CN107541781A - A kind of method for being used to grow borosilicic acid lanthanum crystal - Google Patents
A kind of method for being used to grow borosilicic acid lanthanum crystal Download PDFInfo
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- CN107541781A CN107541781A CN201710993403.4A CN201710993403A CN107541781A CN 107541781 A CN107541781 A CN 107541781A CN 201710993403 A CN201710993403 A CN 201710993403A CN 107541781 A CN107541781 A CN 107541781A
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Abstract
The present invention provides a kind of for growing LaBSiO5Crystal or active ions doping LaBSiO5The method of crystal, is prepared using molten-salt growth method, and molten salt system includes LaBO3、Li2MoO4、SiO2Compound.Withx 1、x 2、x 3LaBO in expression system respectively3、Li2MoO4And SiO2Molar content, then the content ratio of these three compounds need to meet：0<x 1<0.3,0.7≤x 2<1,0<x 3<0.3 andx 1+x 2+x 3=1；The growth temperature section of crystal is 1000 DEG C 850 DEG C.Preparing LaBSiO5During crystal, Y can be adulterated thereto3+、Tm3+、Eu3+Ion etc., the La in these active ions replacement lattices3+Or B3+Ion, so as to prepare the LaBSiO of active ions doping5Crystal.It is related to technical field of optoelectronic functional materials.
Description
Technical field
Present disclosure is used to grow LaBSiO to be a kind of5Crystal or active ions doping LaBSiO5The side of crystal
Method, be related to technical field of optoelectronic functional materials, more particularly, to prepare it is a kind of can be as the work of solid optically functional device
The artificial lens technical field of medium.
Background technology
LaBSiO5Crystal has the properties such as non-linear and ferroelectric piezoelectric concurrently, is a kind of typical multiple functions matrix of materials.Just
It is because the crystal has a variety of properties, the LaBSiO of growing large-size5Monocrystalline attracts the research of people for a long time
Interest.However, the architectural feature due to having silicate and borate in the crystal structure of the compound concurrently, in growth raw material often
Comprising borate and silicate, melt viscosity is big under high temperature fused state, product amorphous state generally in glassy state, so
LaBSiO5The extremely difficult preparation of crystal.
Researchers prepare LaBSiO using solid-phase synthesis or sol-gal process5Or active ions doping
LaBSiO5Polycrystal powder, it have studied architectural feature and photoelectric functional characteristic of these powder crystals etc..In these work, grind
The LaBSiO that the person of studying carefully are synthesized5Crystalline size is micron order, undersized, leads to not to carry out deep performance to it grind
Study carefully and develop.
In order to obtain the LaBSiO of large-size5Crystal, N. I. Leonyuk et al. has attempted high temperature flux growth metrhod.
N.I. Leonyuk et al. is with K2Mo3O10Mixture with KF is fluxing agent, with 2 in 1150 DEG C -700 DEG C of temperature range
DEG C/h rate of temperature fall cooled, finally successfully obtain the LaBSiO that full-size is 2mm5Crystal.But the fluxing agent
Contain KF in system, poisonous and irritant, volatilization at high temperature can damage to human body.
In summary, want to prepare the LaBSiO of large-size5Crystal, two aspect problems are still faced at present：1, melt body
It is that viscosity is big, is unfavorable for crystal precipitation；2, contain fluoride in existing fluxing agent system, it is poisonous.
