CN107204225B - Fluorine-based ferromagnetic semiconductor material and preparation method thereof - Google Patents

Fluorine-based ferromagnetic semiconductor material and preparation method thereof Download PDF

Info

Publication number
CN107204225B
CN107204225B CN201610157611.6A CN201610157611A CN107204225B CN 107204225 B CN107204225 B CN 107204225B CN 201610157611 A CN201610157611 A CN 201610157611A CN 107204225 B CN107204225 B CN 107204225B
Authority
CN
China
Prior art keywords
semiconductor material
temperature
powder
ferromagnetic semiconductor
reactant
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201610157611.6A
Other languages
Chinese (zh)
Other versions
CN107204225A (en
Inventor
靳常青
陈碧娟
邓正
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institute of Physics of CAS
Original Assignee
Institute of Physics of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Institute of Physics of CAS filed Critical Institute of Physics of CAS
Priority to CN201610157611.6A priority Critical patent/CN107204225B/en
Publication of CN107204225A publication Critical patent/CN107204225A/en
Application granted granted Critical
Publication of CN107204225B publication Critical patent/CN107204225B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N50/00—Galvanomagnetic devices
    • H10N50/80—Constructional details
    • H10N50/85—Magnetic active materials

Abstract

The present invention provides a kind of fluorine-based ferromagnetic semiconductor material and preparation method thereof, the chemical formula of the fluorine-based ferromagnetic semiconductor material is (Ba1‑xKx)F(Zn1‑yMny) As, wherein x and y indicates atom content, and 0.05≤x≤0.2,0.025≤y≤0.15.Fluorine-based ferromagnetic semiconductor material of the invention is that block shape, purity is high, stability are good；Carrier type is cavity type, and has Negative magnetoresistance effect.

Description

Fluorine-based ferromagnetic semiconductor material and preparation method thereof
Technical field
The present invention relates to magnetic semiconductor materials, and in particular to fluorine-based ferromagnetic semiconductor material and preparation method thereof.
Background technique
Magnetic semiconductor refers to the partial cation in nonmagnetic semiconductor by magnetic transition metal ion or rare earth metal The magnetic semiconductor formed after ionic compartmentation.Magnetic semiconductor has both the property of semiconductor and magnetic material, be a kind of collection magnetic, Light, electricity are in one, low-power consumption semiconductor device.The storage of information may be implemented in magnetic moment based on magnetic semiconductor, The processing of information may be implemented in charge movement based on carrier in magnetic semiconductor.Therefore the magnetic of magnetic semiconductor preparation is utilized (spin) electronic device can realize simultaneously the storage and processing of information, and be expected to bring a new technological revolution.
Ohno H et al. in 1996 (Ohno H., Shen A., Matsukura F.el al.Appl.Phys.Lett., 1996) it grown (Ga, Mn) As film using low temperature molecular beam epitaxy technology (LT-MBE).Then, Akai, H et al. are in 1998 Year (Akai, H., Phys.Rev.Lett.81,3002-3005,1998) utilizes LT-MBE technology growth (In, Mn) As film.
The preparation process of dilute magnetic semiconductor (Ga, Mn) As or (In, Mn) As are very harsh, and can only prepare non-chemical flat The film of weighing apparatus, therefore can not understand and study its macroscopic properties, magnetic origin and working mechanism.And dilute magnetic semiconductor (Ga, Mn) The magnetic moment and carrier of As or (In, Mn) As are all to be provided by same Doped ions Mn, therefore can not regulate and control (Ga, Mn) respectively The electrical property and magnetism of As or (In, Mn) As.
Summary of the invention
For above-mentioned technical problem of the existing technology, the embodiment provides a kind of fluorine-based ferromagnetic semiconductors Material, the chemical formula of the fluorine-based ferromagnetic semiconductor material are (Ba1-xKx)F(Zn1-yMny) As, wherein x and y indicates that atom contains Amount, and 0.05≤x≤0.2,0.025≤y≤0.15.
Preferably, 0.1≤x≤0.2,0.1≤y≤0.15.
Preferably, the crystal structure of the fluorine-based ferromagnetic semiconductor material is tetragonal crystal system.
