CN108950687A - Boracite crystal, preparation method and use - Google Patents
Boracite crystal, preparation method and use Download PDFInfo
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- CN108950687A CN108950687A CN201810196575.3A CN201810196575A CN108950687A CN 108950687 A CN108950687 A CN 108950687A CN 201810196575 A CN201810196575 A CN 201810196575A CN 108950687 A CN108950687 A CN 108950687A
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
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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
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/35—Non-linear optics
- G02F1/355—Non-linear optics characterised by the materials used
- G02F1/3551—Crystals
Abstract
The invention discloses boracite crystals, preparation method and use, belong to crystal material field.The chemical formula of the boracite crystal is Mg3B7O13Cl, with orthohormbic structure, space group is rhombic system Pca21, point group mm2, cell parameter:The ultraviolet absorption edge of the crystal is 155nm, and has ferroelectricity and nonlinear effect simultaneously；The crystal physicochemistry property is stable, easy to process and save, and can be used for making a variety of optical devices.
Description
Technical field
The invention belongs to crystal material fields, are related to a kind of with the non-linear and ferroelectric photoelectric information functional of deep ultraviolet
Crystal, and in particular to a kind of boracite crystal, preparation method and use.
Background technique
Non-linear optical crystal material is played an important role in laser science and technical field.From 1961 in quartz-crystal
Since finding frequency-doubled effect for the first time in body, it has been found that many novel nonlinear optical crystals, such as β-BaB2O4(BBO)、
LiB3O5(LBO)、CsB3O5(CBO)、CsLiB6O10(CLBO)、YCa4O(BO3)3(YCOB)、KBe2BO3F2(KBBF)、
RbBe2O3F2(RBBF) etc. the commercialization of ultraviolet-infrared band nonlinear optical crystal, is realized, and deep ultraviolet nonlinear optics
The development task of crystal is still very arduous.Although it have been found that many ultraviolet absorption edge 200nm novel non-linearities below
Optical crystal, since its two-fold rate is not moderate (Δ n is~0.06-0.10), phase is mismatched, and it is defeated to cannot achieve deep ultraviolet laser
Out.Currently, only KBBF directly can realize 200nm deep ultraviolet laser output below by two frequencys multiplication.However, due to KBBF's
Layer growth habit and active force weak between layers, it is difficult to obtain large-size crystals that can be practical.Simultaneously as beryllium is first
The toxicity of element, will all bring a negative impact researcher and environment, and also be unfavorable for carrying out deep developmental research.Therefore, compel
Environmental-friendly novel deep ultraviolet nonlinear optical crystal will be developed by being essential.And excellent deep ultraviolet nonlinear optical crystal is not only
It needs that there is short ultraviolet absorption edge, moderate two-fold rate, it is also necessary to have big nonlinear factor (> 0.39pm/V).But
It is analyzed from structural point, the ultraviolet absorption edge and nonlinear factor of crystal are usually contradictory, are obtained by structure Design and optimization
The deep ultraviolet nonlinear optical crystal haveing excellent performance is extremely difficult.
Summary of the invention
The present invention provides a kind of boracite crystal, and the chemical formula of the crystal is Mg3B7O13Cl, the crystal are positive at room temperature
Knot structure, space group Pca21, cell parameter is α=β=γ=90 °.
Preferably, the crystal has X-ray crystal diffraction map substantially as shown in Figure 1a.
Preferably, the crystal has dielectric shown in ferroelectric hysteresis loop spectrogram shown in a basically as in Figure 2 and/or Fig. 2 b
Wen Pu.Preferably, the coercive electric field of the crystal is 41.5kV/cm, and remanent polarization is 0.25 μ C/cm2。
Preferably, the crystal has shown in powder SHG effect map and/or Fig. 3 b substantially as shown in Figure 3a
Through spectrum.Preferably, the ferroelectricity of the crystal-para-electric phase transition temperature (Curie temperature) is 258 DEG C.
