CN107675258B - A kind of iron-based ternary sulfur family monocrystal material of pyrite and preparation method thereof - Google Patents
A kind of iron-based ternary sulfur family monocrystal material of pyrite and preparation method thereof Download PDFInfo
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- CN107675258B CN107675258B CN201710865735.4A CN201710865735A CN107675258B CN 107675258 B CN107675258 B CN 107675258B CN 201710865735 A CN201710865735 A CN 201710865735A CN 107675258 B CN107675258 B CN 107675258B
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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
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
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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
- C30B9/00—Single-crystal growth from melt solutions using molten solvents
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Abstract
The present invention relates to iron-based ternary sulfur family monocrystal material of a kind of pyrite and preparation method thereof, molecular formula FePd2Se6Lattice constant is a=b=c=6.045 (3) angstrom, electronic transport shows as metallicity, magnetic performance is to have apparent hysteresis loop in 1.8K, include following successively step: 1) weighing the source Fe, the source Pd and the source Se, it is fitted into alumina crucible after mixing, then alumina crucible is sealed；2) being placed in high-temperature annealing furnace the alumina crucible of sealing starts setting program heating；Then using centrifugation removal fluxing agent Se, FePd is obtained2Se6Monocrystalline.The iron-based ternary sulfur family monocrystalline FePd of pyrite is prepared from flux growth metrhod in present invention use2Se6, there is at low cost, easy to control, reproducible, the advantages that equipment is simple.
Description
Technical field
The present invention relates to iron-based ternary sulfur family monocrystal materials of a kind of pyrite and preparation method thereof, belong to material science
Field.
Background technique
Iron chalcogenide have charming property, such as superconduction, thermoelectricity and photovoltaic effect and be concerned
(Sci.Technol.Adv.Mat.13,054305,2012；Adv.Energy Mater.1,748,2011；RSC Advances,
4,9424,2014).Currently, the research of most of iron chalcogenides focuses on hexagonal phase and tetragonal phase.Since the overwhelming majority is vertical
Fang Xiangtie sulfur family monocrystalline need to synthesize under high pressure (Inorg Chem, 15,3031,1976；Inorg Chem 7,2208,
1968), and Preparation equipment valuableness requires complexity, so research is just very deficient compared to other two-phases.In recent years, it stands
Square iron chalcogenide is in progress (Adv.Energy Mater.1,748,2011) in terms of photovoltaic research, but sample is
Hydrothermal synthesis it is nanocrystalline, nano material differs larger with the physical property of block materials；Or preparation cube iron sulfur family polycrystal film,
But equipment valuableness require it is complicated and also tend to have miscellaneous phase (J Mater Sci, 48,4914,2013；Thin Solid Films,516,
7116,2008), this is all unfavorable for carrying out more researchs.In addition, an existing most of cube iron chalcogenides are only limitted to binary
Material.It will be apparent that these factors significantly limit the basic physical properties of this kind of material and the research of application.So exploring non-
It is necessary under condition of high voltage and using the compound of the polynary iron content sulfur family of simple device synthesis of cubic structure.
Summary of the invention
A kind of simple, low cost, Gao Chongfu it is an object of the invention to provide in place of overcome the deficiencies in the prior art
Property, iron-based ternary sulfur family monocrystalline of structure and preparation method thereof is prepared under non-condition of high voltage.
The technical proposal adopted by the invention to solve the above technical problems is that a kind of iron-based ternary sulfur family list of pyrite
Brilliant material, molecular formula FePd2Se6, lattice constant is a=b=c=6.045 (3) angstrom, and electronic transport shows as metallicity, magnetic
Sex expression is to have apparent hysteresis loop in 1.8K.
According to the above scheme, the monocrystalline shape of the iron-based ternary sulfur family monocrystal material of the pyrite is with multiple tables
The graininess in face is rodlike.
The preparation method of the iron-based ternary sulfur family monocrystal material of the pyrite includes following successively step:
1) raw material and sealing are weighed
The source Fe, the source Pd and the source Se are weighed by Fe, Pd and Se molar ratio 3:1:6-1:3:30, is packed into alumina crucible after mixing
In, then alumina crucible is sealed；
2) heating, annealing process
Being placed in high-temperature annealing furnace for the alumina crucible of sealing, start setting program heating: room temperature rises to 300 DEG C,
Used time 8-24 hour；300 DEG C rise to 800 DEG C -1050 DEG C, used time 12-36 hour；800 DEG C -1050 DEG C of heat preservations 3-8 hours；800
DEG C -1050 DEG C are cooled to 300 DEG C, and the used time is more than 100 hours；Then using centrifugation removal fluxing agent Se, FePd is obtained2Se6It is single
It is brilliant.
