CN116564706A - Magnetic semiconductor film and preparation method thereof - Google Patents
Magnetic semiconductor film and preparation method thereof Download PDFInfo
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- CN116564706A CN116564706A CN202210100300.1A CN202210100300A CN116564706A CN 116564706 A CN116564706 A CN 116564706A CN 202210100300 A CN202210100300 A CN 202210100300A CN 116564706 A CN116564706 A CN 116564706A
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title description 15
- 239000000758 substrate Substances 0.000 claims abstract description 135
- 238000000151 deposition Methods 0.000 claims abstract description 41
- 230000008021 deposition Effects 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 35
- 238000010438 heat treatment Methods 0.000 claims abstract description 32
- 239000000126 substance Substances 0.000 claims abstract description 16
- 238000004140 cleaning Methods 0.000 claims abstract description 9
- 239000010408 film Substances 0.000 claims description 67
- 239000010409 thin film Substances 0.000 claims description 27
- 239000007789 gas Substances 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000013078 crystal Substances 0.000 claims description 15
- 238000000427 thin-film deposition Methods 0.000 claims description 13
- 239000013077 target material Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229910002367 SrTiO Inorganic materials 0.000 claims description 7
- 229910020068 MgAl Inorganic materials 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 230000000903 blocking effect Effects 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 230000007704 transition Effects 0.000 abstract description 11
- 238000001816 cooling Methods 0.000 abstract description 10
- 229910052748 manganese Inorganic materials 0.000 abstract description 9
- 230000000052 comparative effect Effects 0.000 description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000004544 sputter deposition Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 230000005389 magnetism Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 238000004549 pulsed laser deposition Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- CVXNLQMWLGJQMZ-UHFFFAOYSA-N arsenic zinc Chemical compound [Zn].[As] CVXNLQMWLGJQMZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005307 ferromagnetism Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/14—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates
- H01F41/20—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates by evaporation
- H01F41/205—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates by evaporation by laser ablation, e.g. pulsed laser deposition [PLD]
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/28—Vacuum evaporation by wave energy or particle radiation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/40—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials of magnetic semiconductor materials, e.g. CdCr2S4
- H01F1/401—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials of magnetic semiconductor materials, e.g. CdCr2S4 diluted
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F10/00—Thin magnetic films, e.g. of one-domain structure
- H01F10/08—Thin magnetic films, e.g. of one-domain structure characterised by magnetic layers
- H01F10/10—Thin magnetic films, e.g. of one-domain structure characterised by magnetic layers characterised by the composition
- H01F10/18—Thin magnetic films, e.g. of one-domain structure characterised by magnetic layers characterised by the composition being compounds
- H01F10/193—Magnetic semiconductor compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention provides a method for preparing a magnetic semiconductor film, which comprises the following steps: (1) Placing a polycrystalline magnetic semiconductor target into a film deposition chamber; (2) Respectively placing a K simple substance and a Mn simple substance serving as beam source materials into two beam source furnaces; (3) Cleaning a substrate, and then mounting the cleaned substrate on a substrate table; (4) Then, heating the substrate table and thereby heating the substrate; (5) Controlling the air pressure of the film deposition chamber to be 6-100Pa through nonreactive gas, and then epitaxially growing a film on the substrate by using a molecular beam auxiliary pulse laser deposition method; (6) After the film growth is completed, the film is adjustedThe air pressure of the deposition chamber and cooling the substrate to obtain a magnetic semiconductor film (Ba 1‑x K x )(Zn 1‑y Mn y ) 2 As 2 Wherein 0.08<x≤0.40，0.15<y is less than or equal to 0.30. The invention also provides a magnetic semiconductor film prepared by the method. The method can improve the content of K and Mn in the film, thereby improving the paramagnetic-ferromagnetic transition temperature of the film.
Description
Technical Field
The invention belongs to the field of magnetic semiconductors. In particular, the invention relates to a magnetic semiconductor film with spin doping and charge doping separated from each other and a preparation method thereof.
Background
Semiconductor thin films and magnetic thin films are two major types of base materials for modern information science and technology, wherein semiconductor thin films based on charge physical properties are the material base of integrated circuits, solid-state microwave and laser devices, etc., while magnetic thin films based on spin physical properties are the material base of information storage devices and spintronics devices.
