CN102995107A - Technical method for rapidly growing doped Bi4Ge3O13(BGO) crystal - Google Patents
Technical method for rapidly growing doped Bi4Ge3O13(BGO) crystal Download PDFInfo
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- CN102995107A CN102995107A CN2012104597027A CN201210459702A CN102995107A CN 102995107 A CN102995107 A CN 102995107A CN 2012104597027 A CN2012104597027 A CN 2012104597027A CN 201210459702 A CN201210459702 A CN 201210459702A CN 102995107 A CN102995107 A CN 102995107A
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Abstract
A technical method for rapidly growing a doped Bi4Ge3O13(BGO) crystal belongs to the field of an artificial crystalline material. The growing method is a light floating zone method. According to the method, a raw material bar is prepared firstly, during growth, and a melting zone is formed between seed crystals and the raw material bar and can move from bottom to top, thus completing the single crystal growth. As the Bi4Ge3O13(BGO) doped with AI, Mg, Ca and the like has low melt viscosity, the melting zone is easy to collapse, the crystal grows at a faster speed, simultaneously the bar needs to be fed and grows at an inert atmosphere. The crystal growth technique and process of the doped crystal comprise the following mainly characteristics that the growth atmosphere of the doped crystal can be argon, nitrogen and the like, the flow rate of shielding gas is 0.5-0.6L/min, the growth speed of the crystal is in the range from 10.00 to 13.00mm/h, and the speed of bar feeding is in the range from 1.00 to 2.50mm/h.
Description
Technical field
Patent of the present invention belongs to the artificial crystal material field, is a kind of Fast Growth doping Bi
4Ge
3O
12(BGO) technological method of crystal.
Background technology
Bismuth germanium oxide (Bi
4Ge
3O
12, BGO) be a kind of scintillation crystal, water white transparency.The luminosity of BGO and its crystalline structure are closely related.The BGO crystal belongs to isometric system, with natural mineral Bi
4Si
3O
12Eulytite type structure is identical.4 Bi are arranged in each structure cell
4Ge
3O
12Molecule.Bi
3+By 6 GeO
4Tetrahedron surrounds, among the most contiguous oxygen octahedra that is coordinated in distortion.The most contiguous Bi-O bond distance is respectively 0.219 and 0.267nm.Bi
3+Be the full shell ion of a kind of transition group, have 6s
2Electronic configuration, free Bi
3+With the Bi in crystal field
3+The electronic level of ion comprises ground state and excited state.Because Bi
3+The interaction of static and spin orbital in BGO, the separation between ground state and the excited state reduces, and possible absorption jump is
1s
0→
3p
1With
1s
0→
1p
1Bi
3+Have the C3 symmetry,
1s
0-
3p
0The energy level separation diminishes, and this transition is under an embargo.Work as Bi
3+Be in
3p
1With
1p
1During excited state, because
1p
1Attitude enters rapidly 3p by nonradiative transition (thermal equilibrium)
1Attitude causes Bi
3+Emission spectrum be
3p
1→
1s
0
Nineteen seventies, scientist M.J.Weber and R.R.Monchamp as its spectral quality of solid laser working substance research, have found that BGO under light and x-ray irradiation, at room temperature has very strong luminosity to BGO.Have high effective atomic number (namely the height of ray being stopped ability) and other good physicochemical property in conjunction with BGO, and deliquescence not, they have foretold application prospect (the so-called scintillation crystal of BGO as scintillation crystal of new generation, namely under the bump of high energy particle, the kinetic energy of high energy particle can be become luminous energy and send the crystal of fluorescence).When electronics, gamma-rays or the heavy charged particle of certain energy entered BGO, it can send glaucous fluorescence, recorded intensity and the position of fluorescence, just can calculate energy and the position of incident electron, gamma-rays etc.Scintillation crystal has in fields such as nuclear medicine, high energy physics, nuclear technique, space physics and petroleum prospectings widely to be used.In the scintillation crystal various performance parameters, the items such as density, light output and time of response are important.Because incident is high energy particle, the density of crystal is the bigger the better, and so the crystal thickness of demand will diminish, thereby is easy to growth.Because BGO density is large, light is exported, the time of response is all proper, so BGO becomes important scintillation crystal.The BGO crystal is mixed, also can improve its flicker or other performances.
The BGO crystal adopts melt method for growing usually, common are falling crucible method etc.But the growth methods such as falling crucible method waste time and energy, but also need expensive platinum crucible etc.
Summary of the invention
The purpose of this invention is to provide and a kind ofly should use light float-zone method grow doping Bi
4Ge
3O
12(BGO) technological method of crystal, low-cost, efficiently, grow doping Bi rapidly
4Ge
3O
12(BGO) crystal.
