CN116971033A - Ferroselenide ferroferric single crystal and preparation method thereof - Google Patents

Ferroselenide ferroferric single crystal and preparation method thereof Download PDF

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Publication number
CN116971033A
CN116971033A CN202311043906.7A CN202311043906A CN116971033A CN 116971033 A CN116971033 A CN 116971033A CN 202311043906 A CN202311043906 A CN 202311043906A CN 116971033 A CN116971033 A CN 116971033A
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temperature
quartz tube
ferroselenide
mixed powder
powder
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梅佳伟
张文清
岳磊
郝占阳
王乐
刘才
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Southern University of Science and Technology
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Southern University of Science and Technology
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • 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
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/041—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, milling

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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)
  • General Chemical & Material Sciences (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

The invention discloses a ferroselenide ferroferric single crystal and a preparation method thereof, wherein the preparation method comprises the following steps: mixing the provided ferroselenium ferroferric polycrystal powder with a chemical vapor transport agent to obtain mixed powder; placing the mixed powder at one end of a quartz tube, vacuumizing and sealing the tube; heating the quartz tube, keeping the temperature of the end of the quartz tube, on which the mixed powder is placed, at a first preset temperature for a first preset time, keeping the temperature of the end of the quartz tube, on which the mixed powder is not placed, at a second preset temperature for the first preset time, and naturally cooling to obtain a ferroselenide three-iron monocrystal; wherein the first preset temperature is 712-750 ℃ and is higher than the second preset temperature. The method successfully prepares the ferroferric selenide monocrystal by adopting a chemical vapor transmission method for the first time, has the advantages of simple steps, short growth period, high success rate, large quantity of the obtained monocrystal, good integrity and large size, is suitable for most conventional research means, and makes up the blank of the ferroferric selenide in the aspect of monocrystal preparation.

Description

Ferroselenide ferroferric single crystal and preparation method thereof
Technical Field
The invention relates to the technical field of crystal growth, in particular to a ferroselenide ferroferric single crystal and a preparation method thereof.
Background
Ferroselenide is a monoclinic crystal (polycrystalline) with a lattice constant of a=0.62 nm, b=0.353 nm, c=1.126 nm, α=γ=90°, β=91.73°. The ferroselenide has room-temperature ferromagnetism, the magnetic phase transition temperature (Tc) of the ferroselenide is about 350K, in addition, theoretical calculation prediction and powder polycrystal transportation experiments prove that the ferroselenide is a ferromagnetism semi-metal material, the ferromagnetism semi-metal material shows 100% spin polarization on the fermi level and is an ideal material for spintronic application, so that the ferroselenide has a large potential application prospect in spintronics and the like in the future, and high-quality single crystal materials are needed for further research and exploration of the material.
To date, the research on ferroferric selenide is based on a polycrystalline powder sample prepared by proportioning iron powder and selenium powder according to stoichiometric ratio, and then performing solid-state sintering at high temperature, and cooling. This method cannot obtain a single crystal sample, and therefore, physical properties of the material are limited in many aspects.
Accordingly, the prior art is still in need of improvement and development.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a ferroselenide single crystal and a preparation method thereof, which aims to solve the problem that the conventional method can not prepare the ferroselenide single crystal, so that the physical property research of the ferroselenide material in many aspects is limited.
The technical scheme of the invention is as follows:
in a first aspect of the present invention, there is provided a method for producing a ferroselenide single crystal, comprising the steps of:
providing ferroselenide ferroferric polycrystalline powder and a chemical vapor transport agent;
mixing the ferroselenium ferroferric polycrystalline powder and the chemical vapor transport agent to obtain mixed powder;
placing the mixed powder at one end of a quartz tube, vacuumizing and sealing the tube;
heating the quartz tube, keeping the temperature of the end of the quartz tube, on which the mixed powder is placed, at a first preset temperature for a first preset time, keeping the temperature of the end of the quartz tube, on which the mixed powder is not placed, at a second preset temperature for the first preset time, and naturally cooling to obtain the ferroferric selenide monocrystal;
the first preset temperature is 712-750 ℃, and the decomposition temperature of the chemical vapor transport agent is less than or equal to the first preset temperature.
Optionally, the molar ratio of the ferroferric selenide polycrystalline powder to the chemical vapor transport agent is 1:0.5-1.