As semiconductor lithographic feature sizes continue to decrease so as to approach physical limits on the nanometer scale, it is becoming a challenge whether current state of the art systems developed based on the original physical effects can continue. Breakthrough in new materials including various quantum materials capable of quantum computation, and magnetic semiconductor materials having both semiconductor characteristics and magnetism themselves, has been actively pursued. With the development of information science and technology, there is a need for preparing thin film materials for research into the new material.
The research of the magnetic semiconductor starts in the sixties of the 20 th century, and the concentrated magnetic semiconductor represented by sulfide of Eu and Cr, and the II-VI family diluted magnetic semiconductor, the III-V family diluted magnetic semiconductor and the diluted magnetic oxide caused by doping of magnetic elements are successively experienced, which are several typical material research stages.
A common feature of the above-mentioned classes of magnetically dilute semiconductor materials is that the doping of the magnetic element itself introduces spin doping, which, while introducing magnetism into the material, inevitably also results in a change in the charge doping level of the material. It is believed that spin doping and charge doping in the material must be better compatible.
In recent years, mixThe advent of the hybrid zinc-arsenic based diluted magnetic semiconductor material provides a brand new material research platform (Nat. Commun.2 (2011)) for respectively researching spin doping regulation and charge doping regulation in one material, wherein (Ba) 1-x K x )(Zn 1-y Mn y ) 2 As 2 The polycrystalline system further increased the paramagnetic-ferromagnetic transition temperature (Tc) to 230K (chip. Sci. Bull.59,2524 (2014)), exceeding the record of the 200K curie temperature in the (Ga, mn) As system (nano. Letters.11, 2584 (2011)).
Currently, (Ba) 1-x K x )(Zn 1-y Mn y ) 2 As 2 The films were prepared by Pulsed Laser Deposition (PLD) method (AIP Advance 7,045017 (2017)). The study is currently faced with the following obstacles: the Mn content is lower than or equal to 15%; the content of K is lower and less than or equal to 8 percent. The low Mn doping concentration means that the magnetic ion concentration is low, and the magnetism of the sample is directly influenced; while low K doping concentration means low carrier concentration, which may also affect the ferromagnetism of the sample. Both ultimately result in (Ba 1-x K x )(Zn 1-y Mn y ) 2 As 2 The Tc of the film is lower than 10K and the magnetization is also weak, which greatly limits (Ba 1- x K x )(Zn 1-y Mn y ) 2 As 2 Application prospect of the film. How to regulate the doping content of K, mn and how to increase their content, thereby increasing Tc, becomes (Ba 1-x K x )(Zn 1-y Mn y ) 2 As 2 Emphasis and difficulty in the study of diluted magnetic semiconductors.
Therefore, there is an urgent need for a method capable of increasing (Ba 1-x K x )(Zn 1-y Mn y ) 2 As 2 Method for the K and Mn content of films.
Disclosure of Invention
The object of the present invention is to provide a process for preparing (Ba 1-x K x )(Zn 1-y Mn y ) 2 As 2 A method for forming a thin film, which can increase the K and Mn contents in the thin film, thereby increasing the paramagnetic-ferromagnetic transition temperature (Tc) of the thin film. Tool withIn a bulk way, the film material prepared by the method can improve the Tc of the existing film material from 9K to 160K. It is a further object of the present invention to provide a film material made by the method of the present invention.
The above object of the present invention is achieved by the following technical solutions.
In the context of the present invention, the deposition apparatus of the present invention may employ apparatus already disclosed in the prior art, such as the deposition apparatus disclosed in CN 202576547U. The thin film deposition apparatus includes a thin film deposition chamber including: the cavity shell surrounds a cavity of the film deposition cavity; the target bracket is arranged in the middle of the cavity and is used for placing a target formed by the component A; the substrate table is arranged in the middle of the cavity and is opposite to the target bracket; the laser entrance port is arranged on the side surface of the cavity shell, is obliquely opposite to the target bracket and is used for entering laser to bombard a target on the target bracket to generate plasma plume; the beam source furnace interface is arranged on the side surface of the cavity shell and obliquely opposite to the substrate table and is used for inputting a molecular beam composed of the component B; the laser entrance port and the beam source furnace interface are used for simultaneously entering laser and molecular beam.