The content of the invention
The LaBSiO of large-size is prepared for solution5Crystal problem encountered, the present invention use following technical scheme：
One kind is used to grow borosilicic acid lanthanum（LaBSiO5）The preparation method of crystal, is prepared using molten-salt growth method, and molten salt system includes
LaBO3、Li2MoO4、SiO2Compound.Withx 1、 x 2、 x 3LaBO in expression system respectively3、 Li2MoO4And SiO2Moles hundred
Divide content, then the content ratio of these three compounds needs to meet：0<x 1<0.3, 0.7≤x 2<1, 0<x 3<0.3 andx 1+x 2+x 3=1；
The growth temperature section of crystal is 1000 DEG C -850 DEG C；
The LaBSiO prepared using heretofore described method5Crystal, crystalline size 1-30mm, its crystal structure ginseng
Number is：Trigonal system, space group P31, cell parameter is:A=6.8382, c=6.773, α=β=90 °, γ=120 °, z
=3；
LaBSiO is prepared using the technical method5During crystal, active ions, such as Y can be adulterated thereto as needed3+、 Tm3 +、Eu3+、Ca2+Ion etc., the La in these active ions replacement lattices3+Or B3+Ion, so as to prepare active ions doping
LaBSiO5Crystal is simultaneously finely adjusted control to its crystal structure, wherein, the doping of active ions is 1-10 at%；
In above-mentioned technical method, LaBO3Raw material be La2O3 and H3BO3, Li2MoO4Raw material be Li2CO3And MoO3, in height
Under temperature, above-mentioned raw materials are reacted according to following chemical equation：
La2O3+3H3BO3=2LaBO3+HBO2↑+4H2O↑ Li2CO3+MoO3= Li2MoO4+CO2↑
According to above-mentioned chemical equation, according to the LaBO described in this technology method3、 Li2MoO4And SiO2Mole percent contain
Amount carries out raw material configuration, is transferred in platinum crucible, is placed in high temperature furnace after the raw material weighed is fully ground uniformly.According to
Furnace temperature is risen to 1050 DEG C by 5-10 DEG C/min speed, is incubated 6-72h at such a temperature so as to the abundant congruent melting of melt and make
Gas discharge in melt.According to the difference of chemical composition in melt, the saturation point of system can float between 930 DEG C -1000 DEG C
It is dynamic.By furnace temperature after 1050 DEG C are down to saturation point, control rate of temperature fall that furnace temperature is brought down below into saturation for 1 DEG C/h-10 DEG C/h
Less than 50 DEG C of point, can fully separate out LaBSiO in this process in melt5Crystal；Then furnace temperature quickly can be down to room temperature.This
When take out crucible, you can choose the LaBSiO of water white transparency5Crystal.
By LaBSiO5Crystal or the LaBSiO of active ions doping5Crystal is used to prepare Solid-state Optics device, obtained
Solid-state Optics device system can be used for particle detection, laser device, spectroscopy device, biomedicine or military field.
Beneficial effects of the present invention
Preparation LaBSiO of the present invention5Crystal technology method, using LaBO3、Li2MoO4、SiO2Etc. compound as fused salt
System, wherein not fluoride, asepsis environment-protecting；Meanwhile it is low and have volatile molybdate containing viscosity in high-temperature fusant, significantly
The viscosity of melt is reduced, is advantageous to LaBSiO5Crystal separates out.
Brief description of the drawings
Fig. 1：LaBSiO prepared by embodiment 15Crystal photograph；
Fig. 2：LaBSiO prepared by embodiment 25Crystal photograph；
Fig. 3：LaBSiO prepared by embodiment 35Crystal photograph；
Fig. 4：La prepared by embodiment 40.95Eu0.05BSiO5Crystal photograph；
Fig. 5：La prepared by embodiment 50.97Y0.03BSiO5Crystal photograph；
Fig. 6：La prepared by embodiment 60.95Eu0.05BSiO5Crystal photograph；
Fig. 7：Embodiment 1-5 prepares the XRD spectrum of crystal；
Fig. 8：La prepared by embodiment 40.95Eu0.05BSiO5The fluorescence spectra of crystal（Excitation wavelength=394nm）.
Embodiment
The present invention further illustrates the present invention with the following example, but protection scope of the present invention is not limited to following reality
Apply example
Embodiment 1：
According to LaBO3:Li2MoO4:SiO2=0.2:0.75:0.05 (mol) ratio, gross weight is 30 grams of specification after melting
Weigh La2O3, H3BO3、Li2CO3、MoO3And SiO2Raw material, platinum crucible is transferred to after the raw material weighed is fully ground uniformly
In, it is placed in high temperature furnace.Furnace temperature is risen to 1050 DEG C according to 5 DEG C/min speed, is incubated 12h at such a temperature.By furnace temperature
960 DEG C are down to from 1050 DEG C of speed according to 10 DEG C/h, furnace temperature is then down to 850 DEG C according to 5 DEG C/h speed, it is last quick
It is down to room temperature.After furnace temperature is down to room temperature, crucible is taken out, the crystal of water white transparency is chosen from powder, is cleaned with water, drying
Size is 5*3*2 mm3 LaBSiO5Crystal.
