CN110257916A - Two-dimensional magnetic semiconductor material MnIn2Se4Preparation method and application in optical detector and field effect transistor - Google Patents
Two-dimensional magnetic semiconductor material MnIn2Se4Preparation method and application in optical detector and field effect transistor Download PDFInfo
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- CN110257916A CN110257916A CN201910519508.5A CN201910519508A CN110257916A CN 110257916 A CN110257916 A CN 110257916A CN 201910519508 A CN201910519508 A CN 201910519508A CN 110257916 A CN110257916 A CN 110257916A
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- 239000000463 material Substances 0.000 title claims abstract description 74
- 239000004065 semiconductor Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 31
- 230000005669 field effect Effects 0.000 title claims abstract description 25
- 230000003287 optical effect Effects 0.000 title claims abstract description 11
- 239000013078 crystal Substances 0.000 claims abstract description 42
- VCGXJCPVJQXBGJ-UHFFFAOYSA-N [In].[Mn][Se] Chemical compound [In].[Mn][Se] VCGXJCPVJQXBGJ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000002360 preparation method Methods 0.000 claims abstract description 26
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052738 indium Inorganic materials 0.000 claims abstract description 18
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 16
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 58
- 239000010453 quartz Substances 0.000 claims description 42
- 239000003708 ampul Substances 0.000 claims description 41
- 239000011669 selenium Substances 0.000 claims description 24
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 13
- 239000011630 iodine Substances 0.000 claims description 13
- 229910052740 iodine Inorganic materials 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 9
- 238000005229 chemical vapour deposition Methods 0.000 claims description 8
- 230000009977 dual effect Effects 0.000 claims description 8
- 230000005389 magnetism Effects 0.000 claims description 7
- 230000005540 biological transmission Effects 0.000 claims description 5
- 239000010432 diamond Substances 0.000 claims description 4
- 229910003460 diamond Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 abstract description 7
- 230000005307 ferromagnetism Effects 0.000 abstract description 4
- 229910052748 manganese Inorganic materials 0.000 abstract description 4
- NMHFBDQVKIZULJ-UHFFFAOYSA-N selanylideneindium Chemical compound [In]=[Se] NMHFBDQVKIZULJ-UHFFFAOYSA-N 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 43
- 239000010410 layer Substances 0.000 description 24
- 239000002994 raw material Substances 0.000 description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 12
- 239000002390 adhesive tape Substances 0.000 description 12
- 229910052710 silicon Inorganic materials 0.000 description 12
- 239000010703 silicon Substances 0.000 description 12
- 239000000377 silicon dioxide Substances 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 238000001259 photo etching Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000004630 atomic force microscopy Methods 0.000 description 2
- 239000011011 black crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000238366 Cephalopoda Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
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- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
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Classifications
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/24—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only semiconductor materials not provided for in groups H01L29/16, H01L29/18, H01L29/20, H01L29/22
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
Abstract
A kind of manganese indium selenium crystal, preparation method, two-dimensional magnetic semiconductor material, optical detector and field effect transistor, the preparation method of the manganese indium selenium crystal, including manganese powder, indium grain, selenium powder are mixed, obtain mixture；It is put into heating equipment and grows after obtained mixture vacuum is enclosed in container, obtain manganese indium selenium crystal.Two-dimensional magnetic semiconductor material of the invention has the excellent photoresponse property for visible light, while showing ferromagnetism when temperature is 2K；Manganese indium selenium crystal is prepared using high temperature process furnances, and crystal structure quality height is, it can be achieved that large scale preparation, no pollution to the environment.
Description
Technical field
The invention belongs to technical field of semiconductor, and in particular to a kind of system of two-dimensional magnetic semiconductor material manganese indium selenium
Preparation Method and the application in terms of optical detector and field effect transistor.
Background technique
From two-dimensional material graphene in 2004 by since successfully preparing, two-dimensional material rapidly becomes most because of its excellent property
For popular material, and application potential is proven to have in multiple fields.It is of greatest concern partly to be led for two dimension in two-dimensional material
Body material.This kind of semiconductor material has atomic-level thickness, therefore is considered to have to construct and breaks through the new of the Moore's Law limit
The material of generation field effect transistor.In addition, the two-dimensional semiconductor material of single layer is usually direct band-gap semicondictor, therefore often
Has excellent photoresponse property.Therefore at present two-dimensional semiconductor material before optoelectronic areas shows huge application
Scape.