Illustrative embodiment according to the present invention, the ultraviolet absorption edge of the boracite crystal are 155nm.
Illustrative embodiment according to the present invention, the boracite crystal its second order under 100~200 μm of crystallite dimensions
Nonlinear optical coefficients are about the 1/6 of KDP (potassium dihydrogen phosphate crystal).
According to the present invention, the boracite crystal is colourless transparent crystal.
The present invention also provides the preparation method of boracite crystal, this method includes being passed through by the boracite and fluxing agent of pre-burning
Molten-salt growth obtains boracite crystal.
According to the present invention, it the described method comprises the following steps:
(1) boracite of pre-burning is prepared；
(2) boracite of pre-burning and fluxing agent are mixed, in molten salt furnace after heating, melting, heat preservation, cooling, is obtained
Boracite crystal.
Method produced according to the present invention, the boracite of the pre-burning is with magnesium-containing compound and B2O3And/or H3BO3For raw material,
Weighed, mixing, grinding, tabletting, shove charge are fired；
The magnesium-containing compound is MgCl2、MgO、MgCO3At least one of；
The dosage of the raw material is according to Mg3B7O13The distribution of Cl stoichiometric ratio；
Preferably, the MgCl2Can excessive 0.5~3wt%, such as excess 1.0wt%, 1.5wt%, 2.0wt%,
2.5wt%；
Preferably, the B2O3And/or H3BO3Excessive 1.5~8wt%, for example, excess 3wt%, 3.5wt%, 4.0wt%,
5.0wt%, 6.0wt%, 7.0wt%, 7.5wt%；
The temperature of the firing can be 700 DEG C or more, such as 750~950 DEG C, such as 800~900 DEG C；Firing time can
Think 1~3h, such as 1.5~2.5h, such as 2.0h.
Method produced according to the present invention, the boracite of the pre-burning and the molar ratio of fluxing agent can be 1:(1~6)；
Method produced according to the present invention, the fluxing agent are MgCl2With B2O3Or H3BO3Mixture, wherein MgCl2With
B2O3Or H3BO3Molar ratio can be (1~8): 1, such as (1~6): 1, such as (1~5): 1；Such as can be 1:1,2:1,3:1,
4:1,4.5:1.
Method produced according to the present invention, temperature is is risen to 800~1500 DEG C, such as 950~1400 DEG C by the heating, such as
1000~1200 DEG C；
Soaking time is 0.5~4 day, such as 1~3 day；
Temperature is is reduced to 15~40 DEG C by the cooling, and such as 20~25 DEG C.
The rate of heating and cooling can be identical or different, independently selected from 10~100 DEG C/h, such as 30~60 DEG C/
Hour, such as 40~50 DEG C/h.
Preferably, after cooling, it can also be rinsed with water, obtain boracite crystal.
The present invention also provides the purposes of above-mentioned boracite crystal in the opto-electronic device, for example, for device for non-linear optical,
The fields such as deep ultraviolet window device, optoelectronic switch, solar battery.
Beneficial effects of the present invention:
Boracite crystal provided by the invention, with good ferroelectricity, nonlinear effect, wide transmission region, surely
Fixed physical and chemical performance is not easy to deliquesce, good mechanical property, easy to process, and the polarization cycle by regulating and controlling crystal can be realized
Deep ultraviolet laser output.The crystal is a kind of with good ferroelectricity and the nonlinear photoelectric functional crystal of deep ultraviolet, can be wide
It is general to be applied to the fields such as device for non-linear optical, deep ultraviolet window device, optoelectronic switch, solar battery.
Detailed description of the invention
Fig. 1 is the structure chart of boracite crystal: (a) X-ray single crystal diffraction map (b) space structure figure.
Fig. 2 is the electric property phenogram of 1 boracite crystal of embodiment: (a) ferroelectric hysteresis loop (b) dielectric temperature is composed.