Basis of the present invention is: generally speaking, the speed of growth of light float-zone method is than very fast, the exploration, research cycle and the quickening that are conducive to shorten common crystal are difficult to the flow of research of growing crystal, are widely used in the growth of infusibility high-temperature oxide and intermetallic compound crystal.It is a kind ofly novel to explore the fast crystal growth method of developing for new crystal that the light float-zone method can be called.Because the BGO melt viscosity is little, so difficult with light float-zone method growth (doping) BGO crystal.
With light float-zone method growing crystal, at first to make fuel rod, fuel rod is made flow process as shown in Figure 1, and growing apparatus is as shown in Figures 2 and 3.At first form a melting zone during growth between seed crystal and charge bar, then mobile heating source in the situation of seed crystal, charge bar together (reverse direction) rotation makes the melting zone mobile from bottom to top, finishes single crystal growing.In the method, the stability in melting zone is very important.The melting zone is stablized and not slump.Melting zone stable is that the balance of abutment surface tension force and gravity keeps, and surface tension is pointed to the melt direction, make melt zone keep stable and keep profile, and gravity causes the melting zone slump.The material character of melting zone stable condition and growth and equipment etc. are closely related.The float-zone method growing crystal requires material that larger surface tension and less melt density will be arranged.In addition, the advantage of float-zone method is not need crucible, melt only to contact with the solid of itself, and pollution can be down to bottom line.Therefore, suitable those have the material of very strong dissolving power or reactive behavior when melting temperature especially.Because the float-zone method vegetative point is little, there is not again crucible etc. to stop, can install easily camera head additional, so the process of growth of float-zone method is observed easily.
Specific embodiment of the present invention and technical solution are as follows:
Technical scheme one, in argon gas (Ar) atmosphere the BGO crystal of grow doping
BGO crystal with the float-zone method grow doping will carry out under inert atmosphere usually, and growth atmosphere is often selected argon gas.Concrete growthing process parameter is as follows:
＜1〉in argon gas (Ar) atmosphere, grow 1 ~ 2mol%Al(with respect to Bi) the BGO crystal that mixes
Grow under argon gas atmosphere, the shielding gas flow amount is 0.4 ~ 0.6L/min.Speed of growth scope is 10.00 ~ 13.00mm/h, and the delivery speed scope is 1.00 ~ 2.50mm/h.Be 10.50 ~ 11.50mm/h than the tachyauxesis velocity range, the optimal growth velocity range is 10.80 ~ 11.30 mm/h.
＜2〉in argon gas (Ar) atmosphere, grow 1 ~ 2mol%Mg(with respect to Bi) the BGO crystal that mixes
Grow under argon gas atmosphere, the shielding gas flow amount is 0.4 ~ 0.6L/min.Speed of growth scope is 11.00 ~ 13.00mm/h, and the delivery speed scope is 1.00 ~ 2.50mm/h.Be 11.50 ~ 12.50mm/h than the tachyauxesis velocity range, the optimal growth velocity range is 11.80 ~ 12.00 mm/h.
＜3〉in argon gas (Ar) atmosphere, grow 1 ~ 2mol%Ca(with respect to Bi) the BGO crystal that mixes
Grow under argon gas atmosphere, the shielding gas flow amount is 0.4 ~ 0.6L/min.Speed of growth scope is 10.00 ~ 12.50mm/h, and the delivery speed scope is 1.00 ~ 2.50mm/h.Be 10.50 ~ 11.50mm/h than the tachyauxesis velocity range, the optimal growth velocity range is 10.80 ~ 11.20 mm/h.
Technical scheme two, at nitrogen (N
2) the BGO crystal of grow doping in the atmosphere
BGO crystal with the float-zone method grow doping also can carry out under nitrogen atmosphere.Concrete growthing process parameter is as follows:
The shielding gas flow amount is 0.4 ~ 0.6L/min.Speed of growth scope is 10.00 ~ 12.00mm/h, and the delivery speed scope is 1.50 ~ 2.50mm/h.Be 10.50 ~ 11.50mm/h than the tachyauxesis velocity range, the optimal growth velocity range is 10.80 ~ 11.30 mm/h.
Description of drawings
Fig. 1: preparation doping Bi
4Ge
3O
12The process flow sheet of polycrystal raw material rod
Fig. 2: light crystal growth with floating zone method furnace interior
Fig. 3: light crystal growth with floating zone method synoptic diagram
Embodiment
The invention will be further described below by embodiment, but should not limit protection scope of the present invention with this.
Embodiment 1: in argon gas (Ar) atmosphere the growth mix 1mol%Al(with respect to Bi) the BGO crystal
The BGO crystal of 1mol%Al is mixed in growth in argon gas atmosphere, and argon flow amount is 0.5L/h, and the speed of growth is 10.00mm/h, and delivery speed is 2.00mm/h, and the BGO crystal mass of mixing Al that grows out is good.
Embodiment 2: in argon gas (Ar) atmosphere the growth mix 1mol%Mg(with respect to Bi) the BGO crystal
The BGO crystal of 1mol%Mg is mixed in growth in argon gas atmosphere, and argon flow amount is 0.4L/h, and the speed of growth is 12.00mm/h, and delivery speed is 2.00mm/h, and the BGO crystal mass of mixing Mg that grows out is good.