According to the above scheme, Fe source described in step 1) is high-purity Fe powder or Fe block；The source Pd be high-purity Pd powder or
Pd block；The source Se is high-purity Se powder or Se block.
According to the above scheme, in step 1), sealing alumina crucible material therefor is quartz ampoule, Ta pipe, niobium pipe or iron crucible.
According to the above scheme, when sealing alumina crucible material therefor is quartz ampoule, then alumina crucible is put into quartz
Guan Zhong vacuumizes quartz ampoule and changes argon gas at least 3 times repeatedly, finally vacuumizes and be sealed again；When sealing alumina crucible
Material therefor is Ta pipe, niobium pipe or iron crucible, then alumina crucible is put into iron crucible, Ta pipe or Nd pipe, then true
It is sealed under thin argon atmospher in empty electric arc furnaces.
According to the above scheme, in step 1), argon cleaning 3 times or more, last vacuum is less than 10-1Pa。
According to the above scheme, in step 2), in temperature-rise period, 300 DEG C heat preservation 12-24 hours；In temperature-fall period, every 12-
24 hours, make stove low amplitude vibrations or wave 0.5-30 minutes, 300 DEG C heat preservation 12-24 hours.
The present invention is from fluxing agent with selenium using fe, palladium and selenium as raw material.Weighed raw material is put in crucible
It is interior, it then places into quartz ampoule, the technology of flux is vibrated and removed using stepped annealing process and interval, finally obtain new
Type monocrystalline.
The iron-based ternary sulfur family monocrystalline FePd of pyrite is prepared from flux growth metrhod in present invention use2Se6, provide
A method of it growing pyrite iron sulfur family monocrystal material under non-condition of high voltage, overcomes high compression ring in the prior art
Border and technological deficiency at high cost have at low cost, easy to control, reproducible, the advantages that equipment is simple.Huang of the present invention
Hematite structure iron sulfur family FePd2Se6Monocrystalline, crystal property is good, no miscellaneous phase, and shape is particle or rodlike.Its electronic transport is shown as
Metallicity, it is magnetic then show as 1.8K with apparent hysteresis loop.FePd2Se6The success of monocrystalline is prepared as in non-condition of high voltage
A lower preparation cube iron chalcogenide provides beneficial reference, and this contains magnetic element pyrite monocrystalline and also becomes pair
The physical property of Hubbard Hamiltonian prophesy is compared Potential Vector (the J Appl Phys 50 of research with experimental result
(1979):2308-2311)。
Detailed description of the invention
Fig. 1 is the FePd of the embodiment of the present invention 12Se6The outline drawing of monocrystalline；
Fig. 2 is the FePd of the embodiment of the present invention 12Se6The EDX of monocrystalline is composed；
Fig. 3 is the FePd of the embodiment of the present invention 12Se6The x-ray diffractogram of powder of monocrystalline；
Fig. 4 is the FePd of the embodiment of the present invention 12Se6The resistance temperature curve of monocrystalline；
Fig. 5 is the FePd of the embodiment of the present invention 12Se6The Curve of Magnetic Hysteresis Loop of monocrystalline 1.8K；
Fig. 6 is the FePd of the embodiment of the present invention 22Se6The EDX of monocrystalline is composed；
Fig. 7 is the FePd of the embodiment of the present invention 22Se6The x-ray diffractogram of powder of monocrystalline；
Fig. 8 is the FePd of the embodiment of the present invention 32Se6The EDX of monocrystalline is composed；
Fig. 9 is the FePd of the embodiment of the present invention 32Se6The x-ray diffractogram of powder of monocrystalline；
Specific embodiment
It is further elaborated on the present invention with reference to embodiments, but embodiment is not limitation of the present invention.It is not carrying on the back
From under the spirit and scope of inventive concept, various changes and advantages that will be apparent to those skilled in the art are all included in the present invention
In.
Embodiment 1
The present embodiment is pyrite iron sulfur family monocrystalline FePd2Se6Preparation process and its structure, electricity and magnetic survey
Examination.
