CN111470528A - Tin-containing semiconductor material and preparation method thereof - Google Patents
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 61
- 239000000463 material Substances 0.000 title claims abstract description 47
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 claims abstract description 26
- 239000013078 crystal Substances 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 12
- ZSUXOVNWDZTCFN-UHFFFAOYSA-L Tin(II) bromide Inorganic materials Br[Sn]Br ZSUXOVNWDZTCFN-UHFFFAOYSA-L 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 229910052738 indium Inorganic materials 0.000 claims abstract description 4
- 239000002178 crystalline material Substances 0.000 claims abstract description 3
- 229910052709 silver Inorganic materials 0.000 claims abstract description 3
- 239000004332 silver Substances 0.000 claims abstract description 3
- 239000011261 inert gas Substances 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 18
- KLRHPHDUDFIRKB-UHFFFAOYSA-M indium(i) bromide Chemical compound [Br-].[In+] KLRHPHDUDFIRKB-UHFFFAOYSA-M 0.000 claims description 6
- 150000003606 tin compounds Chemical class 0.000 claims description 6
- 150000002472 indium compounds Chemical class 0.000 claims description 4
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 claims description 4
- 229940100890 silver compound Drugs 0.000 claims description 4
- 150000003379 silver compounds Chemical class 0.000 claims description 4
- 229910021623 Tin(IV) bromide Inorganic materials 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 230000007547 defect Effects 0.000 abstract description 8
- 239000000969 carrier Substances 0.000 abstract description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 239000003708 ampul Substances 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 230000005355 Hall effect Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- JKNHZOAONLKYQL-UHFFFAOYSA-K Indium(III) bromide Inorganic materials Br[In](Br)Br JKNHZOAONLKYQL-UHFFFAOYSA-K 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 238000001894 space-charge-limited current method Methods 0.000 description 3
- 238000000137 annealing Methods 0.000 description 2
- -1 cesium ions Chemical class 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- PNKUSGQVOMIXLU-UHFFFAOYSA-N Formamidine Chemical compound NC=N PNKUSGQVOMIXLU-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 229910001502 inorganic halide Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/006—Compounds containing, besides tin, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/76—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by a space-group or by other symmetry indications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention discloses a tin-containing semiconductor material and a preparation method thereof. The semiconductor material is CsSnBr3In the preparation process, crystals with different carrier concentrations are grown by adding metal simple substances or metal compounds for doping. The preparation method comprises the following steps: reacting CsBr and SnBr2Mixing with metal simple substance or metal compound, heating under the protection of inert gas to react, and slowly cooling to obtain CsSnBr with different carrier concentrations3A semiconductor crystalline material. CsSnBr with simple substance tin added in preparation process3Compared with the semiconductor without the carrier, the carrier concentration of the semiconductor is reduced by 1 order of magnitude, and the defect state density is obviously reduced. Indium doped CsSnBr3The semiconductor has a structure 1010cm‑3A concentration of carriers proximate to the intrinsic semiconductor; silver doped CsSnBr3The semiconductor has a structure 1019cm‑3The concentration of p-type carriers becomes degenerate semiconductor.
Description
Technical Field
The invention relates to a novel tin-containing semiconductor material, which is prepared by changing CsSnBr3The preparation conditions of perovskite materials and doping elements are adopted to obtain a series of semiconductor materials with different carrier concentrations, and the method belongs to the technical field of new materials.
Background
In recent years, halide perovskite materials have been receiving attention due to their excellent semiconductor properties and increasing photoelectric conversion performance. ABX in halide perovskite materials3In the structure, the A-bit element is generally a large ion halfAmmonium, formamidine or cesium ions, the B site is generally a divalent cation of lead, tin and germanium, and X is a halide anion. The B site cations and six halogen anions form common-vertex octahedrons, and the A site cations are positioned in gaps among the octahedrons to form a perovskite structure.
To investigate the properties of halide perovskite materials, spin coating and vapor deposition are currently commonly used to produce thin films. However, the obtained microcrystalline thin film material has more pores, grain boundary inclusions and other defects, which not only hinders the transmission of current carriers in the perovskite material, but also enables the perovskite to be rapidly degraded in the environment. In contrast, a single crystalline bulk perovskite material may have higher carrier mobility, longer carrier diffusion length, and also higher stability to moisture and oxygen in the environment. Halide perovskites containing organic cations are typically grown from solution, whereas all-inorganic halide perovskites do not decompose when melted, and are more suitable for growing single crystals using the bridgman method. For example, CsPbBr3Large-size high-quality single crystals have been obtained by the bridgman method (adv. optical mater.2017,5,1700157; nat. commu.2018, 9,1609; j. phys. chem. L ett.2018,9,5040) but lead-containing perovskite materials are liable to pollute the environment and harm the health of human bodies, and thus are prohibited by the RoHS standard and are greatly limited in the practical application process, and a new class of perovskite materials can be obtained by using tin instead of lead as a B-site cation.
