CN116200829B - Preparation method and application of high-density, fast-decay time scintillation crystal Bi2W2O9 - Google Patents
Preparation method and application of high-density, fast-decay time scintillation crystal Bi2W2O9 Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 132
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
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- 238000001514 detection method Methods 0.000 claims abstract description 7
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims description 28
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 9
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- 229910052697 platinum Inorganic materials 0.000 claims description 7
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- 229910021642 ultra pure water Inorganic materials 0.000 claims description 2
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- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims 3
- 239000002994 raw material Substances 0.000 abstract description 4
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- 238000002109 crystal growth method Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 11
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
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- 229910014323 Lanthanum(III) bromide Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
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- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
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- XKUYOJZZLGFZTC-UHFFFAOYSA-K lanthanum(iii) bromide Chemical compound Br[La](Br)Br XKUYOJZZLGFZTC-UHFFFAOYSA-K 0.000 description 1
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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
- C30B29/16—Oxides
- C30B29/22—Complex oxides
- C30B29/32—Titanates; Germanates; Molybdates; Tungstates
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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
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
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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
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
- C30B11/14—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method characterised by the seed, e.g. its crystallographic orientation
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Abstract
本发明公开一种高密度、快衰减时间的闪烁晶体Bi2W2O9的制备方法和应用，属于闪烁晶体材料技术领域。本发明将元素周期表中最重的稳定元素Bi与重元素W与低维Aurivillius型晶体结构进行有机结合，制备得到一种高密度、快衰减时间的闪烁晶体材料。本发明制备得到的Bi2W2O9晶体的衰减时间短，最小衰减时间为1.40ns，慢分量为41.63ns，是一种超快衰减的闪烁体。本发明合成与晶体生长方法，所使用的原料均可以在市场购得，价格便宜，不含有毒有害元素，便于进行规模化生产，可应用于高能射线、高能粒子的探测和防护等技术领域。
The present invention discloses a preparation method and application of a scintillating crystal Bi 2 W 2 O 9 with high density and fast decay time, belonging to the technical field of scintillating crystal materials. The present invention organically combines Bi, the heaviest stable element in the periodic table, with heavy element W and a low-dimensional Aurivillius-type crystal structure to prepare a scintillating crystal material with high density and fast decay time. The Bi 2 W 2 O 9 crystal prepared by the present invention has a short decay time, a minimum decay time of 1.40ns, and a slow component of 41.63ns, and is an ultrafast decaying scintillator. The synthesis and crystal growth method of the present invention uses raw materials that can be purchased on the market, are cheap, do not contain toxic and harmful elements, are easy to carry out large-scale production, and can be applied to the technical fields of detection and protection of high-energy rays and high-energy particles.
Description
Technical Field
The invention belongs to the technical field of scintillation crystal materials, and particularly relates to a preparation method and application of a scintillation crystal Bi 2W2O9 with high density and fast decay time.
Background
The detection and protection of high-energy rays (X-rays, gamma-rays and the like) and particles (neutrons, beta particles and the like) have important significance in modern society, and the significance is rapidly rising along with the rapid development of nuclear medicine detection and diagnosis and treatment, high-energy physical experiments, freight security supervision and other technologies.
The scintillation crystal refers to a functional crystal material capable of converting energy of high-energy rays or high-energy particles into ultraviolet or visible light band fluorescent pulses. Since NaI: tl was found as a scintillation crystal and put into practical use, researchers have successively found and proposed many excellent scintillation crystals. Currently, practical scintillation crystals are largely divided into two major classes, oxide crystals and halide crystals. The oxide crystal is represented by Bi4Ge3O12(BGO)、PbWO4(PWO)、CdWO4(CWO)、Lu2-xYxSiO5:Ce(LYSO:Ce) and the like, and has the advantages of high density, good stability, strong radiation resistance and the like. The halide crystal is represented by NaI: tl, srI 2:Eu、LaBr3: ce, etc., and has the advantages of high light yield, short decay time, high energy resolution, etc. In recent years, the continuous development of the field of high-energy detection has put new and higher demands on the performance of scintillation crystals. The three most important indicators measuring the performance of scintillation crystals are light yield, energy resolution and fluorescence decay/response time, respectively, and scintillation crystals with high light yield, high energy resolution of less than 3.0% and picosecond order time resolution are the directions of future development.