Optionally, the molar ratio of the ferroferric selenide polycrystalline powder to the chemical vapor transport agent is 1:0.65-0.75.
Optionally, the chemical vapor transport agent comprises at least one of ferric trichloride, ferric tribromide, and ferric triiodide.
Optionally, the preparation method of the ferroselenide ferroferric polycrystalline powder comprises the following steps:
mixing iron powder and selenium powder according to a molar ratio of 3:4, then preserving heat at 900 ℃ for four days, and naturally cooling to obtain the ferroselenium ferroferric selenide polycrystalline powder.
Optionally, at H 2 And in the environment with the O content less than 0.01ppm, grinding and mixing the ferroferric selenide polycrystalline powder and the chemical vapor transport agent to obtain mixed powder.
Optionally, the first preset time is 7-9 days.
Optionally, the second preset temperature is 602-607 ℃.
Optionally, the heating the quartz tube, so that the end of the quartz tube, where the mixed powder is placed, is kept at a first preset temperature for a first preset time, and meanwhile, the end of the quartz tube, where the mixed powder is not placed, is kept at a second preset temperature for a first preset time, and after natural cooling, the step of obtaining the ferroferric selenide monocrystal specifically includes:
providing a double-temperature-zone tube furnace, wherein the double-temperature zone comprises a first temperature zone and a second temperature zone;
placing the quartz tube in the double-temperature-zone tube furnace, so that one end of the quartz tube, on which mixed powder is placed, is positioned in a first temperature zone, and one end of the quartz tube, on which mixed powder is not placed, is positioned in a second temperature zone;
and (3) starting the double-temperature-zone tube furnace to heat, wherein the temperature of the first temperature zone is 712-750 ℃, the temperature of the second temperature zone is 602-607 ℃, heating the quartz tube, naturally cooling after 7-9 days, and obtaining the ferroselenide three-iron single crystal at one end of the quartz tube, at which the mixed powder is not placed.
In a second aspect of the invention, there is provided a ferroselenide single crystal prepared by the method of the invention as described above.
The beneficial effects are that: the method successfully prepares the ferroselenide three-iron monocrystal by adopting a chemical vapor transmission method for the first time, fills up the blank of the ferroselenide three-iron monocrystal preparation, has the advantages of simple steps, short growth period and high success rate (100%), and the obtained ferroselenide three-iron monocrystal has the advantages of large quantity, good integrity and large size, is suitable for most conventional research means such as physical property measurement and the like, and can ensure the quality of the ferroselenide three-iron monocrystal to meet the requirements of various scientific researches and applications.
Drawings
Fig. 1 is a schematic diagram of a structure of a quartz tube, a raw material placement position in the quartz tube, and temperature areas where two ends of the quartz tube are located in an embodiment of the present invention.
FIG. 2 is a diagram showing a three-iron tetra-selenide single crystal according to examples 1 to 4 of the present invention.
FIG. 3 is an XRD pattern of a single crystal of ferroselenide of example 1 of the present invention.
Detailed Description
The invention provides a ferroselenide ferroferric single crystal and a preparation method thereof, which are used for making the purposes, technical schemes and effects of the invention clearer and more definite, and the invention is further described in detail below. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
If there is a description of "first", "second", etc. in an embodiment of the present invention, the description of "first", "second", etc. is for descriptive purposes only and is not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated.
If not specified, the invention is 24 hours for 1 day, for example 96 hours for 4 days and 168 hours for 7 days.
The embodiment of the invention provides a preparation method of a ferroselenide ferroferric single crystal, which comprises the following steps:
s1, providing ferroselenide ferroferric polycrystalline powder and a chemical vapor transport agent;
s2, mixing the ferroselenide ferroferric polycrystalline powder with the chemical vapor transport agent to obtain mixed powder;
s3, placing the mixed powder at one end of a quartz tube, vacuumizing and sealing the tube;
s4, heating the quartz tube, keeping the temperature of the end, where the mixed powder is placed, of the quartz tube at a first preset temperature for a first preset time, keeping the temperature of the end, where the mixed powder is not placed, of the quartz tube at a second preset temperature for the first preset time, and naturally cooling to obtain the ferroselenide single crystal;
wherein the first preset temperature is greater than the second preset temperature, and the first preset temperature is 712-750 ℃.