Embodiment 2：
According to LaBO3:Li2MoO4:SiO2=0.1:0.8:0.1 (mol) ratio, gross weight is 20 grams of specification scale after melting
Take La2O3, H3BO3、Li2CO3、MoO3And SiO2Raw material, it is transferred to after the raw material weighed is fully ground uniformly in platinum crucible,
It is placed in high temperature furnace.Furnace temperature is risen to 1050 DEG C according to 8 DEG C/min speed, is incubated 8h at such a temperature.By furnace temperature from
1050 DEG C of speed according to 15 DEG C/h is down to 950 DEG C, and furnace temperature then is down into 850 DEG C according to 10 DEG C/h speed, last quick
It is down to room temperature.After furnace temperature is down to room temperature, crucible is taken out, the crystal of water white transparency is chosen from powder, is cleaned with water, drying
Size is 4*4*2 mm3 LaBSiO5Crystal.
Embodiment 3：
According to LaBO3:Li2MoO4:SiO2=0.22:0.70:0.08 (mol) ratio, gross weight is 20 grams of specification after melting
Weigh La2O3, H3BO3、Li2CO3、MoO3And SiO2Raw material, platinum crucible is transferred to after the raw material weighed is fully ground uniformly
In, it is placed in high temperature furnace.Furnace temperature is risen to 1050 DEG C according to 8 DEG C/min speed, is incubated 8h at such a temperature.By furnace temperature from
1050 DEG C of speed according to 15 DEG C/h is down to 950 DEG C, and furnace temperature then is down into 850 DEG C according to 10 DEG C/h speed, last quick
It is down to room temperature.After furnace temperature is down to room temperature, crucible is taken out, the crystal of water white transparency is chosen from powder, is cleaned with water, drying
Size is 3*3*2 mm3 LaBSiO5Crystal.
Embodiment 4：
According to La0.95Eu0.05BO3:Li2MoO4:SiO2=0.18:0.72:0.1 (mol) ratio, gross weight is 30 grams after melting
Specification weigh La2O3, Eu2O3、H3BO3、Li2CO3、MoO3And SiO2Raw material, shifted after the raw material weighed is fully ground uniformly
Into platinum crucible, it is placed in high temperature furnace.Furnace temperature is risen to 1050 DEG C according to 8 DEG C/min speed, is incubated at such a temperature
8h.Furnace temperature is down to 950 DEG C from 1050 DEG C of speed according to 15 DEG C/h, furnace temperature is then down to 850 according to 10 DEG C/h speed
DEG C, finally quickly it is down to room temperature.After furnace temperature is down to room temperature, crucible is taken out, the crystal of water white transparency is chosen from powder, it is clear with water
Wash, drying La0.95Eu0.05BSiO5Crystal, that is, adulterate Eu3+Ion concentration is 5at% LaBSiO5Crystal, size 3*3*
2 mm3。
Embodiment 5：
According to La0.97Y0.03BO3:Li2MoO4:SiO2=0.15:0.75:0.1 (mol) ratio, gross weight is 50 grams after melting
Specification weigh La2O3, Y2O3, H3BO3、Li2CO3、MoO3And SiO2Raw material, shifted after the raw material weighed is fully ground uniformly
Into platinum crucible, it is placed in high temperature furnace.Furnace temperature is risen to 1050 DEG C according to 8 DEG C/min speed, is incubated at such a temperature
8h.Furnace temperature is down to 950 DEG C from 1050 DEG C of speed according to 15 DEG C/h, furnace temperature is then down to 850 according to 10 DEG C/h speed
DEG C, finally quickly it is down to room temperature.After furnace temperature is down to room temperature, crucible is taken out, the crystal of water white transparency is chosen from powder, it is clear with water
Wash, drying La0.97Y0.03BSiO5Crystal, that is, adulterate Y3+Ion concentration is 3at% LaBSiO5Crystal, size 3*3*2
mm3。
Embodiment 6：
On the basis of embodiment 4, raw material configuration is carried out according to the proportioning of this, raw material gross weight is 150 grams after controlling melting,
Crystal growth is carried out using top-seeded solution growth：The crystal to be grown out using platinum wire or spontaneous nucleation does seed crystal, by seed
Crystalline substance drops at liquid level at 1035 DEG C, then cools according to daily 1-3 DEG C of speed, and brilliant rotary speed is 5-60 rpms, drop
The warm time is 10-30 days, and the crystal of precipitation is proposed into it is 15*20*13 mm that can obtain size afterwards3La0.95Eu0.05BSiO5It is brilliant
Body.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (8)
1. one kind is used to grow LaBSiO5The method of crystal, it is characterised in that：LaBSiO is prepared using molten-salt growth method5Crystal, fused salt
System includes LaBO3、Li2MoO4、SiO2Compound；Withx 1、 x 2、 x 3LaBO in expression system respectively3、 Li2MoO4With
SiO2Molar content, then the content ratio of these three compounds need to meet 0<x 1<0.3, 0.7≤x 2<1, 0<x 3<0.3 andx 1+x 2+x 3=1；The growth temperature section of crystal is 1000 DEG C -850 DEG C.