Fig. 3 is the optical property phenogram of 1 boracite crystal of embodiment: (a) powder SHG effect map (b) penetrates light
Spectrum.
Specific embodiment
Further detailed description is done to technical solution of the present invention below in conjunction with specific embodiment.The following example
It is merely illustrative the ground description and interpretation present invention, and is not necessarily to be construed as limiting the scope of the invention.It is all to be based on this hair
In the range of the technology that bright above content is realized is encompassed by the present invention is directed to protect.
Unless otherwise indicated, raw materials and reagents used in the following embodiment are commercial goods, or can be by
Perception method preparation.
1 molten-salt growth boracite crystal of embodiment
(1) it prepares the boracite of pre-burning: using analytically pure MgCl2、H3BO3Initial feed is done, according to Mg3B7O13Clization
Learn metering ratio, MgCl2And H3BO3Respectively excess 1wt% and 3wt% weighed, mixed, being ground, shove charge after tabletting, in 800~
Two hours of 900 DEG C of pre-burnings.
(2) crystal growth: using molten-salt growth boracite crystal, includes the following steps: the boracite of pre-burning and helps
Flux (fluxing agent MgCl2And H3BO3The mixture of 1:1 in molar ratio, to ensure not introduce impurity phase) according to molar ratio 1:1
It weighed, mixed, is fitted into platinum crucible, crucible is put into molten salt furnace center, covers bell；With 50 DEG C per hour
Rate is warming up to 1200 DEG C, and melting keeps the temperature two days, is then down to room temperature with 50 DEG C per hour of rate, is rinsed with water, the side of obtaining
Boron stone crystal.The crystal is colorless and transparent, is at room temperature orthohormbic structure, space group Pca21, cell parameter is α=β=γ=90 ° (see Fig. 1 b).
2 molten-salt growth boracite crystal of embodiment
(1) it prepares the boracite of pre-burning: using analytically pure MgO, MgCl2、H3BO3Initial feed is done, according to
Mg3B7O13Cl stoichiometric ratio, by MgO, MgCl2And H3BO3It weighs, wherein MgCl2And H3BO3Respectively excess 3wt% with
5wt%, shove charge after mixing, grinding, tabletting, in two hours of 800~900 DEG C of pre-burnings.
(2) crystal growth: using molten-salt growth boracite crystal, includes the following steps: the boracite of pre-burning and helps
Flux (fluxing agent MgCl2And H3BO3The mixture of 3:1 in molar ratio) it weighed, mixed according to molar ratio 1:2, it is packed into platinum
In golden crucible, crucible is put into molten salt furnace center, covers bell；1180 DEG C are warming up to 50 DEG C per hour of rate, is melted
Melt, keeps the temperature two days, room temperature is then down to 50 DEG C per hour of rate, is rinsed with water, obtains boracite crystal.
3 molten-salt growth boracite crystal of embodiment
(1) it prepares the boracite of pre-burning: using analytically pure MgCl2、H3BO3Initial feed is done, according to Mg3B7O13Clization
Metering ratio is learned, by MgCl2And B2O3It weighs, wherein MgCl2Excessive 2wt%, mixing, grinding, shove charge after tabletting, in 800~
Two hours of 900 DEG C of pre-burnings.
(2) crystal growth: using molten-salt growth boracite crystal, includes the following steps: the boracite of pre-burning and helps
Flux (fluxing agent MgCl2And H3BO3The mixture of 3:1 in molar ratio) it weighed, mixed according to molar ratio 1:4, it is packed into platinum
In golden crucible, crucible is put into molten salt furnace center, covers bell；1150 DEG C are warming up to 50 DEG C per hour of rate, is melted
Melt, keeps the temperature two days, room temperature is then down to 50 DEG C per hour of rate, is rinsed with water, obtains boracite crystal.
The structural characterization of 4 boracite crystal of embodiment
At room temperature, using X-ray single crystal diffraction, the structure of 1 gained boracite crystal of embodiment is measured, such as attached drawing 1a.Institute
It is Mercury CCD (Mo target) single crystal diffractometer with instrument.The crystal structure of embodiment 2 and 3 is same as Example 1.