One, single crystal preparation
1) raw material and sealing, are weighed
The Se powder of Fe of 0.1071g, Pd of 0.4083g and 1.5152g are weighed, is packed into oxidation after ground and mixed
In aluminium crucible, then crucible is put into quartz ampoule.Then applying argon gas is vacuumized to quartz ampoule, 5 times repeatedly, finally pumping is again
Vacuum, pressure 10-3Pa；
2), heating, annealing process
There is the quartz ampoule of crucible to be put in high-temperature annealing furnace envelope, starts setting program heating.Room temperature rises to 300 DEG C, uses
When 12 hours；300 DEG C keep the temperature 12 hours；300 DEG C rise to 900 DEG C, the used time 12 hours；900 DEG C keep the temperature 4 hours；900 DEG C are cooled to
300 DEG C, the used time is more than 200 hours, every 12 hours in this temperature-fall period, makes stove low amplitude vibrations or waves 2 minutes；
300 DEG C keep the temperature 12 hours；Then quartz ampoule is put into a centrifuge removal flux Se, obtains FePd2Se6Monocrystalline.
3), prepared by electrode: with the resistance of four probe method measurement sample, therefore to FePd made from step 2)2Se6Along a on monocrystalline
Axis 4 In electrodes of viscous pressure.
Two, crystal structure is tested
Habit such as Fig. 1；It cuts the EDX on one small monocrystalline SEM and surveys element ratio, sample includes element such as Fig. 2；
It cuts one small monocrystalline to be ground into a powder, test data and be analyzed on x-ray powder diffraction instrument, the XRD spectrum such as Fig. 3 of sample.With
Upper experimental result confirms that monocrystalline molecular formula is FePd2Se6, lattice constant is a=b=c=6.045 (3) angstrom.
Three, electrical performance testing
1) prepared by electrode
Along a axis direction of crystal, with In 4 electrodes of viscous pressure.
2) performance test.
Use the electrical properties of PPMS system testing monocrystalline.Test scope is from 1.8K to 300K.FePd2Se6Monocrystalline is shown
Apparent metallicity, such as Fig. 4.
Four, magnetic performance is tested
Magnetic property measurement is carried out on the MPMS of Quantum Design company.Test is carried out at 1.8K.It measures
Low temperature M-H curve shows that sample shows ferromagnetism in 1.8K, as shown in Figure 5.
Embodiment 2
The present embodiment is pyrite iron sulfur family monocrystalline FePd2Se6Preparation process and its structure.
One, single crystal preparation
1) raw material and sealing, are weighed
It is the Fe powder, Pd powder and Se powder that 3:1:15 weighs certain mass with Fe:Pd:Se, is packed into aluminium oxide after ground and mixed
In crucible, then crucible is put into quartz ampoule.Then applying argon gas is vacuumized to quartz ampoule, 5 times repeatedly, it is true for finally taking out again
Sky, pressure 10-2Pa；
2), heating, annealing process
There is the quartz ampoule of crucible to be put in high-temperature annealing furnace envelope, starts setting program heating.Room temperature rises to 300 DEG C, uses
When 12 hours；300 DEG C keep the temperature 12 hours；300 DEG C rise to 950 DEG C, the used time 24 hours；900 DEG C keep the temperature 4 hours；950 DEG C are cooled to
300 DEG C, the used time is more than 200 hours, every 24 hours in this temperature-fall period, makes stove low amplitude vibrations or waves 1 minute；
300 DEG C keep the temperature 12 hours；Then quartz ampoule is put into a centrifuge removal flux Se, obtains FePd2Se6Monocrystalline.
Two, crystal structure is tested
It cuts the EDX on one small monocrystalline SEM and surveys element ratio, sample includes element such as Fig. 6；Cut one small monocrystalline
It is ground into a powder, test data and is analyzed on x-ray powder diffraction instrument, the XRD spectrum of sample such as Fig. 7, is consistent with embodiment 1
's.
Embodiment 3
The present embodiment is pyrite iron sulfur family monocrystalline FePd2Se6Preparation process and its structure.
