, the incident wavelength is 1064nm, and an infrared light beam 2 with the wavelength of 1064nm is emitted by the Q-switched Nd-YAG laser 1 to be injected into A at room temperature 3 La 4 B 3 O 13 Cl (a=sr, ba) single crystal 3 generates green frequency-doubled light having a wavelength of 532nm, and outgoing beam 4 contains infrared light having a wavelength of 1064nm and green light having a wavelength of 532nm, and is filtered by filter 5 to obtain green laser light having a wavelength of 532 nm.

Claims (10)

1. The two compounds of lanthanum strontium chloroborate and barium lanthanum chloroborate are characterized in that the chemical formula of the compound is A 3 La 4 B 3 O 13 Cl, wherein a=sr, ba, belongs to hexagonal system, space group P6 3 The unit cell parameters are: 1) Sr (Sr) 3 La 4 B 3 O 13 Cl：
Figure FDA0003312096530000011
Figure FDA0003312096530000012
Z＝2，/>
Figure FDA0003312096530000013
2)Ba 3 La 4 B 3 O 13 Cl：/>
Figure FDA0003312096530000014
Z＝2，
Figure FDA0003312096530000015
2. The method for preparing the compounds strontium lanthanum chloroborate and barium lanthanum chloroborate according to claim 1, comprising the following steps: mixing a strontium (barium) compound, a lanthanum compound, a boron compound and a chlorine compound, preparing the strontium (barium) compound, the lanthanum strontium borate and the barium lanthanum borate chloride by adopting a solid phase reaction method, taking out and grinding the strontium (barium) compound, the lanthanum (barium) compound, the boron (boron) compound and the chlorine compound, and the chlorine compound in a molar ratio of 2.5-3.3:3.5-4.2:2.5-3.5:0.7-1.3, uniformly mixing the strontium (barium) compound, the lanthanum compound, the boron compound and the chlorine compound raw materials, putting the grinded materials into a muffle furnace for presintering, cooling to room temperature, taking out and grinding the materials, and putting the grinded materials into the muffle furnace for calcination to prepare the strontium borate chloride and the barium lanthanum borate chloride.
3. The method for preparing the compounds of lanthanum strontium chloroborate and barium lanthanum chloroborate according to claim 2, wherein the strontium (barium) containing compound comprises at least one of strontium hydroxide (barium strontium hydroxide), strontium oxide (barium strontium oxide), and strontium (barium) salt;
the lanthanum-containing compound comprises at least one of lanthanum oxide, lanthanum hydroxide and lanthanum salt;
the boron-containing compound is boron oxide, boron hydroxide and boron salt;
the chlorine-containing compound is at least one of barium chloride and ammonium chloride.
4. The method for preparing the compounds of lanthanum strontium chloroborate and barium lanthanum chloroborate according to claim 3, wherein the strontium (barium) salt comprises at least one of strontium chloride (barium chloride), strontium carbonate (barium carbonate), strontium sulfate (barium sulfate), strontium nitrate (barium nitrate), strontium oxalate (barium oxalate), and strontium acetate (barium acetate);
the lanthanum salt comprises at least one of lanthanum carbonate, lanthanum nitrate, lanthanum chloride, lanthanum oxalate and lanthanum sulfate.
5. Two kinds of nonlinear optical crystal of strontium lanthanum chloroborate and barium lanthanum chloroborate, which are characterized in that the chemical formula is A 3 La 4 B 3 O 13 Cl, wherein a=sr, ba, belongs to hexagonal system, space group P6 3 The unit cell parameters are: 1) Sr (Sr) 3 La 4 B 3 O 13 Cl：
Figure FDA0003312096530000021
Figure FDA0003312096530000022
Z＝2，/>
Figure FDA0003312096530000023
2)Ba 3 La 4 B 3 O 13 Cl：/>
Figure FDA0003312096530000024
Figure FDA0003312096530000025
Z＝2，
Figure FDA0003312096530000026
6. The method for preparing the strontium lanthanum chloroborate and barium lanthanum chloroborate nonlinear optical crystal according to claim 5, wherein the strontium lanthanum chloroborate and barium lanthanum chloroborate nonlinear optical crystal is grown by a high-temperature melt method or a pulling method.