As mentioned above, oxide crystals have a higher density and a higher radiation resistance than halide crystals, but the decay time is generally above 100ns, even in the order of microseconds and milliseconds, for example, BGO crystals have a decay time of about 317ns, CWO has a decay time as high as 12.7 μs, and LYSO: ce crystals have a decay time of less than 100ns, but also up to about 42 ns. PWO crystals (6 ns), YAG: yb crystals (2.5 ns) and YAP: yb crystals (1.5 ns) with shorter decay time, but the light yield of the PWO crystals is generally extremely low, and the existence of Pb element in the crystals can cause serious threat to the environment. Therefore, how to effectively shorten the decay time of oxide crystals and improve the crystal quality is a technical problem to be solved.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a preparation method and application of a scintillation crystal Bi 2W2O9 with high density and fast decay time, the room temperature density of the obtained crystal is as high as 8.84g/cm 3, the minimum decay time is about 1.40ns, and the use requirements of various fields can be met.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
the preparation method of the scintillation crystal Bi 2W2O9 with high density and fast decay time comprises the following preparation steps:
(1) The synthesis and seed crystal preparation of Bi 2W2O9, namely, fully mixing Li 2CO3 and H 3BO3 uniformly, pressing into blocks on a tablet press, placing in a crucible, slowly heating to 390-410 ℃ for 24 hours at constant temperature, grinding after cooling, re-pressing into blocks, heating at 390-410 ℃ for 24 hours, cooling after cooling to obtain Li 2B4O7 pre-sintered material, placing Bi 2O3、WO3 and Li 2B4O7 pre-sintered material in the crucible, heating to 850-950 ℃ for 10 hours at constant temperature, cooling to 690-710 ℃ in 24 hours, pouring into a ceramic disc, cooling to room temperature to obtain a cooling material, carrying out basic crushing treatment on the cooling material, carrying out acid washing with dilute hydrochloric acid, filtering and drying to obtain Bi 2W2O9 micro-crystal grains, namely Bi 2W2O9, wherein the small crystal grains with complete morphology and high transparency can be used as seed crystals;
(2) Determining saturation temperature, namely fully and uniformly mixing Li 2CO3 and H 3BO3, pressing the mixture into blocks on a tablet press, slowly heating the blocks in a crucible to 390-410 ℃ for 24 hours at constant temperature, grinding the blocks after cooling, re-pressing the blocks into blocks after heating the blocks at 390-410 ℃ for 24 hours, cooling the blocks after cooling, repeating the grinding, pressing and sintering processes for 2-5 times to obtain Li 2B4O7 presintered material, mixing Bi 2O3、WO3 and Li 2B4O7 presintered material, placing the mixture in the crucible, keeping the temperature above the crucible by an alumina heat-insulating fiber cylinder, heating the mixture to 850-950 ℃ for 24-48 hours, cooling the mixture to 825-835 ℃ to obtain mixed solution, slowly reducing the Bi 2W2O9 seed crystal obtained in the fixing step (1) to a position 2cm above the liquid level of the mixed solution, staying for 10 minutes, slowly reducing the Bi 2W2O9 seed crystal to lightly touch the liquid level, lifting the seed crystal after 2 hours, repeatedly adjusting the temperature, testing and observing the surface of the seed crystal until the crystallization temperature appears on the surface, namely the saturated temperature T, and controlling deviation not to exceed 2 ℃;
(3) The method comprises the steps of (1) heating the mixed solution obtained in the step (2) to 850-950 ℃ again, keeping the temperature for 10 hours to thoroughly dissolve Bi 2W2O9 mixed crystals possibly generated, then cooling to 2 ℃ above the saturation temperature T, slowly putting Bi 2W2O9 seed crystals into the mixed solution to make the mixed solution lightly touch the liquid surface, cooling to the saturation temperature T for 2 hours, then cooling to 20 ℃ below the saturation temperature T at a rate of 0.01-0.05 ℃ per hour for crystal growth, lifting the crystals from the liquid surface after the growth is finished, cooling to room temperature for 48 hours to obtain Bi 2W2O9 crystals, and obtaining Bi 2W2O9 crystals which can be used for cutting seed crystals required in the preparation step (2).