The embodiment of the invention prepares the ferroselenide ferroferric single crystal by using a chemical vapor transport method, and fills the blank of the ferroselenide ferroferric in the aspect of single crystal preparation. The preparation method has the advantages of simple steps, short growth period, high success rate (about 100%), large number of obtained product single crystals, good integrity of the obtained ferroselenide single crystals, large size, suitability for most conventional research means such as physical property measurement and the like, and capability of ensuring the quality of the ferroselenide single crystals so as to meet the requirements of various scientific researches and applications.
In the invention, the chemical vapor transport method is utilized to carry out nucleation crystallization at the temperature of less than 712-750 ℃ and continuously grow up, thus obtaining the ferroselenide ferroferric single crystal. Specifically, when the chemical vapor transfer agent is taken as an iron trichloride example and a quartz tube is heated, when the temperature is 300 ℃, the trichloro Hua Tie starts to decompose to generate nitrogen and iron, and the generated nitrogen moves from a high temperature area to a low temperature area along with raw materials, so that the raw materials are recrystallized and grow continuously in the low temperature area, and the ferroselenium ferroferric single crystal is formed.
In step S1, the preparation method of the ferroselenide ferroferric polycrystalline powder includes the steps of:
mixing iron powder and selenium powder according to a molar ratio of 3:4, then preserving heat for four days at a temperature of 850-950 ℃, and naturally cooling to obtain the ferroselenium three-iron polycrystalline powder.
Specifically, after mixing iron powder and selenium powder according to a molar ratio of 3:4, placing the mixture in a crucible, placing the crucible in a quartz tube, vacuumizing, sealing the tube, placing the quartz tube in a box-type furnace, heating to 900 ℃ at a speed of 100 ℃/h, preserving heat for four days, stopping heating, and naturally cooling to room temperature to obtain the ferroselenium ferroferric polycrystal.
In some embodiments, the chemical vapor transport agent comprises at least one of ferric trichloride, ferric tribromide, and ferric triiodide. These chemical vapor transport agents can provide ferric ions such that ferric ions are abundant in the environment.
In step S2, in some embodiments, the molar ratio of the ferroselenide polycrystalline powder to the chemical vapor transport agent is 1:0.5-1. For example, the molar ratio of the two is 1:0.5, 1:0.55, 1:0.6, 1:0.65, 1:0.7, 1:0.75, 1:0.8, 1:0.85, 1:0.9, 1:0.95, or 1:1, etc.
In some embodiments, the molar ratio of the ferroselenide polycrystalline powder to the chemical vapor transport agent is 1:0.65 to 0.75.
In some embodiments, at H 2 And (3) grinding and mixing the ferroferric selenide polycrystalline powder and the chemical vapor transport agent in an environment (such as a glove box) with the O content of less than 0.01ppm to obtain mixed powder. Since chemical vapor transport agents such as ferric trichloride are very soluble in water and rapidly deliquesce outside the atmosphere, they are readily available in H 2 And grinding and mixing the ferroferric selenide polycrystalline powder and the chemical vapor transport agent in an environment (such as a glove box) with the O content of less than 0.01 ppm.
In step S3, as shown in fig. 1, the mixed powder (which may be placed in the crucible 3 first) is placed at one end of the quartz tube 1, and after vacuum pumping, the quartz wool 4 is placed at the end of the quartz tube 1 where the mixed powder is not placed, and then the tube is sealed by the quartz column 2 to achieve sealing.
In step S4, the first preset temperature is 712 to 750 ℃, and may be 712 to 713 to 714 to 715 to 716 to 717 to 720 to 730 to 740 to 750, for example.
In some embodiments, the first preset time is 7 to 9 days, for example, 7 days, 7.5 days, 8 days, 8.5 days, 9 days, or the like.
In some embodiments, the second preset temperature is 602 to 607 ℃, for example 602 ℃, 603 ℃, 604 ℃, 605 ℃, 606 ℃, 607 ℃, or the like.