However field of optoelectronic devices is confined to for the research of two-dimensional semiconductor device at present, rarely have based on two dimension half
The magnetic device of conductor material is studied.This is because it is very rare to have magnetic two-dimensional semiconductor material.If can succeed
Prepare it is a kind of both there is magnetism, but also with the two-dimensional semiconductor material of preferable photoelectric property, then can be expected to prepare it is novel from
Optically-active electronics and memory device.Therefore successfully prepare be provided simultaneously with magnetic and excellent photoelectric property two-dimensional semiconductor material it is aobvious
It obtains particularly important.
Summary of the invention
In view of this, one of main object of the present invention is to propose a kind of manganese indium selenium crystal, preparation method, two-dimensional magnetic
Property semiconductor material, optical detector and field effect transistor, at least be partially solved in above-mentioned technical problem at least it
One.
To achieve the goals above, as one aspect of the present invention, a kind of preparation method of manganese indium selenium crystal is provided,
Include the following steps:
(1) manganese powder, indium grain, selenium powder are mixed, obtains mixture；
(2) it is put into heating equipment and grows after enclosing the mixture vacuum that step (1) obtains in container, obtain manganese indium selenium
Crystal.
As another aspect of the present invention, manganese indium selenium crystal made from a kind of preparation method as described above is additionally provided.
As an additional aspect of the present invention, a kind of two-dimensional magnetic semiconductor material is additionally provided, by manganese as described above
Indium selenium crystal obtains after being removed.
As another aspect of the invention, a kind of optical detector is additionally provided, has included two-dimensional magnetic as described above
Semiconductor material.
As another aspect of the invention, a kind of field effect transistor is additionally provided, has included as described above two
Tie up magnetic semiconductor material.
Based on the above-mentioned technical proposal it is found that manganese indium selenium crystal of the invention, preparation method, two-dimensional magnetic semiconductor material
Material, optical detector and field effect transistor one of at least have the advantage that compared with the existing technology:
(1) two-dimensional magnetic semiconductor material (MnIn of the present invention2Se4) with the excellent photoresponse for visible light
Property, while ferromagnetism is shown when temperature is 2K；
(2) to the manganese indium selenium (MnIn2Se4) crystalline material progress mechanical stripping, the two-dimensional magnetic of obtained nanometer grade thickness
Property semiconductor material, can be prepared into high performance photodetector, field effect transistor, and have and prepare novel self-spining device
Potentiality；
(3) the manganese indium selenium crystal is prepared using high temperature process furnances, and crystal structure quality is high, it can be achieved that large scale preparation,
No pollution to the environment.
Detailed description of the invention
Fig. 1 is the X-ray diffractogram of the manganese indium selenium crystal prepared in the embodiment of the present invention 1；
Fig. 2 is the x-ray photoelectron spectroscopy figure of the manganese indium selenium crystal prepared in the embodiment of the present invention 1；
Fig. 3 is the atomic force microscopy diagram of the nanoscale manganese indium selenium thin layer two-dimensional material prepared in the embodiment of the present invention 1；
Fig. 4 A is the photoresponse property figure of the field effect transistor prepared in the embodiment of the present invention 1；
Fig. 4 B is the field-effect property figure of the field effect transistor prepared in the embodiment of the present invention 1；
Fig. 5, which is the manganese indium selenium crystal temperature in superconducting quantum interference device (SQUID) prepared in the embodiment of the present invention 1, to be measured when being 2K
Hysteresis loop.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, and reference
Attached drawing, the present invention is described in further detail.
The invention discloses a kind of preparation methods of manganese indium selenium crystal, include the following steps:
(1) manganese powder, indium grain, selenium powder are mixed, obtains mixture；
(2) it is put into heating equipment and grows after enclosing the mixture vacuum that step (1) obtains in container, obtain manganese indium selenium
Crystal.
Wherein, step (2) are executed after transmission medium being first added in the mixture that step (1) obtains again；
Wherein, the transmission medium is iodine；
Wherein, the mass fraction of the iodine is the 5-10% of mixture gross mass.
Wherein, manganese powder described in step (1), indium grain, selenium powder molar ratio be 1: (1.8-2.2): (3.8-4.2), example
For example 1: 2: 4.
