CN110016719A - A kind of bismuth sulfide compound crystal and preparation method thereof - Google Patents

A kind of bismuth sulfide compound crystal and preparation method thereof Download PDF

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Publication number
CN110016719A
CN110016719A CN201910360222.7A CN201910360222A CN110016719A CN 110016719 A CN110016719 A CN 110016719A CN 201910360222 A CN201910360222 A CN 201910360222A CN 110016719 A CN110016719 A CN 110016719A
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bismuth
sample
crystal
nacl
bismuth sulfide
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CN110016719B (en
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马艳梅
李月
王莹莹
李芳菲
王洪波
马琰铭
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Jilin University
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Jilin University
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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
    • C30B1/00—Single-crystal growth directly from the solid state
    • C30B1/10—Single-crystal growth directly from the solid state by solid state reactions or multi-phase diffusion
    • 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
    • C30B1/00—Single-crystal growth directly from the solid state
    • C30B1/12—Single-crystal growth directly from the solid state by pressure treatment during the growth
    • 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
    • C30B29/46—Sulfur-, selenium- or tellurium-containing compounds

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

A kind of bismuth sulfide compound crystal of the invention and preparation method thereof belongs to technical field of inorganic material synthesis, and it is cubic system crystal that the chemical formula of the bismuth sulfide compound crystal, which is BiS,.The preparation method comprises the following steps: circular sample is made in bismuth trisulfide powder；Two panels NaCl thin slice will be made after the drying of NaCl particle；NaCl thin slice and bismuth trisulfide circular sample are put into diamond anvil cell sample cavity and form sandwiched type structure；It is forced into 32.6GPa；It is heated up to 1500K, is kept for 15 minutes；Release is cooled to normal temperature and pressure, obtains bismuth sulfide crystal BiS.The present invention obtains the bismuth sulfide sample of new chemical metering when crystal form using solid reaction process for the first time experimentally under high-temperature and high-pressure conditions, and such simple sulphur bismuth system compound of structure has potential application in terms of topological property and thermoelectricity capability.