Embodiment 3:In argon gas (Ar) atmosphere the growth mix 1mol%Ca(with respect to Bi) the BGO crystal
The BGO crystal of 1mol%Ca is mixed in growth in argon gas atmosphere, and argon flow amount is 0.6L/h, and the speed of growth is 10.50mm/h, and delivery speed is 2.00mm/h, and the BGO crystal mass of mixing Ca that grows out is good.
Embodiment 4:At nitrogen (N
2) in the atmosphere growth mix 1.5mol%Al(with respect to Bi) the BGO crystal
The BGO crystal of 1.5mol%Al is mixed in growth in nitrogen atmosphere, and nitrogen flow is 0.5L/h, and the speed of growth is 11.00mm/h, and delivery speed is 2.00mm/h, and the BGO crystal mass of mixing Al that grows out is good.
Embodiment 5:At nitrogen (N
2) in the atmosphere growth mix 1.5mol%Mg(with respect to Bi) the BGO crystal
The BGO crystal of 1.5mol%Mg is mixed in growth in nitrogen atmosphere, and nitrogen flow is 0.4L/h, and the speed of growth is 12.00mm/h, and delivery speed is 2.00mm/h, and the BGO crystal mass of mixing Mg that grows out is good.
Embodiment 6:At nitrogen (N
2) in the atmosphere growth mix 1.5mol%Ca(with respect to Bi) the BGO crystal
The BGO crystal of 1.5mol%Ca is mixed in growth in nitrogen atmosphere, and nitrogen flow is 0.5L/h, and the speed of growth is 11.00mm/h, and delivery speed is 2.00mm/h, and the BGO crystal mass of mixing Ca that grows out is good.
Claims (2)
1. Fast Growth doping Bi
4Ge
3O
12(BGO) technological method of crystal is characterized in that using light float-zone method grow doping BGO crystal under inert atmosphere.
2. technological method according to claim 1, its growth atmosphere can be argon gas, nitrogen etc.;
Growth method according to claim 1, its shielding gas flow amount is 0.4 ~ 0.6L/min;
Growth method according to claim 1, its speed of growth scope is 10.00 ~ 13.00mm/h;
Growth method according to claim 1, its delivery speed scope is 1.00 ~ 2.50mm/h.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103526294A (en) * | 2013-10-16 | 2014-01-22 | 中国科学院上海硅酸盐研究所 | Crystalline material with intermediate infrared broadband luminescence property and preparation method thereof |
| CN103541015A (en) * | 2013-10-16 | 2014-01-29 | 中国科学院上海硅酸盐研究所 | Crystalline material with intermediate infrared light-emitting performance, and preparation method thereof |
| CN104562205A (en) * | 2015-01-28 | 2015-04-29 | 中国科学院上海硅酸盐研究所 | Anion-cation co-doped bismuth silicate scintillation crystal and preparation method thereof |
| CN106082330A (en) * | 2016-07-29 | 2016-11-09 | 安徽理工大学 | The Bi that a kind of size is controlled12geO20mesomorphic and synthetic method thereof |
| CN109553132A (en) * | 2018-11-22 | 2019-04-02 | 商丘师范学院 | A kind of bismuth germanium oxide two-dimensional nano piece and preparation method thereof |
-
2012
- 2012-11-15 CN CN2012104597027A patent/CN102995107A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| PINGSHENG YU， ET AL.: "Crystal growth and spectroscopic properties of MoO3 and WO3 doped Bi4Ge3O12 by optical floating zone method", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103526294A (en) * | 2013-10-16 | 2014-01-22 | 中国科学院上海硅酸盐研究所 | Crystalline material with intermediate infrared broadband luminescence property and preparation method thereof |
| CN103541015A (en) * | 2013-10-16 | 2014-01-29 | 中国科学院上海硅酸盐研究所 | Crystalline material with intermediate infrared light-emitting performance, and preparation method thereof |
| CN104562205A (en) * | 2015-01-28 | 2015-04-29 | 中国科学院上海硅酸盐研究所 | Anion-cation co-doped bismuth silicate scintillation crystal and preparation method thereof |
| CN106082330A (en) * | 2016-07-29 | 2016-11-09 | 安徽理工大学 | The Bi that a kind of size is controlled12geO20mesomorphic and synthetic method thereof |
| CN106082330B (en) * | 2016-07-29 | 2017-06-16 | 安徽理工大学 | A kind of controllable Bi of size12GeO20Mesomorphic and its synthetic method |
| CN109553132A (en) * | 2018-11-22 | 2019-04-02 | 商丘师范学院 | A kind of bismuth germanium oxide two-dimensional nano piece and preparation method thereof |
| CN109553132B (en) * | 2018-11-22 | 2021-03-30 | 商丘师范学院 | Bismuth germanate two-dimensional nanosheet and preparation method thereof |
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Application publication date: 20130327 |