In some embodiments, the heating the quartz tube, so that the end of the quartz tube where the mixed powder is placed is kept at a first preset temperature for a first preset time, and meanwhile, the end of the quartz tube where the mixed powder is not placed is kept at a second preset temperature for a first preset time, and after natural cooling, the step of obtaining the ferroferric selenide single crystal specifically includes:
providing a double-temperature-zone tube furnace, wherein the double-temperature zone comprises a first temperature zone and a second temperature zone;
placing the quartz tube in the double-temperature-zone tube furnace, so that one end of the quartz tube, on which mixed powder is placed, is positioned in a first temperature zone, and one end of the quartz tube, on which mixed powder is not placed, is positioned in a second temperature zone;
and (3) starting the double-temperature-zone tube furnace to heat, wherein the temperature of the first temperature zone is 712-750 ℃, the temperature of the second temperature zone is 602-607 ℃, heating the quartz tube, naturally cooling after 7-9 days, and obtaining the ferroselenide three-iron single crystal at one end of the quartz tube, at which the mixed powder is not placed.
In this embodiment, the dual temperature zone tube furnace is opened to raise the temperature for the same time, so that the temperature of the first temperature zone is 712-750deg.C, and the temperature of the second temperature zone is 602-607 deg.C. Therefore, the temperature rising speed of the first temperature zone is different from that of the second temperature zone. And after 7-9 days, stopping heating in the two temperature areas at the same time, and naturally cooling.
The first temperature zone may also be referred to as a high temperature zone and the second temperature zone may also be referred to as a low temperature zone.
The preparation method of the present invention will be described in detail with reference to fig. 1.
Firstly, mixing the ferroselenide ferroferric polycrystal powder and a chemical vapor transport agent (such as ferric trichloride) to obtain mixed powder serving as a raw material.
The raw materials (which can be placed in a crucible 3 in advance) are placed at one end of a quartz tube 1, after vacuumizing, quartz wool 4 is placed at one end of the quartz tube, at which mixed powder is not placed, and then the tube is sealed through a quartz column 2. Then placing the quartz tube 1 in a double-temperature-zone tube furnace for heating, placing one end of the quartz tube, in which mixed powder is placed, at a first preset temperature (a high-temperature zone, 712-750 ℃), placing one end of the quartz tube, in which the mixed powder is not placed, at a second preset temperature (a low-temperature zone, 602-607 ℃), heating powdery raw materials in the high-temperature zone to form gaseous raw materials, forming nuclei in the low-temperature zone to continuously grow, stopping heating in the two temperature zones of the double-temperature-zone tube furnace at the same time after 7-9 days, and preparing the ferroselenide single crystal at one end of the quartz tube, in which the mixed powder is not placed, after natural cooling.
The embodiment of the invention also provides a ferroselenide ferroferric single crystal, wherein the ferroselenide single crystal is prepared by adopting the preparation method disclosed by the embodiment of the invention.
The following is a detailed description of specific examples.
The preparation method of the ferroselenide ferroferric polycrystal adopted in the following example comprises the following steps:
uniformly mixing high-purity iron powder (purity is 99.9%) and high-purity selenium powder (purity is 99.99%) according to a molar ratio of 3:4 to obtain mixed powder, and placing the mixed powder in an alumina crucible;
placing an alumina crucible containing mixed powder in a quartz tube, vacuumizing, sealing the tube, placing the quartz tube in a box furnace, heating to 900 ℃ at the speed of 100 ℃/h, preserving heat for four days, stopping heating, and naturally cooling to room temperature to obtain the ferroselenide ferroferric polycrystal.
Example 1
The embodiment provides a preparation method of ferroferric selenide, which comprises the following steps:
the ferroselenide multiferroic polycrystal was put in a vacuum glove box (H 2 O content is less than 0.01 ppm), adding ferric trichloride powder, grinding and fully mixing to obtain mixed powder, wherein the molar ratio of the ferric selenide polycrystal to the ferric tetrachloride powder is 1:0.6.
Placing the mixed powder into one end of quartz tube, and vacuumizing to make the air pressure of quartz tube mouth be less than 10 -3 Pa, sealing the tube, sealing with adhesive tape, and taking out from the glove box.
And placing the quartz tube into a double-temperature-zone tube furnace (comprising a high-temperature zone and a low-temperature zone), placing one end of the quartz tube, in which the mixed powder is placed, at a high temperature, placing the other end, in which the mixed powder is not placed, in the low-temperature zone, heating the high-temperature zone and the low-temperature zone from the same temperature at the same time, heating the high-temperature zone to 715 ℃ after 7 hours, heating the low-temperature zone to 605 ℃, and preserving the heat for 7 days. And then the heating is stopped in the high temperature area and the low temperature area simultaneously, so that the tube furnace with the double temperature areas is naturally cooled to room temperature, one end of the quartz tube in the low temperature area is provided with a ferroselenide single crystal with good quality, the size is 1.5mm multiplied by 2mm, the actual diagram is shown in figure 2, and the XRD diagram is shown in figure 3.