In one aspect, the present invention provides a method of preparing a magnetic semiconductor thin film, comprising the steps of:
(1) Placing a polycrystalline magnetic semiconductor target into a film deposition chamber;
(2) Respectively placing a K simple substance and a Mn simple substance serving as beam source materials into two beam source furnaces;
(3) Cleaning a substrate, and then mounting the cleaned substrate on a substrate table;
(4) Then, heating the substrate table and thereby heating the substrate;
(5) Controlling the air pressure of the film deposition chamber to be 6-100Pa, preferably 15-75Pa by using non-reactive gas, and then epitaxially growing a film on the substrate by using a molecular beam auxiliary pulse laser deposition method;
(6) After the film growth is completed, the air pressure of the film deposition chamber is adjusted and the substrate is cooled to obtain a magnetic semiconductor film (Ba 1-x K x )(Zn 1-y Mn y ) 2 As 2 Wherein 0.08<x≤0.40，0.15<y is less than or equal to 0.30; preferably, 0.18.ltoreq.x.ltoreq. 0.40,0.23.ltoreq.y.ltoreq.0.30.
The inventors of the present application have unexpectedly found that, in the preparation of a magnetic semiconductor thin film, the use of a non-reactive gas to control the pressure of the deposition chamber during thin film growth, while using elemental K and elemental Mn as beam source materials, can increase the content of K and Mn in the obtained thin film material, thereby increasing Tc. Without wishing to be bound by theory, this may be due to the fact that adjusting the pressure of the deposition chamber as the film grows may better bind the plasma plume from the pulsed laser striking the target between the target and the substrate, increasing the deposition efficiency and reducing the escape of elements in the plasma plume. In addition, the K element and Mn element can increase the content of the K element and Mn element in the plasma plume, thereby increasing the content of the doped element in the film, even the content thereof can break through the range of the target material content, as in the embodiment 2 of the invention, the target material component is Ba 0.7 K 0.3 (Zn 0.85 Mn 0.15 ) 2 As 2 While the film has a composition of Ba 0.67 K 0.33 (Zn 0.75 Mn 0.25 ) 2 As 2 It is evident that the content of doping elements in the film is already higher than the content of doping elements in the target.
In one embodiment of the present invention, the adjusting of the air pressure of the thin film deposition chamber and the cooling of the substrate in step (6) are performed by a method comprising the steps of: and introducing non-reactive gas into the film deposition chamber to adjust the air pressure of the film deposition chamber to 0.1-0.8 atmosphere, cooling the substrate to 250-300 ℃, keeping for 10-30min, and naturally cooling to room temperature.
Preferably, in the method of the present invention, the composition of the polycrystalline magnetic semiconductor target is represented by the following chemical formula: ba (Ba) 1-m K m (Zn 1-n Mn n ) 2 As 2 Wherein m is more than or equal to 0.10 and less than or equal to 0.30,0.10, n is more than or equal to 0.30; preferably, 0.25.ltoreq.m.ltoreq. 0.30,0.15.ltoreq.n.ltoreq.0.20.
Preferably, in the method according to the present invention, after step (3) and before step (4), the method further comprises the steps of:
the height of the substrate table is adjusted to enable the distance between the target material and the substrate to be 2-4cm; and evacuating the thin film deposition chamber such that the vacuum level in the thin film deposition chamber is higher than 1×10 -6 Pa。
Preferably, in the method of the present invention, the heating of the substrate stage in the step (4) is performed by heating the temperature of the substrate to 500-550 ℃ at a heating rate of 10-30 ℃/min.
Preferably, in the method according to the present invention, after step (4) and before step (5), the method further comprises the steps of:
blocking the substrate by using a baffle plate, and then treating the surface of the target material by using pulse laser, wherein the number of pulses is 600-1200; and heating the two beam source furnaces.
Preferably, in the method of the present invention, the heating of the two beam source furnaces is performed by heating the temperature of the beam source furnace charged with the K element to 100 to 300 ℃ and the temperature of the beam source furnace charged with the Mn element to 600 to 950 ℃.
Preferably, in the method of the present invention, the substrate is selected from (001) -oriented SrTiO 3 Single crystal substrate, (001) -oriented Si single crystal substrate, (001) -oriented MgAl 2 O 4 Single crystal substrate or (001) -oriented (La 0.272 Sr 0.728 )(Al 0.648 Ta 0.352 )O 3 A single crystal substrate.
Preferably, in the method of the present invention, the epitaxially growing film in the step (5) is performed under the following conditions: the energy density of the pulse laser is 120-160mJ/mm 2 The laser repetition frequency is 1-5Hz.