Description

A kind of bismuth sulfide compound crystal and preparation method thereof
Technical field
The invention belongs to technical field of inorganic material synthesis, in particular to a kind of V-VI race Bi-S system compound bismuth sulfide The preparation method of crystal and its high temperature and pressure.
Background technique
In recent years, V-VI compounds of group causes science due to its topological insulating property (properties), superconducting property and thermoelectric property etc. Family's extensive concern.Well known V-VI race A2B3Type (A=Sb, Bi；B=S, Se, Te) strong Quantum geometrical phase (SOC) compound- Bi2Te3、Sb2Te3And Bi2Se3It is exactly topological insulating materials the simplest, Bi2Te3It is also the superfine thermoelectricity material of performance Material.Because V-VI compounds of group has unusual physical characteristic, therefore, it is dedicated to finding the other structures shape of V-VI compounds of group State, other stoichiometrics compound be also concerned.The V-VI compounds of group of different stoichiometrics, the crystalline substance of substance Body structure and chemical bond between atoms significant changes, thus there is potential topological property and thermoelectricity capability.But at present in addition to A2B3Type Compound except, synthesize other stoichiometric ratio Bi-S system compounds using high temperature and high pressure method and have not been reported.
Summary of the invention
The purpose of the present invention is to provide the BiS crystal and the compound of a kind of Bi-S system new chemical metering ratio Preparation method.
The technical solution adopted by the invention is as follows:
A kind of bismuth sulfide compound crystal, which is characterized in that the chemical formula of crystal is BiS, is cubic system crystal, space Group is pm-3m, and lattice constant is
A kind of preparation method of bismuth sulfide compound crystal, there is following steps:
1) bismuth trisulfide powder is put into mortar, two anvil faces of diamond anvil cell is placed on after being fully ground Middle tabletting, is made circular sample；
2) it will be placed on tabletting in two anvil faces of diamond anvil cell after NaCl particle heating, drying, it is thin that two panels NaCl is made Piece is as heat insulation layer and transmission medium；
3) wherein a piece of NaCl thin slice is put into the sample cavity of diamond anvil cell；By the bismuth trisulfide sample after tabletting Product are put into the center of the NaCl thin slice；Another NaCl thin slice is put into the sample cavity of diamond anvil cell, sample is covered Sample in chamber forms sandwiched type structure；
4) ruby is put into sample cavity, as pressure calibration material；
5) diamond anvil cell is closed, 32.6GPa is forced into；It is heated up to 1500K, is kept for 15 minutes；
6) release is cooled to normal temperature and pressure, obtains bismuth sulfide crystal BiS.
In step 1), the preferred purity of bismuth trisulfide powder be 99.999% Bi2S3；Made of after tabletting Preferably 80 microns of circular sample diameter；
In step 2), preferably 100 microns of NaCl wafer diameters obtained；
In step 3), preferably 300 microns of diamond anvil cell anvil face diameter used makes a call to a diameter by T301 steel disc The sample cavity is made in 100 microns of hole.
The utility model has the advantages that
The present invention is for the first time experimentally using bismuth trisulfide powder as initial feed, at high temperature under high pressure, using solid Phase reaction method obtains the bismuth sulfide sample that new chemical measures when crystal form, reaction are as follows: Bi2S3→S+2BiS.Such structure letter Single sulphur bismuth system compound has potential application in terms of topological property and thermoelectricity capability.
Detailed description of the invention
Sample assembly schematic diagram in diamond anvil cell when Fig. 1 is present invention preparation BiS crystal.
Fig. 2 is the X ray diffracting spectrum and its index that the present invention prepares BiS crystal stress-relief process under 31.7GPa pressure Change.
Fig. 3 is that BiS crystal prepared by the present invention unloads X ray diffracting spectrum to normal temperature and pressure and its refine and index Change.
Fig. 4 is the crystal structure schematic diagram of BiS crystal prepared by the present invention.
Specific embodiment
Embodiment 1
Use high-purity bismuth trisulfide powder (99.999%) as original material.Raw material are put into mortar, are carried out It is fully ground, the raw material after grinding is placed on tabletting repeatedly in two anvil face of diamond anvil cell that anvil face is 80 microns, compacting At about 80 microns of circular samples of diameter.NaCl is put into heating furnace and is dried, the NaCl particle after taking a drying is placed on anvil face Tabletting in about 100 microns of two anvil face of diamond anvil cell, obtain about 100 microns of diameter of the thin NaCl of two panels as heat insulation layer and Transmission medium.Wherein one thin NaCl piece is put into the sample cavity for the diamond anvil cell that anvil face diameter is 300 microns, it is described Sample cavity is made by the circular holes that T301 steel disc beats 100 microns of diameter.Bismuth trisulfide sample after tabletting is put into diamond Then another thin NaCl piece is put into the sample cavity of diamond anvil cell by the center of NaCl thin slice in the sample cavity of opposed anvils In, the sample in sample cavity is covered, sandwiched type structure is formed, finally puts a ruby in sample cavity, marks object as pressure Matter, sample assembly photo are shown in Fig. 1.Diamond anvil cell is closed, 32.6GPa is slowly forced into, then sample is swashed repeatedly point by point Light heating, temperature 1500K, qtenched sample cooled to room temperature after 15 minutes unload and are depressed into normal pressure to get bismuth sulfide crystal is arrived. During the preparation process, X-ray diffraction measurement is carried out to sample, Fig. 2 is the X ray picture in gradually stress-relief process, a 32.6GPa There is no the diffraction pattern of laser heating, for comparing；B, c, d, e are that pressure drops to different stage after laser heating 1500K is quenched When corresponding diffraction pattern, significant change occurs for diffraction pattern；F is to unload to normal pressure diffraction pattern.(110) of BiS crystal in stress-relief process Crystallographic plane diffraction peak intensity gradually increases, and as shown in phantom in FIG., crystallization is become better and better, while detecting a small amount of simple substance S and NaCl Diffraction maximum.Fig. 3 is the X ray diffracting spectrum and its refine and indexing of the sample unloaded to normal pressure, through known to indexing its be Cubic structure, space group pm-3m, lattice constant areFig. 4 is crystal structure schematic diagram.This new chemical meter The compound BiS crystal structure for measuring proportion simply, under normal temperature and pressure conditions is stabilized, this new function material has potential Topological property and thermoelectricity capability.