Example 2
The embodiment provides a preparation method of ferroferric selenide, which comprises the following steps:
the ferroselenide multiferroic polycrystal was put in a vacuum glove box (H 2 O content is less than 0.01 ppm), adding ferric trichloride powder, grinding and fully mixing to obtain mixed powder, wherein the molar ratio of the ferric selenide polycrystal to the ferric tetrachloride powder is 1:0.7.
Placing the mixed powder into one end of quartz tube, and vacuumizing to make the air pressure of quartz tube mouth be less than 10 -3 Pa, sealing the tube, sealing with adhesive tape, and taking out from the glove box.
And placing the quartz tube into a double-temperature-zone tube furnace (comprising a high-temperature zone and a low-temperature zone), placing one end of the quartz tube, in which the mixed powder is placed, at a high temperature, placing the other end, in which the mixed powder is not placed, in the low-temperature zone, heating the high-temperature zone and the low-temperature zone from the same temperature at the same time, heating the high-temperature zone to 715 ℃ after 7 hours, heating the low-temperature zone to 605 ℃, and preserving the heat for 7 days. And then the heating is stopped in the high temperature area and the low temperature area simultaneously, the tube furnace with the double temperature areas is naturally cooled to room temperature, one end of the quartz tube in the low temperature area is provided with a ferroselenide single crystal with good quality, the size is 1.2mm multiplied by 1mm, the actual graph is shown in figure 2, and the XRD graph is basically the same as that of figure 3.
Example 3
The embodiment provides a preparation method of ferroferric selenide, which comprises the following steps:
the ferroselenide multiferroic polycrystal was put in a vacuum glove box (H 2 O content is less than 0.01 ppm), adding ferric trichloride powder, grinding and fully mixing to obtain mixed powder, wherein the molar ratio of the ferric selenide polycrystal to the ferric tetrachloride powder is 1:0.7.
Placing the mixed powder into one end of quartz tube, and vacuumizing to make the air pressure of quartz tube mouth be less than 10 -3 Pa, sealing the tube, and sealing with adhesive tapeAnd then taken out of the glove box.
And placing the quartz tube into a double-temperature-zone tube furnace (comprising a high-temperature zone and a low-temperature zone), placing one end of the quartz tube, in which the mixed powder is placed, at a high temperature, placing the other end, in which the mixed powder is not placed, in the low-temperature zone, heating the high-temperature zone and the low-temperature zone from the same temperature at the same time, heating the high-temperature zone to 715 ℃ after 7 hours, heating the low-temperature zone to 605 ℃, and preserving the heat for 9 days. And then the heating is stopped in the high temperature area and the low temperature area simultaneously, the tube furnace with the double temperature areas is naturally cooled to room temperature, one end of the quartz tube in the low temperature area is provided with a ferroselenide single crystal with good quality, the size is 1.5mm multiplied by 0.5mm, the actual graph is shown in figure 2, and the XRD graph is basically the same as that of figure 3.
Example 4
The embodiment provides a preparation method of ferroferric selenide, which comprises the following steps:
the ferroselenide multiferroic polycrystal was put in a vacuum glove box (H 2 O content is less than 0.01 ppm), adding ferric trichloride powder, grinding and fully mixing to obtain mixed powder, wherein the molar ratio of the ferric selenide polycrystal to the ferric tetrachloride powder is 1:0.7.
Placing the mixed powder into one end of quartz tube, and vacuumizing to make the air pressure of quartz tube mouth be less than 10 -3 Pa, sealing the tube, sealing with adhesive tape, and taking out from the glove box.
And placing the quartz tube into a double-temperature-zone tube furnace (comprising a high-temperature zone and a low-temperature zone), placing one end of the quartz tube, in which the mixed powder is placed, at a high temperature, placing the other end, in which the mixed powder is not placed, in the low-temperature zone, heating the high-temperature zone and the low-temperature zone from the same temperature at the same time, heating the high-temperature zone to 750 ℃, heating the low-temperature zone to 605 ℃ after 7 hours, and preserving the heat for 9 days. And then the heating is stopped in the high temperature area and the low temperature area simultaneously, the tube furnace with the double temperature areas is naturally cooled to room temperature, one end of the quartz tube in the low temperature area is provided with a ferroselenide single crystal with good quality, the size is 2.2mm multiplied by 1mm, the actual graph is shown in figure 2, and the XRD graph is basically the same as that of figure 3.
