CN114016121B - Method for growing carbonate Raman crystal at low temperature and application - Google Patents

Method for growing carbonate Raman crystal at low temperature and application Download PDF

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CN114016121B
CN114016121B CN202111288952.4A CN202111288952A CN114016121B CN 114016121 B CN114016121 B CN 114016121B CN 202111288952 A CN202111288952 A CN 202111288952A CN 114016121 B CN114016121 B CN 114016121B
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carbonate
crystal
reaction
temperature
raman
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CN114016121A (en
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吕宪顺
王旭平
刘冰
邱程程
禹化健
石强
张锐
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New Material Institute of Shandong Academy of Sciences
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B9/00—Single-crystal growth from melt solutions using molten solvents
    • C30B9/04—Single-crystal growth from melt solutions using molten solvents by cooling of the solution
    • C30B9/08—Single-crystal growth from melt solutions using molten solvents by cooling of the solution using other solvents
    • C30B9/12—Salt solvents, e.g. flux growth
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B28/00—Production of homogeneous polycrystalline material with defined structure
    • C30B28/04—Production of homogeneous polycrystalline material with defined structure from liquids
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides
    • C30B29/22—Complex oxides
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65—Raman scattering

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Abstract

The invention belongs to the technical field of second-order nonlinear crystal preparation, and particularly relates to a method for growing carbonate Raman crystals at low temperature and application thereof, wherein the method comprises the following steps: mixing BaCO 3 Dissolving borate and urea in alcohol, and carrying out flux thermal reaction; and cooling to room temperature after the reaction is finished to obtain the carbonate Raman crystal. The carbonate Raman crystal grows by a flux thermal method, the carbonate crystal can grow at low temperature, the problem that the carbonate crystal is difficult to grow at high temperature is solved, and the frequency shift amount reaches 1057.8cm ‑1 The novel Raman crystal widens the application range of the Raman crystal.