The electric property of 5 boracite crystal of embodiment characterizes
(1) 2000 standard ferroelectricity measuring system of TF is used, the ferroelectric properties of 1 gained boracite crystal of embodiment is characterized
(see Fig. 2 a).
Test condition: the frequency of alternating voltage is 5Hz, and test temperature is 180 DEG C.
Test result: the coercive electric field of crystal is 41.5kV/cm, and remanent polarization is 0.25 μ C/cm2。
(2) Alpha-A dielectric/impedance Analytical high resolution instrument (Novolcontrol, German) is used, implementation is characterized
The dielectric response of 1 gained crystal of example (see Fig. 2 b).
Test condition: 30~400 DEG C of temperature-measuring range, small signal testing voltage 1V.
Test result: the ferroelectricity of crystal-para-electric phase transition temperature (Curie temperature) is 258 DEG C.
The optical property of 6 boracite crystal of embodiment characterizes
(1) at room temperature, using modified Kurtz-Perry method, the powder of 1 gained boracite crystal of embodiment is tested
Frequency-doubled effect (see Fig. 3 a), the results showed that boracite crystal its nonlinear factor under 100~200 μm of crystallite dimensions is about KDP
The 1/6 of (potassium dihydrogen phosphate crystal).
(2) McPherson2000 vacuum ultraviolet line absorption energy disperse spectroscopy is used, 1 gained boracite crystal of embodiment is characterized
Ultraviolet absorption edge (see Fig. 3 b), the results showed that the ultraviolet absorption edge of boracite crystal be 155nm.7 boracite crystal of embodiment
Stability and mechanical performance characterization
At room temperature, the boracite crystal that the growth of embodiment 1 obtains is placed in air after placing one month, without apparent
Moisture absorption phenomenon；
Embodiment 1 is grown obtained boracite crystal to weigh to obtain 1.05g, is placed one month in water, taking-up is dried, title
Weight still 1.05g, without weight change；
Cutting processing is carried out to boracite crystal, does not find problem of Cracking.
Illustrate that boracite crystal has stable physical and chemical performance, is not easy to deliquesce, it is good mechanical property, easy to process.
More than, embodiments of the present invention are illustrated.But the present invention is not limited to above embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. boracite crystal, the chemical formula of the crystal is Mg3B7O13Cl, which is characterized in that the crystal is positive knot at room temperature
Structure, space group Pca21, cell parameter is α=β=γ=90 °；
Preferably, the crystal has X-ray crystal diffraction map substantially as shown in Figure 1a.
2. boracite crystal according to claim 1, which is characterized in that the crystal has shown in a basically as in Figure 2
The spectrum of dielectric temperature shown in ferroelectric hysteresis loop spectrogram and/or Fig. 2 b；
Preferably, the crystal has and penetrates shown in powder SHG effect map and/or Fig. 3 b substantially as shown in Figure 3a
Spectrum；
Preferably, the ultraviolet absorption edge of the boracite crystal is 155nm；
Preferably, the boracite crystal its nonlinear second-order optical susceptibility under 100~200 μm of crystallite dimensions is about KDP's
1/6。
3. the preparation method of boracite crystal as claimed in claim 1 or 2, which is characterized in that this method includes the square boron by pre-burning
Stone and fluxing agent obtain boracite crystal by molten-salt growth.
4. the preparation method of boracite crystal according to claim 3, which is characterized in that the described method comprises the following steps:
(1) boracite of pre-burning is prepared；
(2) boracite of pre-burning and fluxing agent are mixed, in molten salt furnace after heating, melting, heat preservation, cooling, the side's of obtaining boron
Stone crystal.