The embodiments of the present invention also provide a kind of preparation methods of fluorine-based ferromagnetic semiconductor material, including the following steps:
1) it weighs reactant and is uniformly mixed, the atom content ratio of Ba:K:F:Zn:Mn:As is (1- in the reactant X): x:1:(1-y): y:1, wherein 0.05≤x≤0.2,0.025≤y≤0.15；
2) uniformly mixed reactant is subjected to solid phase reaction.
Preferably, further include the following steps:
3) block materials for generating the step 2) are ground；
4) powder for obtaining the step 3) carries out solid phase reaction.
Preferably, the temperature of the solid phase reaction is 700 DEG C~1000 DEG C.
Preferably, the pressure of the solid phase reaction is an atmospheric pressure, and the time is 5~30 hours.
Preferably, the pressure of the solid phase reaction is 1~20GPa, and the time is 1~2 hour.
Preferably, 0.1≤x≤0.2,0.1≤y≤0.15.
Preferably, the reactant is selected from the group that following substance is constituted: BaAs, BaF2, Zn, Mn, KAs, ZnAs, MnAs and As。
Preferably, the reactant is powdered BaAs, BaF2, Zn, As, Mn and KAs.
The present invention is prepared for a kind of fluorine-based ferromagnetic semiconductor material (Ba for belonging to tetragonal crystal system1-xKx)F(Zn1-yMny) As, It is block shape, purity is high, stability are good；Carrier type is cavity type (i.e. p-type), has Electric transport properties abundant；And With Negative magnetoresistance effect.
Detailed description of the invention
Embodiments of the present invention is further illustrated referring to the drawings, in which:
Fig. 1 is the X ray diffracting spectrum of the ferromagnetic semiconductor material according to prepared by the method that embodiment 1 provides；
Fig. 2 is that the ferromagnetic semiconductor material according to prepared by the method that embodiment 1 provides is placed after two months in air X ray diffracting spectrum；
Fig. 3 is the DC magnetic susceptibility and temperature of the ferromagnetic semiconductor material according to prepared by the method that embodiment 1 provides Relation curve；
Fig. 4 is DC magnetic susceptibility and the magnetic field of the ferromagnetic semiconductor material according to prepared by the method that embodiment 1 provides Relation curve；
Fig. 5 is the resistivity of ferromagnetic semiconductor material according to prepared by the method that embodiment 1 provides and the relationship of temperature Curve；
Fig. 6 is the X ray diffracting spectrum of the ferromagnetic semiconductor material according to prepared by the method that embodiment 2 provides；
Fig. 7 is the DC magnetic susceptibility and temperature of the ferromagnetic semiconductor material according to prepared by the method that embodiment 2 provides Relation curve；
Fig. 8 is DC magnetic susceptibility and the magnetic field of the ferromagnetic semiconductor material according to prepared by the method that embodiment 2 provides Relation curve；
Fig. 9 is the resistivity of ferromagnetic semiconductor material according to prepared by the method that embodiment 2 provides and the relationship of temperature Curve；
Figure 10 is the X ray diffracting spectrum of the ferromagnetic semiconductor material according to prepared by the method that embodiment 3 provides；
Figure 11 is the DC magnetic susceptibility and temperature of the ferromagnetic semiconductor material according to prepared by the method that embodiment 3 provides Relation curve；
Figure 12 is DC magnetic susceptibility and the magnetic field of the ferromagnetic semiconductor material according to prepared by the method that embodiment 3 provides Relation curve；
Figure 13 is the resistivity of ferromagnetic semiconductor material according to prepared by the method that embodiment 3 provides and the relationship of temperature Curve；
Figure 14 is the X ray diffracting spectrum of the ferromagnetic semiconductor material according to prepared by the method that embodiment 4 provides；
Figure 15 is the DC magnetic susceptibility and temperature of the ferromagnetic semiconductor material according to prepared by the method that embodiment 4 provides Relation curve；
Figure 16 is DC magnetic susceptibility and the magnetic field of the ferromagnetic semiconductor material according to prepared by the method that embodiment 4 provides Relation curve；
Figure 17 is the resistivity of ferromagnetic semiconductor material according to prepared by the method that embodiment 4 provides and the relationship of temperature Curve；
Figure 18 is the resistivity of ferromagnetic semiconductor material at different temperatures according to prepared by the method that embodiment 4 provides The relation curve of difference and magnetic field；
Figure 19 is the Hall resistance of ferromagnetic semiconductor material according to prepared by the method that embodiment 4 provides and the pass in magnetic field It is curve；