Wherein, growing method described in step (2) includes chemical vapor transportation method or chemical vapour deposition technique；
Wherein, the growth time in step (2) in the heating equipment is 3~5 days, for example, 4 days；
Wherein, heating equipment described in step (2) is tube furnace comprising dual temperature area, temperature end temperature are 900-1100
DEG C, be, for example, 950 DEG C, 800-900 DEG C of low-temperature end temperature, be, for example, 880 DEG C, mixture described in step (1) is placed on hot end
Growth；
It wherein, include that heating equipment heats up 10 hours in growth step described in step (2), heat up speed in temperature-rise period
Rate is 90-100 DEG C per hour and temperature end and low-temperature end temperature difference between the two ends are 65-75 DEG C, the temperature difference is, for example, 70 DEG C；
Wherein, after the container equipped with manganese indium selenium crystal being cooled to 20-30 DEG C after growth step described in step (2)
It opens again.
Wherein, the vacuum degree of container described in step (2) is 10-6-10-4It torr, is, for example, 10-5torr；
Wherein, container described in step (2) includes quartz ampoule or close crucible；
Wherein, internal diameter 1-5cm, a length of 15-25cm of the quartz ampoule, for example, 20cm are, for example, 2cm.
Wherein, the structure expression of the manganese indium selenium crystal is MnIn2Se4, structure is diamond structure, and affiliated space group is
The invention also discloses manganese indium selenium crystal made from a kind of preparation method as described above.
The invention also discloses a kind of two-dimensional magnetic semiconductor materials, after manganese indium selenium crystal as described above is removed
It obtains；
Wherein, the stripping means includes mechanical stripping；
Wherein, the two-dimensional magnetic semiconductor material with a thickness of 2-30nm；
Wherein, the interlayer of the two-dimensional magnetic semiconductor material is combined by Van der Waals for, and atom passes through altogether in layer
Valence link combines；
Wherein, the two-dimensional magnetic semiconductor material has magnetism in 2-5K.
The invention also discloses a kind of optical detectors, have included two-dimensional magnetic semiconductor material as described above.
The invention also discloses a kind of field effect transistors, have included two-dimensional magnetic semiconductor material as described above.
In one embodiment, the present invention is for example, by using following technical solution:
A kind of two-dimensional magnetic semiconductor material of the invention not still two-dimensional semiconductor, is also equipped with certain magnetism.Pass through
Chemical vapour deposition technique, successful growth have gone out MnIn2Se4Crystal, and few layer has been prepared using the method for mechanical stripping
MnIn2Se4Layer material.Few layer MnIn2Se4The very excellent photoresponse property for visible light is shown, while low
Ferromagnetism is shown under temperature.This illustrates MnIn2Se4With the potentiality for preparing novel spin, magneto-optic micro-nano device.
The invention belongs to technical field of semiconductor, and in particular to a kind of two-dimensional magnetic semiconductor material manganese indium selenium and its
Preparation method.The two-dimensional magnetic semiconductor material is with the excellent photoresponse property for visible light and at low temperature with iron
Magnetism, therefore be a kind of two-dimentional dilute magnetic semiconductor haveing excellent performance.The preparation method of manganese indium selenium crystal is, with manganese powder, indium grain and
Selenium powder is raw material, and iodine grain is prepared as the carrier of reaction vapor transportation by chemical vapor transportation method.What the present invention obtained
Two-dimentional manganese indium selenium material (two-dimensional magnetic semiconductor material) is two-dimensional structure, and material interlayer is combined by Van der Waals for, layer
Interior atom is combined by covalent bond, and the method being by mechanically pulling off can prepare the layer material with nanometer grade thickness.
Photoelectricity and Magnetic Test the result shows that manganese indium selenium is that a kind of two dimension for being provided simultaneously with excellent photoresponse, field-effect and magnetism is partly led
Body material, therefore there is high application potential in New Type Magneto device and area of Spintronics.
Specifically, two-dimensional magnetic semiconductor material, is made by chemical vapour deposition technique, the material is manganese indium selenium.