5. according to the preparation method of the boracite crystal of claim 3 or 4, which is characterized in that the boracite of the pre-burning with
Magnesium-containing compound and B2O3And/or H3BO3For raw material, weighed, mixing, grinding, tabletting, shove charge is fired；
Preferably, the magnesium-containing compound is MgCl2、MgO、MgCO3At least one of；
Preferably, the dosage of the raw material is according to Mg3B7O13The distribution of Cl stoichiometric ratio；
Preferably, the MgCl2Can excessive 0.5~3wt%, such as excess 1.0wt%, 1.5wt%, 2.0wt%,
2.5wt%；
Preferably, the B2O3And/or H3BO3Can excessive 1.5~8wt%, such as excess 3wt%, 3.5wt%, 4.0wt%,
5.0wt%, 6.0wt%, 7.0wt%, 7.5wt%.
6. the preparation method of boracite crystal according to claim 5, which is characterized in that the temperature of the firing can be
700 DEG C or more, such as 750~950 DEG C, such as 800~900 DEG C；Firing time can be 1~3h, such as 1.5~2.5h, such as
2.0h。
7. according to the preparation method of any one of claim 3~6 boracite crystal, which is characterized in that the side of the pre-burning
The molar ratio of boron stone and fluxing agent can be 1:(1~6).
8. according to the preparation method of any one of claim 3~7 boracite crystal, which is characterized in that the fluxing agent is
MgCl2With B2O3Or H3BO3Mixture, wherein MgCl2With B2O3Or H3BO3Molar ratio can be (1~8): 1, such as (1~
6): 1, such as (1~5): 1.
9. according to the preparation method of any one of claim 4~8 boracite crystal, which is characterized in that the heating is will
Temperature rises to 800~1500 DEG C, such as 950~1400 DEG C, and such as 1000~1200 DEG C；
Soaking time is 0.5~4 day, such as 1~3 day；
Temperature is is reduced to 15~40 DEG C by the cooling, and such as 20~25 DEG C；
The rate of heating and cooling can be identical or different, independently selected from 10~100 DEG C/h, such as 30~60 DEG C/small
When, such as 40~50 DEG C/h；
Preferably, after cooling, it can also be rinsed with water, obtain boracite crystal.
10. the purposes of boracite crystal as claimed in claim 1 or 2 in the opto-electronic device, such as device for non-linear optical, depth
The fields such as ultraviolet window device, optoelectronic switch, solar battery.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111826715A (en) * | 2020-07-06 | 2020-10-27 | 中国科学院福建物质结构研究所 | Zinc chloroborate nonlinear optical crystal, preparation method and application |
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|---|---|---|---|---|
| CN102352533A (en) * | 2011-02-22 | 2012-02-15 | 中国科学院福建物质结构研究所 | Novel nonlinear optical crystal beryllium-sodium-cesium borate |
| CN102874827A (en) * | 2012-09-27 | 2013-01-16 | 中国科学院福建物质结构研究所 | Preparation method of solid iodine boracite |
-
2018
- 2018-03-09 CN CN201810196575.3A patent/CN108950687B/en active Active
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|---|---|---|---|---|
| CN102352533A (en) * | 2011-02-22 | 2012-02-15 | 中国科学院福建物质结构研究所 | Novel nonlinear optical crystal beryllium-sodium-cesium borate |
| CN102874827A (en) * | 2012-09-27 | 2013-01-16 | 中国科学院福建物质结构研究所 | Preparation method of solid iodine boracite |
Non-Patent Citations (2)
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| TUGBA IBROSKA等: "Synthesis,characterization, and electrical and optical properties of magnesium-type boracite", 《TURKISH JOURNAL OF CHEMISTRY》 * |
| TUGBA IBROSKA等: "Synthesis,characterization,and electrical and optical properties of magnesium-type boracite", 《TURKISH JOURNAL OF CHEMISTRY》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111826715A (en) * | 2020-07-06 | 2020-10-27 | 中国科学院福建物质结构研究所 | Zinc chloroborate nonlinear optical crystal, preparation method and application |
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