Figure 20 is the X ray diffracting spectrum of the ferromagnetic semiconductor material according to prepared by the method that embodiment 5 provides；
Figure 21 is the DC magnetic susceptibility and temperature of the ferromagnetic semiconductor material according to prepared by the method that embodiment 5 provides Relation curve；
Figure 22 is DC magnetic susceptibility and the magnetic field of the ferromagnetic semiconductor material according to prepared by the method that embodiment 5 provides Relation curve；
Figure 23 is the resistivity of ferromagnetic semiconductor material according to prepared by the method that embodiment 5 provides and the relationship of temperature Curve；
Figure 24 is the X ray diffracting spectrum of the ferromagnetic semiconductor material according to prepared by the method that embodiment 6 provides；
Figure 25 is the DC magnetic susceptibility and temperature of the ferromagnetic semiconductor material according to prepared by the method that embodiment 6 provides Relation curve；
Figure 26 is DC magnetic susceptibility and the magnetic field of the ferromagnetic semiconductor material according to prepared by the method that embodiment 6 provides Relation curve；
Figure 27 is the resistivity of ferromagnetic semiconductor material according to prepared by the method that embodiment 6 provides and the relationship of temperature Curve；
Figure 28 is the X ray diffracting spectrum of the ferromagnetic semiconductor material according to prepared by the method that embodiment 7 provides；
Figure 29 is the DC magnetic susceptibility and temperature of the ferromagnetic semiconductor material according to prepared by the method that embodiment 7 provides Relation curve；
Figure 30 is DC magnetic susceptibility and the magnetic field of the ferromagnetic semiconductor material according to prepared by the method that embodiment 7 provides Relation curve；
Figure 31 is the X ray diffracting spectrum of the ferromagnetic semiconductor material according to prepared by the method that embodiment 8 provides；
Figure 32 is the DC magnetic susceptibility and temperature of the ferromagnetic semiconductor material according to prepared by the method that embodiment 8 provides Relation curve；
Figure 33 is DC magnetic susceptibility and the magnetic field of the ferromagnetic semiconductor material according to prepared by the method that embodiment 8 provides Relation curve；
Figure 34 is the resistivity of ferromagnetic semiconductor material according to prepared by the method that embodiment 8 provides and the relationship of temperature Curve；
Figure 35 is the X ray diffracting spectrum of the ferromagnetic semiconductor material according to prepared by the method that embodiment 9 provides；
Figure 36 is the DC magnetic susceptibility and temperature of the ferromagnetic semiconductor material according to prepared by the method that embodiment 9 provides Relation curve；
Figure 37 is DC magnetic susceptibility and the magnetic field of the ferromagnetic semiconductor material according to prepared by the method that embodiment 9 provides Relation curve；
Figure 38 is the resistivity of ferromagnetic semiconductor material according to prepared by the method that embodiment 9 provides and the relationship of temperature Curve；
Figure 39 is the X ray diffracting spectrum of the ferromagnetic semiconductor material according to prepared by the method that embodiment 10 provides；
Figure 40 is the DC magnetic susceptibility and temperature of the ferromagnetic semiconductor material according to prepared by the method that embodiment 10 provides Relation curve；
Figure 41 is DC magnetic susceptibility and the magnetic field of the ferromagnetic semiconductor material according to prepared by the method that embodiment 10 provides Relation curve；
Figure 42 is the resistivity of ferromagnetic semiconductor material according to prepared by the method that embodiment 10 provides and the pass of temperature It is curve；
Figure 43 is resistance of the ferromagnetic semiconductor material under different magnetic field according to prepared by the method that embodiment 10 provides The relation curve of rate and temperature；
Figure 44 be Figure 43 resistivity and temperature relation curve low-temperature space partial enlarged view；
Figure 45 is the X ray diffracting spectrum of the ferromagnetic semiconductor material according to prepared by the method that embodiment 11 provides；
Figure 46 is the DC magnetic susceptibility and temperature of the ferromagnetic semiconductor material according to prepared by the method that embodiment 11 provides Relation curve；
Figure 47 is DC magnetic susceptibility and the magnetic field of the ferromagnetic semiconductor material according to prepared by the method that embodiment 11 provides Relation curve.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, pass through below in conjunction with attached drawing specific real Applying example, the present invention is described in more detail.