CsSnBr3Exists stably in a cubic phase at room temperature, has good thermal stability, can be passivated by air, and has a band gap size suitable for preparing a photoelectric conversion device (Angew. chem. int. Ed.2018,57,13154). It should be noted that, unlike the lead element, the tin element is also stabilized with Sn2+And Sn4+Two valence states, which make tin-containing perovskite materials susceptible to contain Sn4 +Sn vacancy defects and corresponding p-type doping are produced (j.am. chem. soc.2012,134, 8579; j.phys. chem.c.2018,122, 13926). Doping the semiconductor can increase the conductivity of the material, but will accelerate the recombination of electrons and holes. Therefore, it is currently one of ordinary skill to adjust the doping state of tin-containing perovskite materials according to different application directionsAn important research direction. There are reports (adv. mater.2014,26,7122) of growing CsSnI3Adding 20% SnF in mol ratio when crystallizing2Can have a carrier concentration of 1019cm-3Reduced to 1017cm-3However, such a high addition ratio exceeds the normal doping concentration range, and the adjustment effect on the carrier concentration is not significant enough.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: a tin-containing semiconductor material and a preparation method thereof are provided, and the carrier concentration in a semiconductor is regulated and controlled by changing preparation and doping conditions.
In order to solve the problems, the invention provides a tin-containing semiconductor material which is characterized in that the tin-containing semiconductor material is CsSnBr3In the preparation process, crystals with different carrier concentrations are grown by adding metal simple substances or metal compounds for doping.
Preferably, the raw material of the tin-containing semiconductor material comprises CsBr and SnBr2And a simple metal or a metal compound.
More preferably, the simple metal or the metal compound is any one or more of a simple tin or a tetravalent tin compound, an indium simple substance or an indium compound, and a silver simple substance or a silver compound.
Further, the tetravalent tin compound is SnBr4Or Cs2SnBr6。
Further, the indium compound is InBr.
Further, the silver compound is AgBr.
Further, the mass of the tin simple substance is not less than CsBr and SnBr2The sum of the masses of (a) and (b).
Furthermore, the mole number of the tetravalent tin compound, other metal simple substance or metal compound is not more than SnBr25% of the mole number.
The invention also provides a preparation method of the tin-containing semiconductor material, which is characterized in that CsBr and SnBr are added2Mixing with metal simple substance or metal compound in inert gasHeating for reaction under the protection of a body, and slowly cooling to obtain CsSnBr with different carrier concentrations3A semiconductor crystalline material.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention is realized by adding CsSnBr3In element is doped In the semiconductor material, so that the carrier concentration of the semiconductor material is reduced by 6 orders of magnitude and is close to the level of an intrinsic semiconductor.
2. The invention is realized by adding CsSnBr3Simple substance tin is added in the preparation process of the semiconductor material, so that the carrier concentration of the semiconductor material is reduced by 1 order of magnitude, and the defect state density is obviously reduced.
3. The invention is realized by adding CsSnBr3Ag element is doped in the semiconductor material, so that the carrier concentration of the semiconductor material is increased by 3 orders of magnitude, and the level of a degenerate semiconductor is reached.
4. The invention provides at 1010To 1019cm-3A method for controlling the carrier concentration of tin-containing semiconductor materials within a range.
5. The doped tin-containing semiconductor material of the present invention does not contain the toxic elements lead or cadmium.
6. The preparation method of the doped tin-containing semiconductor material is simple, does not produce waste liquid or byproducts, and is suitable for large-scale production.
Drawings
FIG. 1 is a CsSnBr treated with metallic tin3A crystal photograph;
FIG. 2 is a CsSnBr treated with metallic tin3X-ray diffraction patterns of crystals and powders;
FIG. 3 is CsSnBr doped with indium3Semiconductor device structure and space charge limited current (SC L C) test results;
FIG. 4 is CsSnBr doped with InBr3A crystal photograph;
FIG. 5 is a CsSnBr doped with AgBr3Powder X-ray diffraction pattern;
FIG. 6 is an undoped CsSnBr3Semiconductor device structure and space charge limited current (SC L C) test results.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.
The starting material CsBr referred to in examples 1 to 4 and comparative example 1 was purified from a commercial reagent, SnBr, according to the method of J.Phys.chem. L ett.2019,10,36992Synthesized and purified according to the method of angelw.chem.int.ed.2018, 57,13154.