Preferably, in the method of the present invention, the non-reactive gas is selected from one or more of argon, helium and nitrogen.
In another aspect, the present invention provides a magnetic semiconductor thin film prepared by the method of the present invention, the composition of which is represented by the following chemical formula: (Ba) 1-x K x )(Zn 1-y Mn y ) 2 As 2 Wherein 0.08<x≤0.40， 0.15<y≤0.30。
The invention has the following beneficial effects:
the method can prepare a high-quality single-phase single-orientation epitaxial film along a c-axis, improves the content of K and Mn in the film, and further improves the paramagnetic-ferromagnetic transition temperature (Tc) of the film, wherein the Tc can reach 160K at most. The material prepared by the invention has potential application prospect in electronic devices.
Drawings
Embodiments of the present invention are described in detail below with reference to the attached drawing figures, wherein:
FIG. 1 is a schematic view showing the crystal structure of a thin film material prepared according to an embodiment of the present invention. FIG. 1 shows that the crystal structure satisfies space group I4/mmm, and the chemical formula is AB 2 C 2 . Corresponding to the material of the invention, the A site is Ba atom and the substitution site is doped with K atom; the B site is Zn atom, and substitution site is doped with Mn atom; the C position is an As atom.
Fig. 2 is an X-ray diffraction full spectrum of the diluted magnetic semiconductor thin film prepared in example 1 according to the present invention.
FIG. 3 is an M-T graph of a diluted magnetic semiconductor thin film prepared according to example 1 of the present invention; wherein the applied external field is 1000Oe.
Fig. 4 is an X-ray diffraction full spectrum of the diluted magnetic semiconductor thin film prepared in example 2 according to the present invention.
FIG. 5 is an M-T graph of a diluted magnetic semiconductor thin film prepared according to example 2 of the present invention; wherein the applied external field is 1000Oe.
Fig. 6 is an X-ray diffraction full spectrum of the diluted magnetic semiconductor thin film prepared in example 3 according to the present invention.
FIG. 7 is an M-T graph of a diluted magnetic semiconductor thin film prepared according to example 3 of the present invention; wherein the applied external field is 1000Oe.
Fig. 8 is an X-ray diffraction full spectrum of the diluted magnetic semiconductor thin film prepared in comparative example 1 according to the present invention.
FIG. 9 is an M-T graph of a diluted magnetic semiconductor thin film prepared according to comparative example 1 of the present invention; wherein the applied external field is 1000Oe.
FIG. 10 is an X-ray diffraction pattern of the diluted magnetic semiconductor thin film prepared in comparative example 2 according to the present invention.
FIG. 11 is an M-T graph of a diluted magnetic semiconductor thin film prepared in accordance with comparative example 2 of the present invention; wherein the applied external field is 1000Oe.
FIG. 12 is an X-ray diffraction pattern of the diluted magnetic semiconductor thin film prepared in comparative example 3 according to the present invention.
Detailed Description
The following detailed description of the invention is provided in connection with the accompanying drawings that are presented to illustrate the invention and not to limit the scope thereof.
Example 1
(1) Preparation of polycrystalline Ba 0.7 K 0.3 (Zn 0.85 Mn 0.15 ) 2 As 2 And fixing the target on a target support, and then loading the target support into the thin film deposition chamber.
(2) And respectively placing beam source materials consisting of K simple substance and Mn simple substance into two beam source furnaces.
(3) Preparation of (001) -oriented SrTiO 3 And ultrasonically cleaning the monocrystalline substrate by using acetone and alcohol for 5 minutes, drying by using compressed nitrogen, mounting the cleaned substrate on a substrate table through a feed inlet, and adjusting the position of the substrate table to enable the target to be right below the substrate. The distance between the target and the substrate is controlled to be about 2 cm.
(4) The multistage vacuum pump is turned on when the vacuum degree of the chamber is better than 1×10 -6 At Pa, heating of the substrate table is started, and the substrate temperature is heated to 540 ℃ at a heating rate of 30 ℃/min.
(5) When the vacuum degree of the vacuum chamber is better than 2 multiplied by 10 -5 And when Pa, closing a valve between the chamber and the molecular pump, and introducing Ar gas to the chamber through the inflation system until the pressure of the chamber is 15Pa. The substrate was blocked with a baffle plate and then the target surface was pre-sputtered with a pulsed laser with a number of pulses of approximately 600. At the same time heat respectivelyTwo beam source furnaces are provided with two beam source materials, K and Mn.