The structure expression of the two-dimensional magnetic semiconductor material is MnIn2Se4, it is diamond shape Rhombohedral Xiang Liufang
Structure, affiliated space group are
A kind of preparation method of two-dimensional magnetic material as described above passes through chemistry using manganese powder, indium grain, selenium powder as raw material
Vapour deposition process carries out Material growth, and obtained crystal is two-dimensional magnetic semiconductor material.Wherein, the preparation method includes
Following steps:
(1) manganese powder, indium grain, selenium powder and transmission medium iodine grain are matched and is uniformly mixed according to molar ratio；
(2) raw mixture in step (1) is placed in a quartz ampoule, quartz ampoule is evacuated and hermetically sealed；
(3) quartz ampoule in step (2) is placed in the tube furnace with dual temperature area, is grown by chemical vapour deposition technique
After 4 days, two-dimensional magnetic semiconductor crystalline material is obtained.
Wherein, the manganese powder, indium grain, selenium powder amount be respectively 0.01mol, 0.02mol and 0.04mol, iodine grain quality
For 0.7g.
Wherein, the temperature end in the dual temperature area is 950 DEG C, and low-temperature end is 880 DEG C, during the growth process, reaction raw materials
Mixture is placed in the temperature end.
Wherein, after step (3) further include:
(4) by carrying out mechanical stripping to the two-dimensional magnetic semiconductor crystalline material, the two of nanometer grade thickness can be obtained
Tie up magnetic semiconductor material thin layer.
In one embodiment, the present invention is for example, by using following technical solution:
A kind of two-dimensional magnetic semiconductor material, while there is excellent photoresponse, field benefit and magnetism；The magnetic two dimension half
Conductor material is manganese indium selenium.
Wherein, the chemical expression of manganese indium selenium crystal is MnIn2Se4, structure is Rhombohedral (diamond shape) Xiang Liufang
Structure, affiliated space group are
Wherein, with manganese powder, indium grain and selenium powder as pre-reaction material, using iodine as the load of vapor transportation in reaction process
Body grows to obtain two-dimensional magnetic semiconductor crystalline material by chemical vapor transportation method.
A kind of preparation method of manganese indium selenium crystal the following steps are included:
(1) 0.01 mole of manganese powder, 0.02 mole of indium grain, 0.04 mole of selenium powder and 0.7 gram of iodine grain are placed in a quartz
Guan Zhong, and be uniformly mixed.
(2) mixing material in step (1) is enclosed in quartz ampoule.
(3) it will be vacuumized in the quartz ampoule in step (2), later sealed silica envelope.
(4) mixing material in step (3) is placed in one end of quartz ampoule, and quartz ampoule is placed in the height with dual temperature area
In warm tube furnace.It is grown 4 days by chemical vapor transportation method, so that quartz ampoule is down to room temperature later.
(5) quartz ampoule in step (4) is broken into pieces, the black gray expandable crystal for being attached to inner surface of silica tube is MnIn2Se4
Crystal carefully collects them.
Wherein, step (1) manganese powder, indium grain, selenium powder are respectively 0.01mol, 0.02mol and 0.04mol, iodine grain quality
For 0.7g.
Wherein, quartz ampoule a length of 20cm, internal diameter 2cm described in step (2).
Wherein, vacuum degree described in step (3) is 10-5torr.
Wherein, the temperature end of double temperature-area tubular furnaces described in step (4) is 950 DEG C, and low-temperature end is 880 DEG C.
Wherein, the heating-up time described in step (4) is 10 hours, keeps heating rate constant in temperature-rise period, and high temperature
It is 70 DEG C that end is constant with low-temperature end temperature difference between the two ends.
Wherein, MnIn described in step (5)2Se4Crystal can be by mechanically pulling off the two dimension half that method is prepared into nanometer grade thickness
Conductor material.
Explanation is further elaborated to technical solution of the present invention below by way of specific embodiment combination attached drawing.It should be noted that
, following specific embodiments are only as example, the scope of protection of the present invention is not limited thereto.
Chemicals used in following embodiments and raw material are commercially available gained or are made by oneself by well known preparation method
It obtains.
Embodiment 1
A kind of two-dimensional magnetic semiconductor material (MnIn2Se4) preparation method sequentially include the following steps:
(1) by growth raw material 0.55g manganese powder (Mn), 2.3g indium grain (In), 3.16g selenium powder (Se) and as transporting agent
0.7g iodine grain (I2) (purity is 99.99%) be placed in a test tube, stir.