Further, the molar ratio of Li 2CO3、H3BO3、Bi2O3、WO3 in step (1) is 1:4:1:3.
Further, the crucible in the step (1) and the step (2) is a platinum crucible.
Further, the molar ratio of Li 2CO3、H3BO3、Bi2O3、WO3 in step (2) is 1:4:1:3, and the molar amount of Li 2CO3、H3BO3、Bi2O3、WO3 in step (2) can be determined according to the actual desired target crystal size.
Further, the Bi 2W2O9 seed crystal obtained in the step (1) is fixed by a platinum wire in the step (2).
Further, the crystal growth period in the step (3) is 10-40 days, and the crystal rotation speed is controlled to be 10-40r/min.
Furthermore, the rotation speed of the crystal in the step (3) is controlled to be 15-25r/min.
The preparation method of the scintillation crystal Bi 2W2O9 with high density and fast decay time is applied, and the obtained crystal is used in the technical fields of detection and protection of high-energy rays and high-energy particles.
The invention organically combines the heaviest stable element Bi and the heaviest element W in the periodic table with the low-dimensional Aurivillius crystal structure by taking the oxide crystal with high density, high light yield and fast decay time as the main research direction, and provides Bi 2W2O9 as a new generation of high-density and fast decay time scintillation crystal material. In the Aurivillius structure, the [ Bi 2O2]2+ fluorite structure layer and the [ W 2O7]2- perovskite structure layer are effectively stacked in a three-dimensional space, so that the Bi and the W can effectively occupy the space to a greater extent, and the large crystal density and the high ray cut-off capability are obtained. Meanwhile, the low-dimensional layered structure enables Bi 2W2O9 crystals to have strong dielectric confinement and quantum confinement effects, exciton combination energy is high, non-radiative recombination probability is reduced, attenuation time is effectively reduced, and further the novel scintillation crystal material with high density and fast attenuation time is obtained.
The Bi 2W2O9 crystal provided by the invention can be used as a high-density and fast-scintillation time scintillation crystal, is used for detecting high-energy rays and high-energy particles, and can be used for but not limited to devices such as TOF-PET (time of flight) of positron computer tomography equipment, energy measuring devices of high-energy physical experiments, environmental radiation level monitors, traffic site security detectors of airports, stations and the like.
The Bi 2W2O9 crystal prepared by the method can be used as an intrinsic luminescent scintillator, and meanwhile, rare earth ions such as Ce 3+、Yb3+ can be doped during crystal growth, so that the energy level structure is optimized, the light yield is improved, and the Bi 2W2O9 crystal can be used as an extrinsic luminescent scintillator.
Bi 2W2O9 prepared by the method can be prepared into a composite material with glass, resin, rubber, fiber and the like, and is used for protecting high-energy rays and high-energy particles, for example, in the application fields of human body radiation shielding clothing, gamma ray shielding and the like.
Meanwhile, the invention provides a Bi 2W2O9 seed crystal, namely a synthesis method of Bi 2W2O9 particles or powder, which can obtain Bi 2W2O9 particles and powder with purity of 99.9% or more, and is used in the fields of ray shielding and protection but not limited to.
The invention provides a growth method of Bi 2W2O9 crystal, which can obtain Bi 2W2O9 crystal with centimeter level and larger size, has good crystal transparency and no macroscopic crack, and can meet the requirements of characterization and application of scintillation crystal.
Advantageous effects
(1) The Bi2W2O9 crystal prepared by the method has the room temperature density of 8.84g/cm < 3 >, the effective atomic number of 76, which is higher than PWO crystal, has strong blocking ability to high-energy rays and particles such as X-rays, gamma-rays and the like, and can be used as a ray shielding and protecting material;
(2) The Bi2W2O9 crystal prepared by the method has two fluorescence emission peaks in the optical transmission range of 400-500nm, has stronger fluorescence emission under the excitation of X rays, and has small self-absorption, and the emission peak is positioned in the optical transmission range of the crystal;
(3) The decay time of the Bi2W2O9 crystal prepared by the method is about 1.40ns, the slow component is 41.63ns, but the slow component only has 2% of decay time contribution, so that the crystal is an ultrafast decaying scintillator;
(4) According to the synthesis method of Bi2W2O9, the used raw materials can be purchased in the market, the price is low, toxic and harmful elements are not contained, and the large-scale production is convenient;
(5) The synthesis method of Bi2W2O9 provided by the invention has the advantages that the required conditions are easy to realize, the operation is simple, the Bi2W2O9 crystal with the centimeter-level size can be obtained, the crystal has high transparency, and the orientation, the scintillation performance test and the scintillation device design application of the crystal can be carried out.