Example 1: metallic tin treated CsSnBr3Semiconductor device and method for manufacturing the same
A tin-containing semiconductor material is prepared by the following steps: in a nitrogen atmosphere, 10.6g (50.0mmol) CsBr and 13.9g (50.0mmol) SnBr were weighed2The solid, after mixing well and grinding well, was filled into a glass ampoule containing about 1/3 atmospheres of nitrogen gas along with 40 grams of tin shot and sealed by melting. The neck of the ampoule was placed vertically downward for bridgeman crystal growth under the following conditions: the heating rate is 5 ℃ and min-1The heat preservation temperature is 490 ℃, the heat preservation time is 3 hours, and the seed crystal rod descending speed is 2 mm.h-1Annealing at 280 deg.c for 3 hr, and final cooling to room temperature. The resulting sample is shown in FIG. 1, and the crystal surface is bright and free of cracks and significant macro-inclusions.
The crystal was cut, ground and polished in a nitrogen atmosphere into a circular thin plate having a diameter of about 13mm and a thickness of 0.95mm, and its X-ray diffraction pattern is shown in FIG. 2(a) and is represented by [100 ]]And (4) crystal orientation. The X-ray diffraction pattern of the powder-ground part of the crystals is shown in fig. 2(b), and the index results of the diffraction pattern are: cubic system, Pm-3m space group, cell parameter of
This result indicates that the product of this example is CsSnBr3A single crystal phase of (a).
In CsSnBr3Four gold electrodes are evaporated on the edge of the wafer, and the Hall effect of the wafer is measured by Van der Pauw method, so that the result shows that the sample contains p-type carriers with the concentration of 6.2 × 1015cm-3Carrier mobility of 67cm2·V-1·s-1. This result demonstrates that metallic tin treatment renders CsSnBr comparable to comparative example 13The defect state density in the semiconductor is reducedAn order of magnitude.
Example 2: CsSnBr doped with In3Semiconductor device and method for manufacturing the same
A tin-containing semiconductor material is prepared by the following steps: in a nitrogen atmosphere, 10.6g (50.0mmol) CsBr and 13.9g (50.0mmol) SnBr were weighed2The solid, after mixing well and grinding well, was charged into a glass ampoule containing about 1/3 atmospheres of nitrogen gas along with 0.057g (0.50mmol) of indium pellets and melt sealed. The ampoule was heated at 460 ℃ for 8 hours with rolling motion to give a dark liquid which, after cooling to room temperature, gave a black solid.
Taking part of black solid, grinding and polishing to obtain a size of about 1 × 1cm in a nitrogen environment2Square thin sheet with thickness of 0.82mm, gold electrodes were evaporated at four corners of the thin sheet, and the Hall effect was measured by Van der Pauw method, which indicated that the sample contained p-type carriers with a concentration of 4.1 × 1010cm-3Carrier mobility of 61cm2·V-1·s-1。
Gold-plated electrodes are evaporated on the upper and lower surfaces of another crystal sheet with a thickness of 1.02mm, the device structure and the current-voltage characteristic curve are shown in FIG. 3, and the defect filling limit voltage V isTFL16 V. analysis of the results according to the standard space charge limited current model gave a defect state density in the sample of 6.7 × 1010cm-3. The above results all illustrate the indium-doped CsSnBr3Defects in the semiconductor have been significantly eliminated.
Example 3: CsSnBr doped with InBr3Semiconductor device and method for manufacturing the same
A tin-containing semiconductor material is prepared by the following steps: in a nitrogen atmosphere, 10.6g (50.0mmol) of CsBr and 13.9g (50.0mmol) of SnBr were weighed2And 0.10g (0.50mmol) of InBr as a solid, mixed well and ground thoroughly, then charged into a glass tube with a conical bottom containing about 1/3 atmospheres of nitrogen and sealed by melting. The growth conditions of the Bridgman crystal are as follows: the heating rate is 5 ℃ and min-1The heat preservation temperature is 490 ℃, the heat preservation time is 3 hours, and the seed crystal rod descending speed is 2 mm.h-1Annealing at 280 deg.c for 3 hr, and final cooling to room temperature. The resulting sample is bright and crack-free, with no obvious macro-inclusions, as shown in fig. 4.
The crystal was cut, ground and polished in a nitrogen atmosphere into a circular sheet having a diameter of about 13mm and a thickness of 2.30mm, four gold electrodes were deposited on the edge of the sheet, and the Hall effect was measured by the Van der Pauw method, which revealed that the sample contained a p-type carrier concentration of 3.0 × 1010cm-3Carrier mobility of 74cm2·V-1·s-1. This result demonstrates that CsSnBr doped with InBr3Defects in the semiconductor have been significantly eliminated.