(6) After the pre-sputtering is completed, the baffle is removed, so that plasma plumes obtained by pulse laser bombardment of the target material and K, mn beams obtained by a heating beam source furnace are deposited on the substrate, namely, a molecular beam auxiliary pulse laser deposition method is used for growing films on the substrate, the deposition pulse number is 1200, and the deposition time is 5min.
(7) After the film grows, ar gas is introduced to the air pressure of the film deposition chamber of 0.1 atmosphere, the temperature of the substrate is reduced to 300 ℃ at the cooling rate of 10 ℃/min, the substrate is kept for 30min, and then the heater is turned off, so that the substrate is naturally cooled to the room temperature.
The diluted magnetic semiconductor film prepared in this example was single-phase, single-orientation epitaxially grown (Ba) 0.82 K 0.18 )(Zn 0.70 Mn 0.30 ) 2 As 2 The XRD diffraction of the film is shown in figure 2, and the M-T test result is shown in figure 3. FIG. 2 shows that the sample is grown in the (001) orientation SrTiO 3 Single-phase, single-orientation epitaxial growth (Ba) along the c-axis on a substrate 1-x K x )(Zn 1-y Mn y ) 2 As 2 A film. Fig. 3 shows that the paramagnetic-ferromagnetic transition temperature of the sample is 120K.
Example 2
(1) Preparation of polycrystalline Ba 0.7 K 0.3 (Zn 0.85 Mn 0.15 ) 2 As 2 And fixing the target on a target support, and then loading the target support into the thin film deposition chamber.
(2) And respectively placing beam source materials consisting of K simple substance and Mn simple substance into two beam source furnaces.
(3) Preparation of (001) -oriented MgAl 2 O 4 And ultrasonically cleaning the monocrystalline substrate by using acetone and alcohol for 5 minutes, drying by using compressed nitrogen, mounting the cleaned substrate on a substrate table through a feed inlet, and adjusting the position of the substrate table to enable the target to be right below the substrate. The distance between the target and the substrate is controlled to be about 2.5 cm.
(4) The multistage vacuum pump is turned on when the vacuum degree of the chamber is better than 1×10 -6 At Pa, heating of the substrate table is started, and the substrate temperature is heated to 550 ℃ at a heating rate of 20 ℃/min.
(5) When the vacuum degree of the vacuum chamber is better than 2 multiplied by 10 -5 And when Pa, closing a valve between the chamber and the molecular pump, and introducing Ar gas to the chamber through the inflation system until the pressure of the chamber is 45Pa. The substrate was blocked with a baffle plate and then the target surface was pre-sputtered with a pulsed laser with a number of pulses of approximately 600. Simultaneously, two beam source furnaces respectively filled with two beam source materials of K and Mn are heated.
(6) After the pre-sputtering is completed, the baffle is removed, so that plasma plumes obtained by pulse laser bombardment of the target material and K, mn beams obtained by a heating beam source furnace are deposited on the substrate, namely, a molecular beam auxiliary pulse laser deposition method is used for growing films on the substrate, the deposition pulse number is 600, and the deposition time is 5min.
(7) After the film grows, ar gas is introduced to the air pressure of the film deposition chamber of 0.1 atmosphere, the temperature of the substrate is reduced to 300 ℃ at the cooling rate of 10 ℃/min, the substrate is kept for 30min, and then the heater is turned off, so that the substrate is naturally cooled to the room temperature.
The diluted magnetic semiconductor film prepared in this example was single-phase, single-orientation epitaxially grown (Ba) 0.67 K 0.33 )(Zn 0.75 Mn 0.25 ) 2 As 2 The XRD diffraction of the film is shown in figure 4, and the M-T test result is shown in figure 5. FIG. 4 shows that the sample was MgAl grown in the (001) orientation 2 O 4 Single-phase, single-orientation epitaxial growth (Ba) along the c-axis on a substrate 1-x K x )(Zn 1-y Mn y ) 2 As 2 A film. Fig. 5 shows that the paramagnetic-ferromagnetic transition temperature of the sample is 160K.
Example 3
(1) Preparation of polycrystalline Ba 0.7 K 0.3 (Zn 0.85 Mn 0.15 ) 2 As 2 And fixing the target on a target support, and then loading the target support into the thin film deposition chamber.
(2) And respectively placing beam source materials consisting of K simple substance and Mn simple substance into two beam source furnaces.