7. The method according to claim 6, characterized in that the specific operations are performed according to the following steps:
a. heating up to melt the single-phase polycrystalline powder of the lanthanum strontium chloroborate and the barium lanthanum chloroborate compound obtained in any one of claims 1-4 or the mixture of the single-phase polycrystalline powder of the lanthanum strontium chloroborate and the barium lanthanum chloroborate obtained in any one of claims 1-4 and a fluxing agent to obtain a mixed melt, and cooling or growing at constant temperature to prepare a compound lanthanum strontium chloroborate and a barium lanthanum chloroborate crystal;
or directly heating a mixture of a barium (strontium) -containing compound, a lanthanum-containing compound, a boron-containing compound and a chlorine-containing compound or a mixture of a barium-containing compound, a lanthanum-containing compound, a boron-containing compound and a chlorine-containing compound with a fluxing agent to melt to obtain a mixed melt, and cooling or growing at constant temperature to prepare compound lanthanum strontium chloroborate and barium lanthanum chloroborate crystals;
b. placing the crucible containing the mixed solution prepared in the step a into a crystal growth furnace, fixing seed crystals on seed rods, lowering the seed crystals to be in contact with the liquid surface of the mixed solution or the mixed solution for remelting, and reducing the temperature to saturation; and (3) cooling or growing at constant temperature to prepare the compound lanthanum strontium chloroborate and the compound lanthanum barium chloroborate.
8. The method of claim 7, wherein the molar ratio of lanthanum strontium chloroborate and barium lanthanum chloroborate compound single-phase polycrystalline powder to flux is 1:1-20; the method comprises the steps of carrying out a first treatment on the surface of the Or wherein the molar ratio of the barium (strontium) -containing compound, the lanthanum-containing compound, the boron-containing compound, and the chlorine-containing compound to the fluxing agent is 3:4:3:1:1-20; the single fluxing agent comprises one or more of barium oxide (strontium oxide), boric acid, barium chloride (strontium chloride), sodium chloride, lithium chloride, potassium chloride, lead oxide, sodium carbonate, potassium carbonate and lithium carbonate, and the composite fluxing agent comprises SrCl 2 (BaCl 2 )-H 3 BO 3 、PbO-H 3 BO 3 、NaCl-H 3 BO 3 、LiCl-H 3 BO 3 、Na 2 CO 3 -H 3 BO 3 、Li 2 CO 3 -H 3 BO 3 、K 2 CO 3 -H 3 BO 3 、SrCl 2 (BaCl 2 )-PbO、NaCl-PbO、LiCl-PbO、Na 2 CO 3 -PbO、Li 2 CO 3 -PbO、K 2 CO 3 -PbO、PbO-H 3 BO 3 、SrCl 2 (BaCl 2 )-H 3 BO 3 -PbO、NaCl-H 3 BO 3 -PbO、LiCl-H 3 BO 3 -PbO、Na 2 CO 3 -H 3 BO 3 -PbO、Li 2 CO 3 -H 3 BO 3 -PbO、K 2 CO 3 -H 3 BO 3 -PbO、LiCl-SrCl 2 (BaCl 2 )-H 3 BO 3 、NaCl-SrCl 2 (BaCl 2 )-H 3 BO 3 、NaCl-LiCl-H 3 BO 3 、LiCl-Na 2 CO 3 -H 3 BO 3 、LiCl-K 2 CO 3 -H 3 BO 3 、NaCl-Na 2 CO 3 -H 3 BO 3 、NaCl-K 2 CO 3 -H 3 BO 3 、KCl-Na 2 CO 3 -H 3 BO 3 -SrCl 2 (BaCl 2 )、KCl-Na 2 CO 3 -H 3 BO 3 、KCl-K 2 CO 3 -H 3 BO 3 、KCl-K 2 CO 3 -H 3 BO 3 -SrCl 2 (BaCl 2 )、NaCl-Na 2 CO 3 -H 3 BO 3 、NaCl-Na 2 CO 3 -H 3 BO 3 -SrCl 2 (BaCl 2 )、NaCl-LiCl-H 3 BO 3 -SrCl 2 (BaCl 2 )、KCl-LiCl-H 3 BO 3 -SrCl 2 (BaCl 2 )、PbO-H 3 BO 3 -SrCl 2 (BaCl 2 )、K 2 CO 3 -PbO-SrCl 2 (BaCl 2 )、NaCl-PbO-SrCl 2 (BaCl 2 )、NaCl-H 3 BO 3 -SrCl 2 (BaCl 2 )、NaCl-H 3 BO 3 -SrCl 2 (BaCl 2 )、LiCl-H 3 BO 3 -SrCl 2 (BaCl 2 )、LiCl-Na 2 CO 3 -H 3 BO 3 -SrCl 2 (BaCl 2 ) One or more of the following.