Description

Method for growing carbonate Raman crystal at low temperature and application
Technical Field
The invention belongs to the technical field of second-order nonlinear crystal preparation, and particularly relates to a method for growing a carbonate Raman crystal at a low temperature and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Natural CaCO 3 The crystal is rare, and the artificial crystal is difficult to grow. Because the carbonate crystal is difficult to grow at high temperature, the related research of the carbonate Raman crystal is lacked for a long time, and the popularization and the application of the crystal are seriously limited. In addition, the frequency shift of the existing Raman crystal is small, and the application of the Raman crystal is further limited. Therefore, it is important how to provide a method for growing carbonate-based raman crystals at low temperature and broaden the frequency shift amount of the raman crystals.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a method for growing carbonate Raman crystals at low temperature and application thereof, and Ba is grown by a flux thermal method 5 (CO 3 ) 2 (BO 3 ) 2 The carbonate Raman crystal can grow at low temperature, solves the problem that the carbonate crystal is difficult to grow at high temperature, and obtains the frequency shift amount of 1057.8cm -1 The novel Raman crystal widens the application range of the Raman crystal.
Specifically, the invention is realized by the following technical scheme:
in a first aspect of the invention, a method of growing a carbonate raman crystal at low temperature, the method comprising: mixing BaCO 3 Dissolving borate and urea in alcohol, and carrying out flux thermal reaction; and cooling to room temperature after the reaction is finished to obtain the carbonate Raman crystal.
In a second aspect of the invention, a carbonate Raman crystal is prepared by the method.
In a third aspect of the invention, the method and/or the carbonate raman crystal are used in the fields of optical molecular imaging, structural analysis, biological monitoring and medical treatment.
One or more embodiments of the present invention have the following advantageous effects:
(1) Growth of Ba by flux-thermal method 5 (CO 3 ) 2 (BO 3 ) 2 Carbonate Raman crystals capable of obtaining crystals containing a planar conjugated structure [ CO ] 3 ] 2- The flux thermal method of growing Ba at low temperature 5 (CO 3 ) 2 (BO 3 ) 2 The carbonate Raman crystal overcomes the problem that the carbonate crystal is difficult to grow at high temperature.
(2) The flux thermal method is growing Ba 5 (CO 3 ) 2 (BO 3 ) 2 The carbonate Raman crystal provides a low-temperature environment, and in the reaction process, the carbonate, the borate and the urea are dissolved in the alcohol, so that the crystal nucleus grows uniformly and stably. In the flux thermal reaction, the existence of the alcohol can provide better growth atmosphere for crystal growth and increaseThe stability and crystallinity of crystal growth are improved.
(3) In some embodiments, by controlling the temperature reduction process of the crystal, not only can the stability of the crystal be improved but also the nucleation of the crystal can be reasonably controlled, and the size of the crystal is larger than that of the crystal which is not subjected to the reasonable temperature reduction process.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
FIG. 1 BaCO synthesized by the flux thermal method described in example 1 3 X-ray diffraction patterns of the powders;
FIG. 2 Ba grown by flux thermal method as described in example 1 5 (CO 3 ) 2 (BO 3 ) 2 A crystal picture;
FIG. 3 flux-thermally grown Ba as described in example 1 5 (CO 3 ) 2 (BO 3 ) 2 An X-ray diffraction pattern of the crystal;
FIG. 4 Ba prepared in example 1 5 (CO 3 ) 2 (BO 3 ) 2 Spontaneous Raman spectrum of the crystal.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Experimental procedures without specific conditions noted in the following examples, generally according to conventional conditions or according to conditions recommended by the manufacturers.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The carbonate crystal is easy to decompose when prepared under the high temperature condition, and the preparation research on the carbonate Raman crystal is very little at present. Some researches on the preparation of carbonate crystals have the preparation temperature of 700-900 ℃, substances for avoiding the decomposition of the carbonate crystals need to be added during the preparation, the preparation difficulty and the cost are improved, the carbonate Raman crystals with better crystal forms cannot be obtained, and the requirements cannot be met at all. Therefore, the invention provides a low-temperature growth Ba 5 (CO 3 ) 2 (BO 3 ) 2 A method and application of carbonate Raman crystal.
In one or more embodiments of the present invention, a method for low temperature growth of a carbonate raman crystal, the method comprising: mixing BaCO 3 Dissolving borate and urea in alcohol, and carrying out flux thermal reaction; and cooling to room temperature after the reaction is finished to obtain the carbonate Raman crystal.
Currently, ba is prepared in an open system 5 (CO 3 ) 2 (BO 3 ) 2 The method for preparing the carbonate Raman crystal has the problems of low preparation purity, complex preparation method and the like, and cannot meet the actual requirements. In addition, the carbonate Raman crystal is prepared in a container such as a crucible, the preparation temperature is high, the unbalance of raw material components is easily caused, the crystal growth process cannot be controlled, and the stability of the obtained crystal is poor. Different from the prior art, the invention directly mixes BaCO 3 The borate and the urea are dissolved in alcohol to carry out flux thermal reaction. The flux thermal method reaction is carried out in an autoclave in a sealing way, and the temperature of the flux thermal method reaction is 150-220 ℃, preferably 200 ℃; or the time of the flux thermal method reaction is 18 to 30 hours, and preferably 24 hours. Under the condition, the alcohol environment provides an optimal environment for stable formation of crystal nucleus, and the sealed flux thermal method has stable crystal growth and higher crystallinity, thereby meeting the requirement of preparing the carbonate Raman crystal under the low-temperature condition.