Claims (5)

1. a kind of bismuth sulfide compound crystal, which is characterized in that the chemical formula of crystal is BiS, is cubic system crystal, space group For pm-3m, lattice constant is
2. a kind of preparation method of bismuth sulfide compound crystal described in claim 1, there is following steps:
1) bismuth trisulfide powder is put into mortar, tabletting in two anvil faces of diamond anvil cell is placed on after being ground, Circular sample is made；
2) it will be placed on tabletting in two anvil faces of diamond anvil cell after NaCl particle heating, drying, two panels NaCl thin slice is made and makees For heat insulation layer and transmission medium；
3) wherein a piece of NaCl thin slice is put into the sample cavity of diamond anvil cell；Bismuth trisulfide sample after tabletting is put Enter the center of the NaCl thin slice；Another NaCl thin slice is put into the sample cavity of diamond anvil cell, is covered in sample cavity Sample, formed sandwiched type structure；
4) ruby is put into sample cavity, as pressure calibration material；
5) diamond anvil cell is closed, 32.6GPa is forced into；It is heated up to 1500K, is kept for 15 minutes；
6) release is cooled to normal temperature and pressure, obtains bismuth sulfide crystal BiS.
3. a kind of preparation method of bismuth sulfide compound crystal according to claim 2, which is characterized in that in step 1) In, the bismuth trisulfide powder is the Bi that purity is 99.999%2S3；Manufactured circular sample diameter is 80 micro- after tabletting Rice.
4. a kind of preparation method of bismuth sulfide compound crystal according to claim 2, which is characterized in that in step 2) In, NaCl wafer diameters obtained are 100 microns.
5. a kind of preparation method of bismuth sulfide compound crystal according to claim 2, which is characterized in that in step 3) In, diamond anvil cell anvil face diameter used is 300 microns, and institute is made by the hole that T301 steel disc makes a call to 100 microns of diameter The sample cavity stated.
CN201910360222.7A 2019-04-30 2019-04-30 Bismuth sulfide compound crystal and preparation method thereof Expired - Fee Related CN110016719B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114293259A (en) * 2021-12-06 2022-04-08 电子科技大学长三角研究院(湖州) Boron nitride crystal and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150275396A1 (en) * 2014-03-26 2015-10-01 Reinhard Boehler High pressure single crystal diamond anvils
CN106501046A (en) * 2016-12-06 2017-03-15 中国工程物理研究院流体物理研究所 The assembly method of adiabatic salt piece and sample in diamond anvil cell laboratory sample hole
JP2019064885A (en) * 2017-10-04 2019-04-25 国立研究開発法人物質・材料研究機構 Hard material containing rhenium nitride, method for producing the same, and cutting tool using the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150275396A1 (en) * 2014-03-26 2015-10-01 Reinhard Boehler High pressure single crystal diamond anvils
CN106501046A (en) * 2016-12-06 2017-03-15 中国工程物理研究院流体物理研究所 The assembly method of adiabatic salt piece and sample in diamond anvil cell laboratory sample hole
JP2019064885A (en) * 2017-10-04 2019-04-25 国立研究開発法人物質・材料研究機構 Hard material containing rhenium nitride, method for producing the same, and cutting tool using the same

Non-Patent Citations (2)

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Title
GUANGTAO LIU ET AL.: "Unexpected Semimetallic BiS2 at High Pressure and High Temperature", 《J.PHYS.CHEM.LETT.》 *
李芳菲: "含氢分子体系的高温高压物性研究", 《中国博士学位论文全文数据库 基础科学辑》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114293259A (en) * 2021-12-06 2022-04-08 电子科技大学长三角研究院(湖州) Boron nitride crystal and preparation method thereof

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