Drawings
FIG. 1 is a graph showing the comparison of the Bi 2W2O9 seed crystal X-ray diffraction pattern synthesized in example 1 of the present invention with a theoretical fit pattern;
FIG. 2 is a diagram of Bi 2W2O9 cm single crystal grown in example 2 of the present invention;
FIG. 3 is an emission spectrum of Bi 2W2O9 crystals of the present invention;
FIG. 4 is a graph showing fluorescence decay of Bi 2W2O9 crystals of the present invention;
Fig. 5 is a schematic diagram of the basic structure of a scintillation device based on Bi 2W2O9 crystals.
Detailed Description
The technical scheme of the present invention is further described below with reference to specific examples, but is not limited thereto.
Example 1
Bi 2O3、WO3 and Li 2CO3、H3BO3 were used as raw materials. 0.1mol of Li 2CO3 and 0.4mol of H 3BO3 are thoroughly and uniformly mixed, pressed into blocks on a tablet press, and placed in a platinum crucible and slowly heated to 400 ℃ for 24 hours. Grinding after cooling, re-pressing into blocks, heating at 400 ℃ for 24 hours, cooling and obtaining the Li 2B4O7 presintered material. After 0.1mol of Bi 2O3、0.3molWO3 and Li 2B4O7 pre-sintered material are fully mixed, the mixture is placed in a platinum crucible, heated to 900 ℃ and kept at constant temperature for 10 hours, cooled to 700 ℃ in 24 hours, and then poured into a ceramic disc for rapid cooling. And (3) carrying out basic crushing treatment on the cooling material, carrying out acid washing by adopting dilute hydrochloric acid, further washing by adopting ultrapure water, filtering and drying to obtain the micro grains of Bi 2W2O9. The obtained micro Bi 2W2O9 crystal grains are ground and then subjected to powder X-ray diffraction test, the diffraction pattern of the micro Bi 2W2O9 crystal grains is well matched with the theoretical diffraction pattern fitted based on the Bi 2W2O9 crystal structure, as shown in figure 1, and Bi 2W2O9 is obtained by adopting the method of the embodiment 1.
Example 2
Bi 2O3、WO3 and Li 2CO3、H3BO3 were used as raw materials. 1mol of Li 2CO3 and 4mol of H 3BO3 are thoroughly and uniformly mixed, pressed into blocks on a tablet press, and placed in a platinum crucible and slowly heated to 400 ℃ for 24 hours. Grinding after cooling, re-pressing into blocks, heating at 400 ℃ for 24 hours, and cooling. Repeating grinding, tabletting and sintering at 400 ℃ for 3 times to obtain the Li 2B4O7 pre-sintered material. Fully mixing 1mol of Bi 2O3、3mol WO3 with the Li 2B4O7 presintered material, placing the mixture in a platinum crucible, performing heat preservation on the upper part of the platinum crucible by using an alumina heat preservation fiber cylinder, heating the mixture to 850 ℃ for 24 hours, and heating the mixture to 900 ℃ for 10 hours. Cooling to 830 ℃, fixing Bi 2W2O9 seed crystal by a platinum wire, slowly lowering the temperature to 2cm above the liquid level, staying for 10 minutes, slowly lowering to enable the seed crystal to lightly touch the liquid level, lifting the seed crystal after 2 hours, and observing the dissolution or growth of the surface of the seed crystal. In this way, the saturation temperature T is precisely determined, the deviation not exceeding 2 ℃. After the saturation temperature T was determined, the solution was again kept at 900 ℃ for 10 hours to thoroughly dissolve Bi 2W2O9 hetero-crystals that may be produced. Then cooling to 2 ℃ above the saturation temperature T, and slowly adding Bi 2W2O9 seed crystal to make the Bi 2W2O9 seed crystal lightly touch the liquid surface. Cooling to saturation temperature T for 2h, and then cooling to about 20 ℃ below saturation temperature at a rate of 0.01-0.05 ℃ per h. And (3) lifting the crystal off the liquid level, and cooling to room temperature for 48 hours to obtain Bi 2W2O9 single crystals, as shown in figure 2.