Further, the autoclave is a polytetrafluoroethylene-lined autoclave.
Meanwhile, in order to ensure that the prepared Raman crystal has a larger size, the specific method for reducing the temperature to room temperature comprises the following steps: after the reaction is finished under the condition of low temperature, the temperature is reduced to room temperature at the cooling rate of 8-12 ℃/day, preferably at the cooling rate of 10 ℃/day. Meanwhile, the temperature reduction process is important for improving the stability and the crystallinity of the crystal.
Wherein the alcohol is 1, 2-propanediol. BaCO 3 The stoichiometric ratio of boric acid to urea is 3-8; preferably, the ratio is 5. BaCO 3 After the borate and the urea are dissolved in the alcohol, the mixture is heated to 40-70 ℃ and stirred to react for 10-30min until the powder is completely dissolved.
The BaCO 3 The synthesis method comprises the following steps: weighing BaS and (NH) according to stoichiometric ratio 4 ) 2 CO 3 Placing the mixture in an ultrasonic cleaning machine, raising the temperature to 40-60 ℃, slowly injecting sufficient deionized water, and then ultrasonically cleaning for 20-30 minutes until the reaction is completely carried out; the reaction product was filtered 3-5 times with deionized water using a vacuum filtration machine to remove (NH) 4 ) 2 S; transferring the powder obtained after suction filtration into a crucible, placing the crucible in a muffle furnace, and keeping the temperature at 90-110 ℃ for 8-15 hours to remove residual moisture; wherein BaS and (NH) 4 ) 2 CO 3 The stoichiometric ratio of (1) to (1-1.1), the optimal ratio of (1).
In one or more embodiments of the invention, a carbonate raman crystal is prepared by the above method.
In one or more embodiments of the invention, any of the methods and/or the carbonate-based raman crystals are used in the fields of optical molecular imaging, structural analysis, biological monitoring, and medical treatment.
The present invention is described in further detail below with reference to specific examples, which are intended to be illustrative of the invention and not limiting.
Examples
Novel Raman crystal material Ba 5 (CO 3 ) 2 (BO 3 ) 2 Comprising:
1：BaCO 3 synthesis of powders
In stoichiometric ratioAnalytically pure BaS (12.38 g), (NH) was weighed 4 ) 2 CO 3 (7.62 g) placing the mixture in an ultrasonic cleaning machine, raising the temperature to 50 ℃, slowly injecting enough deionized water, and then ultrasonically cleaning for 30 minutes until the reaction is completely carried out;
the reaction equation is as follows:
BaS+(NH 4 ) 2 CO 3 ＝BaC0 3 ↓+(NH 4 ) 2 S
the reaction product was filtered with deionized water 5 times under vacuum using a VF204A vacuum filter to remove (NH) 4 ) 2 And S. And transferring the powder obtained after suction filtration into a corundum crucible, placing the corundum crucible in a muffle furnace, and keeping the temperature at 100 ℃ for 12 hours to remove residual moisture. A portion of the powder was ground and used for XRD testing. The phase structure (Cu K alpha) of the treated powder was measured at room temperature using a Japanese Rigaku Intelligent multifunctional X-ray diffractometer Smartlab SE, and the results are shown in FIG. 1, indicating that the resulting reaction product was BaCO 3 And (3) powder.
2: ultrasonic dispersion
Measuring 100ml of 1, 2-propylene glycol by using a measuring cylinder, and pouring into a 200ml beaker; weighing 8.01g of BaCO prepared in step 1 3 Powder, 1.5g of H 3 BO 3 And 0.49g CH 4 N 2 O and transferring it into a beaker; the beaker is placed on an ultrasonic stirring mixer and heated to 50 ℃ and then stirred for 20 minutes until the powder is completely dispersed and dissolved.
3：Ba 5 (CO 3 ) 2 (BO 3 ) 2 By flux-thermal growth of crystals
Transferring the solution obtained in the step 2 into a 200ml autoclave (polytetrafluoroethylene lining), sealing, putting into a muffle furnace, slowly heating to 200 ℃, and keeping the temperature for 24 hours; cooling to room temperature at a cooling rate of 10 ℃/day, and repeatedly cleaning with deionized water to obtain Ba s (CO 3 ) 2 (BO 3 ) 2 The crystal (as shown in FIG. 2) and XRD experiment result (FIG. 3) show that the grown crystal is Ba 5 (CO 3 ) 2 (BO 3 ) 2 And (4) crystals.
4：Ba 5 (CO 3 ) 2 (BO 3 ) 2 Spontaneous Raman spectroscopy of crystals
Taking Ba grown in step 3 5 (CO 3 ) 2 (BO 3 ) 2 Fully grinding the crystal by using an agate mortar for spontaneous Raman spectrum testing, wherein a LABRAMHR800 Raman spectrum analyzer (JOBIN YVON) is adopted for testing, the testing temperature is room temperature, and the measuring range is 100-1500 cm -1 The excitation wavelength was 632.8nm He-Ne laser (800 mw) collected in a back-scattered configuration. As shown in FIG. 4, the strongest Raman peak in the Raman spectrum is located at 1057.8cm -1 Corresponding to (CO) 3 ) 2- Radical full-symmetric respiratory vibration with half-height width of 9.7cm -1 And can be used for picosecond pulse Raman lasers.
5: applications 1
YAG as Nd pump to realize 1.06 micron laser output via LiNbO 3 After electro-optically modulating Q, passing Ba 5 (CO 3 ) 2 (BO 3 ) 2 The crystal realizes 1199nm laser output.
6: application 2
YAG as Nd pump to output 1.06 micron laser via LiNbO 3 After electro-optical Q-switching, frequency multiplication is carried out through a nonlinear optical crystal BBO to obtain 532nm laser, and then frequency multiplication light is led to pass through Ba 5 (CO 3 ) 2 (BO 3 ) 2 The crystal realizes 564nm yellow laser output.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described above, or equivalents may be substituted for elements thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (12)