(2) prepare the quartz ampoule that internal diameter is 2cm, be successively cleaned by ultrasonic 30 minutes using alcohol, acetone and deionized water, set
Enter drying box drying.By quartz ampoule as in high temperature process furnances, 1 hour is kept the temperature at 950 DEG C, it is miscellaneous in quartz ampoule to remove
Matter.It is cooled to room temperature later to quartz ampoule, mixed growth raw material is carefully placed in one end of quartz ampoule.It will be quartzy by vacuum pump
Intraductal atmospheric pressure is evacuated to 10-5Torr is placed and is cooled to room temperature for a period of time to quartz ampoule using oxyhydrogen flame by quartzy channel closure.
(3) quartz ampoule is placed in the tube furnace with dual temperature area, one end that wherein quartz ampoule fills growth raw material is placed in
The temperature end of tube furnace, the other end are then placed in the low-temperature end of tube furnace.By chemical vapour deposition technique carry out Material growth, first
Step-up temperature rate is per hour 100 DEG C, and to temperature end to 1050 DEG C, low-temperature end keeps the temperature 24 hours, heated up to after 980 DEG C
The temperature difference of journey high temperature end and low-temperature end remains 70 DEG C.Second stage, with 10 DEG C per hour of rate of temperature fall by temperature end
It is down to 950 DEG C, low-temperature end is down to 880 DEG C, and the temperature difference of temperature-fall period high temperature end and low-temperature end remains 70 DEG C and keeps the temperature 3
It, is down to room temperature for the temperature of tube furnace with 10 DEG C per hour of rate of temperature fall later.Quartz ampoule is carefully cut into taking-up wherein
Grey black crystal (i.e. manganese indium selenium crystal), X-ray diffraction (XRD) and X-ray photoelectron spectroscopic analysis (XPS) are carried out, such as Fig. 1
And shown in Fig. 2, wherein there is not the simple substance of tri- kinds of elements of Mn, In, Se and the peak position of other compounds, and the test knot of XPS
Also the peak position of the simple substance of tri- kinds of elements of Mn, In, Se is not found in fruit.
(4) by gained MnIn2Se4Crystal, which is placed on Scotch, (to be thought high) on adhesive tape, after doubling adhesive tape 3 to 5 times, by adhesive tape
On there is the position of sample to be carefully attached to the heavily doped silicon on piece with silica oxide layer, with finger with dynamics appropriate repeatedly
Pressure-like product slowly shut down adhesive tape after ten minutes, and the MnIn of nanometer grade thickness can be obtained on silicon wafer2Se4Layer material (i.e. two-dimensional magnetic
Property semiconductor material).Source-drain electrode can be prepared in MnIn by techniques such as photoetching or electron beam exposures2Se4The both ends of thin layer,
Using the silicon dioxide layer of silicon wafer as dielectric, heavily doped silicon is grid, obtains field effect transistor and optical detector.
Fig. 3 is the atomic force microscopy diagram for the manganese indium selenium thin layer two-dimensional material that the present embodiment is prepared, and Fig. 4 A is this reality
Applying example and photoresponse property figure Fig. 4 B of manganese indium selenium thin layer two-dimensional material field effect transistor is prepared is manganese indium selenium thin layer two dimension
Material field effect transistor field-effect property figure, field-effect tube current on/off ratio under the illumination of 532nm is two magnitudes in figure
Illustrate that the field effect transistor that the present embodiment is prepared has excellent field-effect property and for the excellent of visible light wave range
Different photoresponse property, and illumination opening the light than regulating and controlling to the field effect transistor can be passed through.In test process, it is applied to
The voltage of field effect transistor source-drain electrode is 10V.
Fig. 5 is MnIn in the embodiment of the present invention2Se4The magnetic hysteresis measured when temperature is 2K in superconducting quantum interference device (SQUID) is returned
Line chart, in Fig. 5, MnIn2Se4Hysteresis loop in the 2K that superconducting quantum interference device (SQUID) (squid) measures shows MnIn2Se4In temperature
There is ferromagnetism when degree is 2K.
Embodiment 2
A kind of two-dimensional magnetic semiconductor material (MnIn2Se4) preparation method sequentially include the following steps:
(1) by growth raw material 0.55g manganese powder (Mn), 2.53g indium grain (In), 3.32g selenium powder (Se) and as transporting agent
0.7g iodine grain (I2) (purity is 99.99%) be placed in a test tube, stir.