(3) Preparing a (001) oriented Si single crystal substrate, sequentially ultrasonically cleaning the Si single crystal substrate for 5 minutes by using acetone and alcohol, drying the Si single crystal substrate by using compressed nitrogen, soaking the Si single crystal substrate for 20 seconds by using an HF solution with the concentration of 2%, and finally washing the residual HF solution by using deionized water and alcohol respectively. The cleaned substrate is arranged on a substrate table through a feed inlet, and then the position of the substrate table is adjusted to ensure that the target is right below the substrate, and the distance between the target and the substrate is controlled to be about 2.0 cm.
(4) The multistage vacuum pump is turned on when the vacuum degree of the chamber is better than 1×10 -6 At Pa, heating of the substrate table is started, and the substrate temperature is heated to 540 ℃ at a heating rate of 20 ℃/min.
(5) When the vacuum degree of the vacuum chamber is better than 2 multiplied by 10 -5 And when Pa, closing a valve between the chamber and the molecular pump, and introducing Ar gas to the chamber through the inflation system until the pressure of the chamber is 75Pa. The substrate was blocked with a baffle plate and then the target surface was pre-sputtered with a pulsed laser with a number of pulses of approximately 600. Simultaneously, two beam source furnaces respectively filled with two beam source materials of K and Mn are heated.
(6) After the pre-sputtering is completed, the baffle is removed, so that plasma plumes obtained by pulse laser bombardment of the target material and K, mn beams obtained by a heating beam source furnace are deposited on the substrate, namely, a molecular beam auxiliary pulse laser deposition method is used for growing films on the substrate, the deposition pulse number is 1200, and the deposition time is 5min.
(7) After the film grows, ar gas is introduced to the air pressure of the film deposition chamber of 0.1 atmosphere, the temperature of the substrate is reduced to 300 ℃ at the cooling rate of 10 ℃/min, the substrate is kept for 30min, and then the heater is turned off, so that the substrate is naturally cooled to the room temperature.
The diluted magnetic semiconductor film prepared in this example was single-phase, single-orientation epitaxially grown (Ba) 0.60 K 0.40 )(Zn 0.77 Mn 0.23 ) 2 As 2 The XRD diffraction of the film is shown in FIG. 6, and the M-T test result is shown in FIG. 7. FIG. 6 shows that the sample was a single-phase, single-orientation epitaxially grown (Ba) on a (001) -oriented Si substrate 1-x K x )(Zn 1- y Mn y ) 2 As 2 A film. FIG. 7 shows the paramagnetic-ferromagnetic transition of the sampleThe temperature was 120K.
Comparative example 1
(1) Preparation of polycrystalline Ba 0.7 K 0.3 (Zn 0.85 Mn 0.15 ) 2 As 2 And fixing the target on a target support, and then loading the target support into the thin film deposition chamber.
(2) Preparation of (001) -oriented SrTiO 3 And ultrasonically cleaning the monocrystalline substrate by using acetone and alcohol for 5 minutes, drying by using compressed nitrogen, mounting the substrate on a substrate table through a feed inlet, and adjusting the position of the substrate table to ensure that the target is right below the substrate, wherein the distance between the target and the substrate is controlled to be about 2 cm.
(4) The multistage vacuum pump is turned on when the vacuum degree of the chamber is better than 1×10 -6 At Pa, heating of the substrate table is started, and the substrate temperature is heated to 540 ℃ at a heating rate of 30 ℃/min.
(5) When the vacuum degree of the vacuum chamber is better than 2 multiplied by 10 -5 And when Pa, closing a valve between the chamber and the molecular pump, and introducing Ar gas to the chamber through the inflation system until the pressure of the chamber is 5Pa. The substrate was blocked with a baffle plate and then the target surface was pre-sputtered with a pulsed laser with a number of pulses of approximately 600.
(6) After the pre-sputtering is completed, the baffle is removed, so that plasma plumes obtained by pulse laser bombarding the target material are deposited on the substrate, the deposition pulse number is 1200, and the deposition time is 5min.
(7) After the film grows, ar gas is introduced to the air pressure of the film deposition chamber of 0.1 atmosphere, the temperature of the substrate is reduced to 300 ℃ at the cooling rate of 10 ℃/min, the substrate is kept for 30min, and then the heater is turned off, so that the substrate is naturally cooled to the room temperature.