Example 4: CsSnBr doped with AgBr3Semiconductor device and method for manufacturing the same
A tin-containing semiconductor material is prepared by the following steps: in a nitrogen atmosphere, 4.17g (19.6mmol) CsBr and 5.40g (19.4mmol) SnBr were weighed2、0.17g(0.20mmol)Cs2SnBr6And 0.075g (0.40mmol) of AgBr as a solid, mixed well and ground thoroughly, then charged to a glass ampoule containing about 1/3 atmospheres of nitrogen and sealed by melting. The ampoule was heated at 460 ℃ for 12 hours with rolling motion to give a dark liquid which, after cooling to room temperature, gave a black solid.
In a nitrogen atmosphere, a part of the black solid was ground into powder, and the X-ray diffraction pattern thereof is shown in fig. 5. The index result of the diffraction pattern is: cubic system, Pm-3m space group, cell parameter of
This result indicates that the product of this example is CsSnBr3The AgBr did not phase separate.
Taking part of black solid, grinding and polishing to obtain a size of about 5 × 4mm2Square thin sheet with thickness of 1.02mm, gold electrodes were evaporated at four corners of the thin sheet, and the Hall effect was measured by Van der Pauw method, which indicated that the sample contained p-type carriers with a concentration of 1.5 × 1019cm-3The carrier mobility is 20cm2·V-1·s-1. This result illustrates AgBr-doped CsSnBr3The carrier concentration within the semiconductor is significantly increased, becoming a degenerately doped semiconductor.
Comparative example 1: undoped CsSnBr3Semiconductor device and method for manufacturing the same
In a nitrogen atmosphere, 10.6g (50.0mmol) CsBr and 13.9g (50.0mmol) SnBr were weighed2The solids, after mixing well and grinding thoroughly, are placed in a glass ampoule containing nitrogen at about 1/3 atmospheres and sealed by melting. The ampoule was heated at 460 ℃ for 8 hours to give a clear wine-red liquid which, after cooling to room temperature, gave a black solid.
Taking part of black solid, grinding and polishing to obtain a size of about 1 × 1cm in a nitrogen environment2Square thin sheet with thickness of 1.32mm, gold electrodes were evaporated on four corners of the thin sheet, and the Hall effect was measured by Van der Pauw method, which indicated that the sample contained p-type carriers with a concentration of 8.5 × 1016cm-3Carrier mobility of 23cm2·V-1·s-1. Gold electrodes were vapor-deposited on the upper and lower surfaces of another crystal wafer having a thickness of 1.13mm, and the device structure and the current-voltage characteristic curve thereof are shown in FIG. 6, and only an ohmic characteristic region in which the current linearly changes with the voltage appears in the applied voltage range of 0 to 40V. The above results all illustrate undoped CsSnBr3There are a large number of defects in the semiconductor material.
Claims (9)
1. A tin-containing semiconductor material is characterized in that the tin-containing semiconductor material is CsSnBr3In the preparation process, crystals with different carrier concentrations are grown by adding metal simple substances or metal compounds for doping.
2. The tin-containing semiconductor material of claim 1, wherein the starting material comprises CsBr, SnBr2And a simple metal or a metal compound.
3. The tin-containing semiconductor material of claim 2, wherein the elemental metal or metal compound is any one or more of elemental tin or tetravalent tin compound, elemental indium or indium compound, and elemental silver or silver compound.
4. The tin-containing semiconducting material of claim 3, wherein the tetravalent tin compound is SnBr4Or Cs2SnBr6。
5. The tin-containing semiconductor material of claim 3, wherein the indium compound is InBr.
6. The tin-containing semiconductor material of claim 3, wherein the silver compound is AgBr.
7. The tin-containing semiconductor material of claim 3, wherein the elemental tin has a mass not less than CsBr and SnBr2The sum of the masses of (a) and (b).
8. The tin-containing semiconductor material of any one of claims 3 to 7, wherein the mole number of the tetravalent tin compound, the other elemental metal or the metal compound is not more than SnBr25% of the mole number.
9. A method for preparing a tin-containing semiconductor material as claimed in any one of claims 2 to 8, characterized in that CsBr, SnBr2Mixing with metal simple substance or metal compound, heating under the protection of inert gas to react, and slowly cooling to obtain CsSnBr with different carrier concentrations3A semiconductor crystalline material.
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| CN115432731A (en) * | 2022-10-12 | 2022-12-06 | 电子科技大学 | Inversion type Cs 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 Hybrid composite material and preparation method thereof |
| CN116199253A (en) * | 2023-02-24 | 2023-06-02 | 中山大学 | Seleno perovskite and preparation method and application thereof |
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