(2) prepare the quartz ampoule that internal diameter is 2cm, be successively cleaned by ultrasonic 30 minutes using alcohol, acetone and deionized water, set
Enter drying box drying.By quartz ampoule as in high temperature process furnances, 1 hour is kept the temperature at 950 DEG C, it is miscellaneous in quartz ampoule to remove
Matter.It is cooled to room temperature later to quartz ampoule, mixed growth raw material is carefully placed in one end of quartz ampoule.It will be quartzy by vacuum pump
Intraductal atmospheric pressure is evacuated to 10-STorr is placed and is cooled to room temperature for a period of time to quartz ampoule using oxyhydrogen flame by quartzy channel closure.
(3) quartz ampoule is placed in the tube furnace with dual temperature area, one end that wherein quartz ampoule fills growth raw material is placed in
The temperature end of tube furnace, the other end are then placed in the low-temperature end of tube furnace.By chemical vapour deposition technique carry out Material growth, first
Step-up temperature rate is per hour 90 DEG C, and to temperature end to 1020 DEG C, low-temperature end keeps the temperature 24 hours, temperature-rise period to after 950 DEG C
The temperature difference of high temperature end and low-temperature end remains 70 DEG C.Second stage is dropped temperature end with 10 DEG C per hour of rate of temperature fall
To 920 DEG C, low-temperature end is down to 850 DEG C, and the temperature difference of temperature-fall period high temperature end and low-temperature end remains 70 DEG C and keeps the temperature 3 days,
The temperature of tube furnace is down to by room temperature with 10 DEG C per hour of rate of temperature fall later.Quartz ampoule is carefully cut and takes out ash therein
Black crystals (i.e. manganese indium selenium crystal)；(4) by gained MnIn2Se4Crystal is placed on Scotch adhesive tape, doubling adhesive tape 3 to 5 times
Afterwards, the position for having sample on adhesive tape is carefully attached to the heavily doped silicon on piece with silica oxide layer, with finger with appropriate
Dynamics pressure-like product slowly shut down adhesive tape after ten minutes repeatedly, the MnIn of nanometer grade thickness can be obtained on silicon wafer2Se4Thin layer material
Expect (i.e. two-dimensional magnetic semiconductor material).Source-drain electrode can be prepared in MnIn by techniques such as photoetching or electron beam exposures2Se4
The both ends of thin layer, using the silicon dioxide layer of silicon wafer as dielectric, heavily doped silicon is grid, obtains field effect transistor and light is visited
Survey device.
Embodiment 3
(1) by growth raw material 0.55g manganese powder (Mn), 2.07g indium grain (In), 3g selenium powder (Se) and as the 0.8g for transporting agent
Iodine grain (I2) (purity is 99.99%) be placed in a test tube, stir.
(2) prepare the quartz ampoule that internal diameter is 2cm, be successively cleaned by ultrasonic 30 minutes using alcohol, acetone and deionized water, set
Enter drying box drying.By quartz ampoule as in high temperature process furnances, 1 hour is kept the temperature at 950 DEG C, it is miscellaneous in quartz ampoule to remove
Matter.It is cooled to room temperature later to quartz ampoule, mixed growth raw material is carefully placed in one end of quartz ampoule.It will be quartzy by vacuum pump
Intraductal atmospheric pressure is evacuated to 10-STorr is placed and is cooled to room temperature for a period of time to quartz ampoule using oxyhydrogen flame by quartzy channel closure.