Embodiment 1
The present embodiment provides a kind of preparation methods of ferromagnetic semiconductor material, including the following steps:
1) by 2.547 grams of BaAs powder, 3.506 grams of BaF in the glove box filled with argon gas2Powder, 2.224 grams of Zn powder, 1.498 Gram As powder, 0.330 gram of Mn powder and 0.912 gram of KAs powder uniformly mix that (wherein the atom content ratio of Ba:K:F:Zn:Mn:As is 0.8:0.2:1:0.85:0.15:1), reactant is fitted into niobium pipe, and by the niobium seal of tube under the protection of argon gas；
2) the niobium pipe equipped with reactant is put into the quartz ampoule filled with an atmospheric pressure argon gas, and sealed silica envelope；
3) quartz ampoule is placed in high temperature furnace, 800 DEG C at a temperature of be sintered 20 hours；
4) bulk material obtained after the completion of sintering ground under the protection of argon gas mixing, tabletting, be fitted into niobium pipe simultaneously Sealing；
5) the niobium pipe of step 4) is put into the quartz ampoule filled with an atmospheric pressure argon gas, and sealed silica envelope；
6) quartz ampoule is placed in high temperature furnace, 800 DEG C at a temperature of be sintered 20 hours.
The blocky product that step 6) is obtained is ground into powder, and carries out X-ray diffraction analysis.Fig. 1 is that its X-ray is spread out Map is penetrated, as can be drawn from Figure 1, which belongs to tetragonal crystal system, and identical as the structure of ZrCuSiAs, all diffraction maximums are all The corresponding indices of diffraction are found, and do not have miscellaneous peak, i.e., there is no the reactant for having neither part nor lot in solid phase reaction, illustrate prepared by the above method (the Ba of high-purity is gone out0.8K0.2)F(Zn0.85Mn0.15)As.During carrying out solid phase reaction to reactant, double sintering is advantageous It is sufficiently reacted in reactant, improves the purity of product.
Blocky product prepared by step 6) is placed after two months in air, then carries out X-ray diffraction analysis, Fig. 2 Its X ray diffracting spectrum is shown, there is no miscellaneous peaks in diffraction maximum as can be seen from Figure 2, illustrate that the product can be in air It is stabilized.
Fig. 3 is the DC magnetic susceptibility of sample and the relation curve of temperature, and wherein ZFC is the cold curve of null field, and ZF is the cold song in field Line.(Ba as can be seen from Figure 30.8K0.2)F(Zn0.85Mn0.15) As ferromagnetic transformation temperature Tc=20K.
Fig. 4 is the DC magnetic susceptibility of sample and the relation curve in magnetic field, from Fig. 4 it can be observed that it is with hysteresis loop, Coercivity is 11200Oe.
Fig. 5 is the resistivity of sample and the relation curve of temperature, as can be seen from Figure 5, (Ba0.8K0.2)F(Zn0.85Mn0.15) electricity Resistance rate increases with the reduction of temperature, the conduction property with semiconductor, and due to scattering of spinning, resistance is near Tc Sharply become larger.