The diluted magnetic semiconductor film prepared in this comparative example was single-phase (Ba) 0.91 K 0.09 )(Zn 0.85 Mn 0.15 ) 2 As 2 The XRD diffraction of the film is shown in FIG. 8, and the M-T test result is shown in FIG. 9. FIG. 8 shows that the sample is grown in the (001) orientation SrTiO 3 Single-phase, single-orientation epitaxial growth (Ba) along the c-axis on a substrate 1-x K x )(Zn 1-y Mn y ) 2 As 2 A film. Fig. 9 shows that the paramagnetic-ferromagnetic transition temperature of the sample is 9K. This comparative example shows that if the growth pressure is not within the range required by the present invention and no beam source material is used, the paramagnetic-ferromagnetic transition temperature of the prepared sample is only 9K.
Comparative example 2
(1) Preparation of polycrystalline Ba 0.7 K 0.3 (Zn 0.85 Mn 0.15 ) 2 As 2 And fixing the target on a target support, and then loading the target support into the thin film deposition chamber.
(2) Preparation of (001) -oriented MgAl 2 O 4 And ultrasonically cleaning the monocrystalline substrate by using acetone and alcohol for 5 minutes, drying by using compressed nitrogen, mounting the cleaned substrate on a substrate table through a feed inlet, and adjusting the position of the substrate table to enable the target to be right below the substrate. The distance between the target and the substrate is controlled to be about 2.5 cm.
(4) The multistage vacuum pump is turned on when the vacuum degree of the chamber is better than 1×10 -6 At Pa, heating of the substrate table is started, and the substrate temperature is heated to 550 ℃ at a heating rate of 20 ℃/min.
(5) When the vacuum degree of the vacuum chamber is better than 2 multiplied by 10 -5 And when Pa, closing a valve between the chamber and the molecular pump, and introducing Ar gas to the chamber through the inflation system until the pressure of the chamber is 40Pa. The substrate was blocked with a baffle plate and then the target surface was pre-sputtered with a pulsed laser with a number of pulses of approximately 600.
(6) After the pre-sputtering is completed, the baffle is removed, so that plasma plumes obtained by pulse laser bombarding the target material are deposited on the substrate, the deposition pulse number is 600, and the deposition time is 5min.
(7) After the film grows, ar gas is introduced to the air pressure of the film deposition chamber of 0.1 atmosphere, the temperature of the substrate is reduced to 300 ℃ at the cooling rate of 10 ℃/min, the substrate is kept for 30min, and then the heater is turned off, so that the substrate is naturally cooled to the room temperature.
The diluted magnetic semiconductor film prepared in this comparative example was single-phase (Ba) 0.85 K 0.15 )(Zn 0.85 Mn 0.15 ) 2 As 2 Film, whichXRD diffraction is shown in FIG. 10, and M-T test results are shown in FIG. 11. FIG. 10 shows the sample as MgAl grown in the (001) orientation 2 O 4 Single-phase, single-orientation epitaxial growth (Ba) along the c-axis on a substrate 1-x K x )(Zn 1- y Mn y ) 2 As 2 A film. Fig. 11 shows that the paramagnetic-ferromagnetic transition temperature of the sample is 70K. This comparative example shows that the paramagnetic-ferromagnetic transition temperature of the prepared sample is not too high if the beam source material is not used even though the growth pressure is within the range required by the present invention.
Comparative example 3
(1) Preparation of Ba 0.7 K 0.3 (Zn 0.85 Mn 0.10 ) 2 As 2 The target (polycrystalline) is fixed on the target holder, and then the target holder is loaded into the thin film deposition chamber.
(2) Preparation of (001) -oriented SrTiO 3 And ultrasonically cleaning the monocrystalline substrate by using acetone and alcohol for 5 minutes, drying by using compressed nitrogen, mounting the substrate on a substrate table through a feed inlet, and adjusting the position of the substrate table to ensure that the target is right below the substrate, wherein the distance between the target and the substrate is controlled to be about 2.5 cm.
(4) The multistage vacuum pump is turned on when the vacuum degree of the chamber is better than 1×10 -6 At Pa, heating of the substrate table is started, and the substrate temperature is heated to 540 ℃ at a heating rate of 20 ℃/min.