In summary, the invention provides a ferroselenide three-iron single crystal and a preparation method thereof, the invention adopts a chemical vapor transmission method to successfully prepare the ferroselenide three-iron single crystal for the first time, the blank of the ferroselenide three-iron single crystal in the aspect of single crystal preparation is made up, the preparation method provided by the invention has the advantages of simple steps, short growth period and high success rate (100%), the obtained ferroselenide three-iron single crystal has the advantages of large quantity, good integrity and large size, and is suitable for most conventional research means such as physical property measurement and the like, and meanwhile, the quality of the ferroselenide three-iron single crystal can be ensured to meet various scientific research and application requirements.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.

Claims (10)

1. The preparation method of the ferroselenide ferroferric single crystal is characterized by comprising the following steps:
providing ferroselenide ferroferric polycrystalline powder and a chemical vapor transport agent;
mixing the ferroselenium ferroferric polycrystalline powder and the chemical vapor transport agent to obtain mixed powder;
placing the mixed powder at one end of a quartz tube, vacuumizing and sealing the tube;
heating the quartz tube, keeping the temperature of the end of the quartz tube, on which the mixed powder is placed, at a first preset temperature for a first preset time, keeping the temperature of the end of the quartz tube, on which the mixed powder is not placed, at a second preset temperature for the first preset time, and naturally cooling to obtain the ferroferric selenide monocrystal;
the first preset temperature is 712-750 ℃, and the decomposition temperature of the chemical vapor transport agent is less than or equal to the first preset temperature.
2. The method of claim 1, wherein the molar ratio of the tri-iron tetra-selenide polycrystalline powder to the chemical vapor transport agent is 1:0.5 to 1.
3. The method of claim 2, wherein the molar ratio of the tri-iron tetra-selenide polycrystalline powder to the chemical vapor transport agent is 1:0.65 to 0.75.
4. The method of claim 1, wherein the chemical vapor transport agent comprises at least one of ferric trichloride, ferric tribromide, and ferric triiodide.
5. The method of preparing the ferroselenide polycrystalline powder according to claim 1, wherein the method of preparing the ferroselenide polycrystalline powder comprises the steps of:
mixing iron powder and selenium powder according to a molar ratio of 3:4, then preserving heat for four days at a temperature of 850-950 ℃, and naturally cooling to obtain the ferroselenium three-iron polycrystalline powder.
6. The process according to claim 1, wherein in H 2 And in the environment with the O content less than 0.01ppm, grinding and mixing the ferroferric selenide polycrystalline powder and the chemical vapor transport agent to obtain mixed powder.
7. The method of claim 1, wherein the first predetermined time is 7 to 9 days.
8. The method of claim 7, wherein the second predetermined temperature is 602-607 ℃.
9. The method of manufacturing as set forth in claim 8, wherein the heating the quartz tube to keep the end of the quartz tube where the mixed powder is placed at a first preset temperature for a first preset time, and to keep the end of the quartz tube where the mixed powder is not placed at a second preset temperature for a first preset time, and naturally cooling the end of the quartz tube to obtain the ferroselenide single crystal comprises:
providing a double-temperature-zone tube furnace, wherein the double-temperature zone comprises a first temperature zone and a second temperature zone;
placing the quartz tube in the double-temperature-zone tube furnace, so that one end of the quartz tube, on which mixed powder is placed, is positioned in a first temperature zone, and one end of the quartz tube, on which mixed powder is not placed, is positioned in a second temperature zone;
and (3) starting the double-temperature-zone tube furnace to heat, wherein the temperature of the first temperature zone is 712-750 ℃, the temperature of the second temperature zone is 602-607 ℃, heating the quartz tube, naturally cooling after 7-9 days, and obtaining the ferroselenide three-iron single crystal at one end of the quartz tube, at which the mixed powder is not placed.
10. A ferroselenide single crystal prepared by the method of any one of claims 1 to 9.
CN202311043906.7A 2023-08-17 2023-08-17 Ferroselenide ferroferric single crystal and preparation method thereof Pending CN116971033A (en)

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