Example 3
The fluorescence emitted by the scintillation crystal under the excitation of high-energy rays/particles should be in the sensitive interval of a photomultiplier tube PMT or a silicon photomultiplier SiPM. Based on the Bi 2W2O9 single crystal grown in example 2, the fluorescence emission spectrum of the Bi 2W2O9 crystal was measured using a steady state/transient fluorescence spectrometer. As shown in figure 3, bi 2W2O9 has a wider emission band between 400 and 600nm, and the emission band is just positioned in the sensitive interval of PMT and SiPM, thereby meeting the requirements of the luminescent band of the scintillation crystal
Example 4
The decay time of the luminescence of the scintillation crystal under the excitation of high-energy rays/particles is an important parameter for ultra-fast scintillation crystals. Based on the Bi 2W2O9 single crystal obtained by growth in example 2, the fluorescence decay curve of the Bi 2W2O9 crystal was measured. As shown in FIG. 4, bi 2W2O9 exhibits a three exponential decay characteristic, a fast component of 1.40ns contributing 78% to the decay lifetime of fluorescence, another fast component of 5.22ns contributing 20% to the decay time of fluorescence, and a slow component of 41.63ns contributing only 2% to the decay lifetime of fluorescence. Therefore, bi 2W2O9 exhibits extremely fast fluorescence decay characteristics as an ultrafast scintillator.
Example 5
Similarly, based on the Bi 2W2O9 crystal grown in example 2, a 10mm by 5mm sample was cut, end-face polished, side roughened. One end face is coupled with a PMT by silicone grease. The crystal and the PMT are sealed and in a camera bellows, the other end face of the crystal is irradiated by a radioactive source, bi 2W2O9 is subjected to scintillation and luminescence, and then signals are processed by the PMT, a rear-end electronic system and the like, so that information carried in high-energy rays can be analyzed and processed. The basic structure of the scintillation detection device is shown in fig. 5.
It should be noted that the above-mentioned embodiments are merely some, but not all embodiments of the preferred mode of carrying out the invention. It is evident that all other embodiments obtained by a person skilled in the art without making any inventive effort, based on the above-described embodiments of the invention, shall fall within the scope of protection of the invention.
Claims (6)
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| CN102559180A (en) * | 2011-05-05 | 2012-07-11 | 中国科学院福建物质结构研究所 | Photoluminescent crystal material bismuth-europium tungstate and preparation method for same |
| CN114561704A (en) * | 2022-01-29 | 2022-05-31 | 临沂大学 | Flux growth method and application of large-size bismuth tungstate crystal |
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| CN111717936A (en) * | 2020-08-07 | 2020-09-29 | 上海应用技术大学 | A method for preparing WO3 nanosheets by microwave intercalation |
| CN112522786B (en) * | 2020-11-10 | 2022-02-01 | 临沂大学 | Self-excited Raman composite functional crystal bismuth tungsten molybdate and crystal growth method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102559180A (en) * | 2011-05-05 | 2012-07-11 | 中国科学院福建物质结构研究所 | Photoluminescent crystal material bismuth-europium tungstate and preparation method for same |
| CN114561704A (en) * | 2022-01-29 | 2022-05-31 | 临沂大学 | Flux growth method and application of large-size bismuth tungstate crystal |
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| Title |
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| Insights into the polymorphism of Bi2W2O9: single crystal growth and a complete survey of the variable-temperature thermal and dielectric properties;Xiangxin Tian et al.;《CrystEngComm》;20180322;参见正文第2页右栏晶体生长部分 * |
| Xiangxin Tian et al..Insights into the polymorphism of Bi2W2O9: single crystal growth and a complete survey of the variable-temperature thermal and dielectric properties.《CrystEngComm》.2018,参见正文第2页右栏晶体生长部分. * |
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