(5) When the vacuum degree of the vacuum chamber is better than 2 multiplied by 10 -5 And when Pa, closing a valve between the chamber and the molecular pump, and introducing Ar gas to the chamber through the inflation system until the pressure of the chamber is 110Pa. The substrate was blocked with a baffle plate and then the target surface was pre-sputtered with a pulsed laser with a number of pulses of approximately 600.
(6) After the pre-sputtering is completed, the baffle is removed, so that plasma plumes obtained by pulse laser bombarding the target material are deposited on the substrate, the deposition pulse number is 1200, and the deposition time is 5min.
(7) After the film grows, ar gas is introduced to the air pressure of the film deposition chamber of 0.1 atmosphere, the temperature of the substrate is reduced to 300 ℃ at the cooling rate of 10 ℃/min, the substrate is kept for 30min, and then the heater is turned off, so that the substrate is naturally cooled to the room temperature.
The diluted magnetic semiconductor film prepared in this comparative example was a film containing a hetero-phase (Ba 1-x K x )(Zn 1-y Mn y ) 2 As 2 The XRD diffraction of the film is shown in FIG. 12. As can be seen from FIG. 12, the impurity phase of the sample is (Ba) along the (103) crystal direction 1-x K x )(Zn 1- y Mn y ) 2 As 2 A film. This comparative example shows that the prepared samples contain a hetero-phase if the growth pressure is outside the range required by the present invention.
Claims (10)
1. A method of preparing a magnetic semiconductor thin film comprising the steps of:
(1) Placing a polycrystalline magnetic semiconductor target into a film deposition chamber;
(2) Respectively placing a K simple substance and a Mn simple substance serving as beam source materials into two beam source furnaces;
(3) Cleaning a substrate, and then mounting the cleaned substrate on a substrate table;
(4) Then, heating the substrate table and thereby heating the substrate;
(5) Controlling the air pressure of the film deposition chamber to be 6-100Pa through nonreactive gas, and then epitaxially growing a film on the substrate by using a molecular beam auxiliary pulse laser deposition method;
(6) After the film growth is completed, the air pressure of the film deposition chamber is adjusted and the substrate is cooled to obtain a magnetic semiconductor film (Ba 1-x K x )(Zn 1-y Mn y ) 2 As 2 Wherein 0.08<x≤0.40，0.15<y≤0.30。
2. The method of claim 1, wherein the composition of the polycrystalline magnetic semiconductor target is represented by the formula: ba (Ba) 1-m K m (Zn 1-n Mn n ) 2 As 2 Wherein m is more than or equal to 0.10 and less than or equal to 0.30,0.10, n is more than or equal to 0.30.
3. The method of claim 1, wherein after step (3) and before step (4), the method further comprises the steps of:
the height of the substrate table is adjusted to enable the distance between the target material and the substrate to be 2-4cm; and evacuating the thin film deposition chamber such that the vacuum level in the thin film deposition chamber is higher than 1×10 -6 Pa。
4. The method of claim 1, wherein the heating of the substrate table in step (4) is performed by heating the temperature of the substrate to 500-550 ℃ at a ramp rate of 10-30 ℃/min.
5. The method of claim 1, wherein after step (4) and before step (5), the method further comprises the steps of:
blocking the substrate by using a baffle plate, and then treating the surface of the target material by using pulse laser, wherein the number of pulses is 600-1200; and heating the two beam source furnaces.
6. The method of claim 5, wherein the heating of the two beam source furnaces is performed by heating the temperature of the beam source furnace charged with the K element to 100-300 ℃ and the temperature of the beam source furnace charged with the Mn element to 600-950 ℃.
7. The method of claim 1, wherein the substrate is selected from (001) oriented SrTiO 3 Single crystal substrate, (001) -oriented Si single crystal substrate, (001) -oriented MgAl 2 O 4 Single crystal substrate or (001) -oriented (La 0.272 Sr 0.728 )(Al 0.648 Ta 0.352 )O 3 A single crystal substrate.
8. The method of claim 1, wherein the epitaxially growing film in step (5) is performed under the following conditions: the energy density of the pulse laser is 120-160mJ/mm 2 The laser repetition frequency is 1-5Hz.
9. The method of claim 1, wherein the non-reactive gas is selected from one or more of argon, helium, and nitrogen.
10. A magnetic semiconductor thin film produced by the method of any one of claims 1 to 9, having a composition represented by the following chemical formula: (Ba) 1-x K x )(Zn 1-y Mn y ) 2 As 2 Wherein 0.08<x≤0.40，0.15<y≤0.30。
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