(3) quartz ampoule is placed in the tube furnace with dual temperature area, one end that wherein quartz ampoule fills growth raw material is placed in
The temperature end of tube furnace, the other end are then placed in the low-temperature end of tube furnace.By chemical vapour deposition technique carry out Material growth, first
Step-up temperature rate is per hour 10 DEG C, and to temperature end to 1080 DEG C, low-temperature end keeps the temperature 24 hours, heated up to after 1010 DEG C
The temperature difference of journey high temperature end and low-temperature end remains 70 DEG C.Second stage, with 95 DEG C per hour of rate of temperature fall by temperature end
It is down to 980 DEG C, low-temperature end is down to 910 DEG C, and the temperature difference of temperature-fall period high temperature end and low-temperature end remains 70 DEG C and keeps the temperature 3
It, is down to room temperature for the temperature of tube furnace with 10 DEG C per hour of rate of temperature fall later.Quartz ampoule is carefully cut into taking-up wherein
Grey black crystal (i.e. manganese indium selenium crystal)；(4) by gained MnIn2Se4Crystal is placed on Scotch adhesive tape, doubling adhesive tape 3 to
After 5 times, the position for having sample on adhesive tape is carefully attached to the heavily doped silicon on piece with silica oxide layer, with finger with suitable
When dynamics pressure-like product slowly shut down adhesive tape after ten minutes repeatedly, the MnIn of nanometer grade thickness can be obtained on silicon wafer2Se4Thin layer
Material (i.e. two-dimensional magnetic thin layers of semiconductor material).Source-drain electrode can be prepared in by techniques such as photoetching or electron beam exposures
MnIn2Se4The both ends of thin layer, using the silicon dioxide layer of silicon wafer as dielectric, heavily doped silicon is grid, obtains field effect transistor
Pipe and optical detector.
Particular embodiments described above has carried out further in detail the purpose of the present invention, technical scheme and beneficial effects
Describe in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in protection of the invention
Within the scope of.
Claims (10)
1. a kind of preparation method of manganese indium selenium crystal, includes the following steps:
(1) manganese powder, indium grain, selenium powder are mixed, obtains mixture；
(2) it is put into heating equipment and grows after enclosing the mixture vacuum that step (1) obtains in container, it is brilliant to obtain manganese indium selenium
Body.
2. preparation method according to claim 1, which is characterized in that
Step (2) are executed after transmission medium is first added in the mixture that step (1) obtains again；
Preferably, the transmission medium is iodine；
As further preferred, the mass fraction of the iodine is the 5-10% of mixture gross mass.
3. preparation method according to claim 1, which is characterized in that
Manganese powder described in step (1), indium grain, selenium powder molar ratio be 1: (1.8-2.2): (3.8-4.2), preferably 1: 2: 4.
4. preparation method according to claim 1, which is characterized in that
Growing method described in step (2) includes chemical vapor transportation method or chemical vapour deposition technique；
Preferably, the growth time in step (2) in the heating equipment is 3~5 days, preferably 4 days；
Preferably, heating equipment described in step (2) is tube furnace comprising dual temperature area, temperature end temperature are 900-1100
DEG C, preferably 950 DEG C, 800-900 DEG C of low-temperature end temperature, preferably 880 DEG C, by mixture described in step (1) be placed on hot end growth；
It include that heating equipment heats up 10 hours in growth step described in step (2), in temperature-rise period as further preferred
Heating rate be per hour 90-100 DEG C and temperature end and low-temperature end temperature difference between the two ends be 65-75 DEG C, preferably 70 DEG C of the temperature difference；
Preferably, after the container equipped with manganese indium selenium crystal is cooled to 20-30 DEG C after growth step described in step (2)
It opens again.
5. preparation method according to claim 1, which is characterized in that
The vacuum degree of container described in step (2) is 10-6-10-4Torr, preferably 10-5torr；
Preferably, container described in step (2) includes quartz ampoule or close crucible；
As further preferred, a length of 15-25cm of the quartz ampoule, preferably 20cm, internal diameter 1-5cm, preferably 2cm.
6. preparation method according to claim 1, which is characterized in that
The structure expression of the manganese indium selenium crystal is MnIn2Se4, structure is diamond structure, and affiliated space group is
7. manganese indium selenium crystal made from a kind of preparation method as claimed in any one of claims 1 to 6.
8. a kind of two-dimensional magnetic semiconductor material, which is characterized in that remove manganese indium selenium crystal as claimed in claim 7
After obtain；
Preferably, the stripping means includes mechanical stripping；
Preferably, the two-dimensional magnetic semiconductor material with a thickness of 2-30nm；
Preferably, the layer of the two-dimensional magnetic semiconductor material is asked and combined by Van der Waals for, atom passes through altogether in layer
Valence link combines；
Preferably, the two-dimensional magnetic semiconductor material has magnetism in 2-5K.
9. a kind of optical detector, which is characterized in that included two-dimensional magnetic semiconductor material as claimed in claim 8.
10. a kind of field effect transistor, which is characterized in that included two-dimensional magnetic semiconductor material as claimed in claim 8.
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