2. according to claim 1 be used to grow LaBSiO5The method of crystal, it is characterised in that：The LaBO3Raw material
For La2O3 and H3BO3, Li2MoO4Raw material be Li2CO3And MoO3。
3. LaBSiO made from growing method as claimed in claim 25Crystal, it is characterised in that：The LaBSiO5Crystal knot
Structure parameter is：Trigonal system, space group P31, cell parameter is:A=6.8382, c=6.773, α=β=90 °, γ=
120 °, z=3.
4. LaBSiO according to claim 35Crystal, it is characterised in that：Described LaBSiO5The size of crystal is 1-
30 millimeters.
A kind of 5. LaBSiO for growth activation ion doping5The method of crystal, it is characterised in that：The active ions are mixed
Miscellaneous amount is 1-10 at%, and the active ions are Y3+、Tm3+Or Eu3+；The LaBSiO of active ions doping is prepared using molten-salt growth method5
Crystal, molten salt system include La1-yMyBO3、Li2MoO4、SiO2Compound, wherein M are Y, Tm or Eu, 0.01≤y≤0.1；Withx 1、 x 2、 x 3La in expression system respectively1-yMyBO3、 Li2MoO4And SiO2Molar content, then these three compounds
Content ratio need to meet 0<x 1<0.3, 0.7≤x 2<1, 0<x 3<0.3 andx 1+x 2+x 3=1；The growth temperature section of crystal is 1000
℃-850℃。
6. the LaBSiO according to claim 5 for growth activation ion doping5The method of crystal, it is characterised in that：Institute
State La1-yMyBO3Raw material be M2O3、La2O3 and H3BO3, Li2MoO4Raw material be Li2CO3And MoO3。
7. the LaBSiO that active ions made from growing method as claimed in claim 6 adulterate5Crystal.
8. LaBSiO as claimed in claim 35The LaBSiO of active ions doping described in crystal or claim 75Crystal
Using, it is characterised in that：Described LaBSiO5Crystal or the LaBSiO of active ions doping5Crystal is preparing Solid-state Optics device
In application.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113322508A (en) * | 2021-05-27 | 2021-08-31 | 福州大学 | Growth method and application of high-temperature phase lanthanum borosilicate crystal |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831705A (en) * | 2009-03-13 | 2010-09-15 | 中国科学院福建物质结构研究所 | Method for growing YAl3(BO3)4 crystals by tungstate cosolvent system |
| CN102244257A (en) * | 2011-06-15 | 2011-11-16 | 清华大学深圳研究生院 | High-temperature manganic acid lithium cathode material and preparation method thereof |
-
2017
- 2017-10-23 CN CN201710993403.4A patent/CN107541781A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831705A (en) * | 2009-03-13 | 2010-09-15 | 中国科学院福建物质结构研究所 | Method for growing YAl3(BO3)4 crystals by tungstate cosolvent system |
| CN102244257A (en) * | 2011-06-15 | 2011-11-16 | 清华大学深圳研究生院 | High-temperature manganic acid lithium cathode material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| LINGYUN LI ET AL.: "Flux Exploration, Growth, and Optical Spectroscopic Properties of Large Size LaBSiO5 and Eu3+-Substituted LaBSiO5 Crystals", 《CRYST. GROWTH DES.》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113322508A (en) * | 2021-05-27 | 2021-08-31 | 福州大学 | Growth method and application of high-temperature phase lanthanum borosilicate crystal |
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