One, single crystal preparation
1) raw material and sealing, are weighed
It is the Fe powder, Pd powder and Se powder that 1:3:20 weighs certain mass with Fe:Pd:Se, is packed into aluminium oxide after ground and mixed
In crucible, then crucible is put into quartz ampoule.Then applying argon gas is vacuumized to quartz ampoule, 5 times repeatedly, it is true for finally taking out again
Sky, pressure 10-2Pa；
2), heating, annealing process
There is the quartz ampoule of crucible to be put in high-temperature annealing furnace envelope, starts setting program heating.Room temperature rises to 300 DEG C, uses
When 10 hours；300 DEG C keep the temperature 10 hours；300 DEG C rise to 1000 DEG C, the used time 24 hours；1000 DEG C keep the temperature 4 hours；1000 DEG C of drops
For temperature to 300 DEG C, the used time is more than 220 hours, every 48 hours in this temperature-fall period, makes stove low amplitude vibrations or waves 2 points
Clock；300 DEG C keep the temperature 12 hours；Then quartz ampoule is put into a centrifuge removal flux Se, obtains FePd2Se6Monocrystalline.
Two, crystal structure is tested
It cuts the EDX on one small monocrystalline SEM and surveys element ratio, sample includes element such as Fig. 8；Cut one small monocrystalline
Be ground into a powder, test data and analyzed on x-ray powder diffraction instrument, the powder X-ray RD spectrum of the sample such as Fig. 9, with embodiment 1 and
2 are consistent.
Claims (8)
1. a kind of iron-based ternary sulfur family monocrystal material of pyrite, molecular formula FePd2Se6, lattice constant a=b=c
=6.045 (3) angstrom, electronic transport show as metallicity, and magnetic performance is to have apparent hysteresis loop in 1.8K.
2. the iron-based ternary sulfur family monocrystal material of pyrite as described in claim 1, it is characterised in that the pyrite
The monocrystalline shape of the iron-based ternary sulfur family monocrystal material of structure is the graininess or rodlike with multiple surfaces.
3. the preparation method of the iron-based ternary sulfur family monocrystal material of pyrite described in claim 1, include it is following successively
Step:
1) raw material and sealing are weighed
The source Fe, the source Pd and the source Se are weighed by Fe, Pd and Se molar ratio 3:1:6-1:3:30, is fitted into alumina crucible after mixing,
Then alumina crucible is sealed；
2) heating, annealing process
Being placed in high-temperature annealing furnace for the alumina crucible of sealing, start setting program heating: room temperature rises to 300 DEG C, the used time
8-24 hours；300 DEG C rise to 800 DEG C -1050 DEG C, used time 12-36 hour；800 DEG C -1050 DEG C of heat preservations 3-8 hours；800℃-
1050 DEG C are cooled to 300 DEG C, and the used time is more than 100 hours；Then using centrifugation removal fluxing agent Se, FePd is obtained2Se6Monocrystalline.
4. the preparation method of the iron-based ternary sulfur family monocrystal material of pyrite according to claim 3, it is characterised in that
The source Fe described in step 1) is high-purity Fe powder or Fe block；The source Pd is high-purity Pd powder or Pd block；The source Se is high-purity Se
Powder or Se block.
5. the preparation method of the iron-based ternary sulfur family monocrystal material of pyrite according to claim 3, it is characterised in that
In step 1), sealing alumina crucible material therefor is quartz ampoule, Ta pipe, niobium pipe or iron crucible.
6. the preparation method of the iron-based ternary sulfur family monocrystal material of pyrite according to claim 3, it is characterised in that
When sealing alumina crucible material therefor is quartz ampoule, then alumina crucible is put into quartz ampoule, quartz ampoule is vacuumized
It changes argon gas at least 3 times repeatedly, finally vacuumizes and be sealed again；When sealing alumina crucible material therefor is Ta pipe, niobium pipe
Or iron crucible, then alumina crucible is put into iron crucible, Ta pipe or Nd pipe, then in thin argon gas in vacuum arc furnace ignition
It is sealed under atmosphere.
7. the preparation method of the iron-based ternary sulfur family monocrystal material of pyrite according to claim 6, it is characterised in that
In step 1), last vacuum is less than 10-1Pa。
8. the preparation method of the iron-based ternary sulfur family monocrystal material of pyrite according to claim 3, it is characterised in that
In step 2), in temperature-rise period, 300 DEG C heat preservation 12-24 hours；In temperature-fall period, every 12-24 hours, stove is made slightly to shake
It is dynamic or wave 0.5-30 minutes, 300 DEG C heat preservation 12-24 hours.
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