9. A method according to claim 8, characterized in that the KCl-H is fluxing agent 3 BO 3 、SrCl 2 (BaCl 2 )-H 3 BO 3 、PbO-H 3 BO 3 、NaCl-H 3 BO 3 Or LiCl-H 3 BO 3 The mol ratio of chloride to boric acid in the fluxing agent is 0.1-10:0.2-20; the Na is 2 CO 3 -H 3 BO 3 、Li 2 CO 3 -H 3 BO 3 Or K 2 CO 3 -H 3 BO 3 The molar ratio of carbonate to boric acid in the fluxing agent is 0.2-15:0.1-30; the KCl-PbO, srCl 2 (BaCl 2 ) The molar ratio of chloride to lead oxide in the PbO, naCl-PbO and LiCl-PbO fluxing agent is 0.5-19:0.5-26; the Na is 2 CO 3 -PbO、Li 2 CO 3 -PbO、K 2 CO 3 The molar ratio of carbonate to lead oxide in the PbO fluxing agent is 0.2-15:1-19; the KCl-H 3 BO 3 -PbO、SrCl 2 (BaCl 2 )-H 3 BO 3 -PbO、NaCl-H 3 BO 3 -PbO、LiCl-H 3 BO 3 The molar ratio of chloride to boric acid and lead oxide in the PbO fluxing agent is 0.1-10:0.2-13:1-21; the Na is 2 CO 3 -H 3 BO 3 -PbO、Li 2 CO 3 -H 3 BO 3 -PbO、K 2 CO 3 -H 3 BO 3 The molar ratio of carbonate to boric acid to lead oxide in the PbO fluxing agent is 1-13:0.5-19:0.4-26; the NaCl-KCl-H 3 BO 3 、NaCl-SrCl 2 (BaCl 2 )-H 3 BO 3 、NaCl-LiCl-H 3 BO 3 、LiCl-SrCl 2 (BaCl 2 )-H 3 BO 3 、LiCl-SrCl 2 (BaCl 2 )-H 3 BO 3 The mol ratio of the first chloride to the second chloride and boric acid in the fluxing agent is 0.1-21:1-16:0.7-20; the LiCl-Na 2 CO 3 -H 3 BO 3 、LiCl-K 2 CO 3 -H 3 BO 3 、NaCl-Na 2 CO 3 -H 3 BO 3 、NaCl-K 2 CO 3 -H 3 BO 3 、KCl-Na 2 CO 3 -H 3 BO 3 、KCl-K 2 CO 3 -H 3 BO 3 The mol ratio of chloride to carbonate to boric acid in the fluxing agent is 1-10:0.5-14:1-20; the KCl-Na 2 CO 3 -H 3 BO 3 -SrCl2(BaCl2)、KCl-K 2 CO 3 -H 3 BO 3 -SrCl 2 (BaCl 2 )、NaCl-SrCl 2 (BaCl 2 )-Na 2 CO 3 -H 3 BO 3 、LiCl-SrCl 2 (BaCl 2 )-Na 2 CO 3 -H 3 BO 3 The mole ratio of the first chloride to the second chloride and boric acid in the fluxing agent is 0.1-23:1-17:0.7-23:1-24.
10. The use of the strontium lanthanum chloroborate and barium lanthanum chloroborate nonlinear optical crystal according to claim 5, wherein the strontium lanthanum chloroborate and barium lanthanum chloroborate nonlinear optical crystal is used for preparing a frequency multiplication generator, an upper frequency converter, a lower frequency converter or an optical parametric oscillator.
CN202111219639.5A 2021-10-20 2021-10-20 Compound lanthanum strontium chloroborate and lanthanum barium chloroborate, nonlinear optical crystal thereof and preparation method and application thereof Pending CN115991481A (en)

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