1. A method for growing a carbonate Raman crystal at a low temperature is characterized by comprising the following steps: mixing BaCO 3 Dissolving borate and urea in alcohol, and carrying out flux thermal reaction; reaction ofCooling to room temperature to obtain carbonate Raman crystal;
the flux thermal method reaction is carried out in a high-pressure kettle in a sealing way; the temperature of the flux thermal method reaction is 150-220 ℃.
2. The method for growing the carbonate Raman crystal at the low temperature according to claim 1, wherein the time of the flux thermal reaction is 18-30h.
3. The method for growing a carbonate raman crystal at a low temperature according to claim 1, wherein the temperature of the flux thermal reaction is 200 ℃; the time of the flux thermal method reaction is 24 hours.
4. The method for growing a carbonate raman crystal according to claim 1, wherein the alcohol is 1, 2-propanediol.
5. The method of claim 1, wherein BaCO is BaCO 3 And the stoichiometric ratio of the boric acid to the urea is 3-8.
6. The method of claim 1, wherein BaCO is BaCO 3 The stoichiometric ratio of boric acid to urea is 5.
7. The method for growing carbonate Raman crystals at low temperature according to claim 1, wherein the autoclave is an autoclave lined with polytetrafluoroethylene; or, the specific method for reducing the temperature to the room temperature comprises the following steps: after the reaction is finished under the condition of low temperature, the temperature is reduced to room temperature at the cooling rate of 8-12 ℃/day.
8. The method for growing the carbonate Raman crystal at the low temperature according to claim 7, wherein the temperature is reduced to room temperature at a cooling rate of 10 ℃/day after the reaction is completed under the low temperature condition.
9. The method of claim 1, wherein BaCO is BaCO 3 After the borate and the urea are dissolved in the alcohol, the mixture is heated to 40-70 ℃ and stirred to react for 10-30min until the powder is completely dissolved.
10. The method of claim 3, wherein the BaCO is BaCO 3 The synthesis method comprises the following steps: weighing BaS and (NH) according to stoichiometric ratio 4 ) 2 CO 3 Placing the mixture in an ultrasonic cleaning machine, raising the temperature to 40-60 ℃, slowly injecting sufficient deionized water, and then ultrasonically cleaning for 20-30 minutes until the reaction is completely carried out; the reaction product was filtered 3-5 times with deionized water using a vacuum filtration machine to remove (NH) 4 ) 2 S; transferring the powder obtained after suction filtration into a crucible, placing the crucible in a muffle furnace, and keeping the temperature at 90-110 ℃ for 8-15 hours to remove residual moisture.
11. The method of claim 10, wherein the BaS and (NH) are mixed with each other to form a carbonate Raman crystal 4 ) 2 CO 3 The stoichiometric ratio of (A) is 1.
12. The method of claim 10, wherein the BaS and (NH) are mixed with each other to form a carbonate Raman crystal 4 ) 2 CO 3 1.03, and the ratio of (b) to (c) is 1.
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