Embodiment 2
The present embodiment provides a kind of preparation methods of ferromagnetic semiconductor material, including the following steps:
1) by 2.547 grams of BaAs powder, 3.506 grams of BaF in the glove box filled with argon gas2Powder, 2.355 grams of Zn powder, 1.498 Gram As powder, 0.22 gram of Mn powder and 0.912 gram of KAs powder uniformly mix that (wherein the atom content ratio of Ba:K:F:Zn:Mn:As is 0.8:0.2:1:0.9:0.1:1), reactant is fitted into niobium pipe, and by the niobium seal of tube under the protection of argon gas；
2) the niobium pipe equipped with reactant is put into the quartz ampoule filled with an atmospheric pressure argon gas, and sealed silica envelope；
3) quartz ampoule is placed in high temperature furnace, 850 DEG C at a temperature of be sintered 20 hours；
4) bulk material obtained after the completion of sintering ground under the protection of argon gas mixing, tabletting, be fitted into niobium pipe simultaneously Sealing；
5) niobium pipe is put into the quartz ampoule filled with an atmospheric pressure argon gas, and sealed silica envelope；
6) quartz ampoule is placed in high temperature furnace, 850 DEG C at a temperature of be sintered 20 hours.
The blocky product that step 6) is obtained is ground into powder, and carries out X-ray diffraction analysis.Fig. 6 is that its X-ray is spread out Map is penetrated, as can be drawn from Figure 6, which belongs to tetragonal crystal system, and identical as the structure of ZrCuSiAs, all diffraction maximums are all The corresponding indices of diffraction are found, and do not have miscellaneous peak, i.e., there is no the reactant for having neither part nor lot in solid phase reaction, illustrate prepared by the above method (the Ba of high-purity is gone out0.8K0.2)F(Zn0.9Mn0.1)As。
Fig. 7 is the DC magnetic susceptibility of sample and the relation curve of temperature, and wherein ZFC is the cold curve of null field, and ZF is the cold song in field Line, as can be seen from Figure 7 the ferromagnetic transformation temperature Tc=23K of the material.
Fig. 8 is the DC magnetic susceptibility of sample and the relation curve in magnetic field, from Fig. 8 it can be observed that it is with hysteresis loop, And coercivity is 9110Oe.
Fig. 9 is the resistivity of sample and the relation curve of temperature, as can be seen from Figure 9, (Ba0.8K0.2)F(Zn0.9Mn0.1) As Resistivity increases with the reduction of temperature, the conduction property with semiconductor, and due to scattering of spinning, resistance is attached in Tc Closely sharply become larger.
Embodiment 3
The present embodiment provides a kind of preparation methods of ferromagnetic semiconductor material, including the following steps:
1) by 2.547 grams of BaAs powder, 3.506 grams of BaF in the glove box filled with argon gas2Powder, 2.420 grams of Zn powder, 1.498 Gram As powder, 0.165 gram of Mn powder and 0.912 gram of KAs powder uniformly mix that (wherein the atom content ratio of Ba:K:F:Zn:Mn:As is 0.8:0.2:1:0.925:0.075:1), and by reactant it is fitted into niobium pipe, and by the niobium seal of tube under the protection of argon gas；
2) the niobium pipe equipped with reactant is put into the quartz ampoule filled with an atmospheric pressure argon gas, and sealed silica envelope；
3) quartz ampoule is placed in high temperature furnace, 750 DEG C at a temperature of be sintered 20 hours；
4) bulk material obtained after the completion of sintering ground under the protection of argon gas mixing, tabletting, be fitted into niobium pipe simultaneously Sealing；
5) niobium pipe is put into the quartz ampoule filled with an atmospheric pressure argon gas, and sealed silica envelope；
6) quartz ampoule is placed in high temperature furnace, 750 DEG C at a temperature of be sintered 20 hours.
The blocky product that step 6) is obtained is ground into powder, and carries out X-ray diffraction analysis.Figure 10 is its X-ray Diffracting spectrum, as can be drawn from Figure 10, the reactant belong to tetragonal crystal system, diffraction identical as the structure of ZrCuSiAs, all Peak all finds the corresponding indices of diffraction, and does not have miscellaneous peak, i.e., there is no the reactant for having neither part nor lot in solid phase reaction, illustrates the above method Ferromagnetic semiconductor material (the Ba of high-purity is prepared0.8K0.2)F(Zn0.925Mn0.075)As。
Figure 11 is the DC magnetic susceptibility of sample and the relation curve of temperature, and wherein ZFC is the cold curve of null field, and ZF is the cold song in field Line, as can be seen from Figure 11 the ferromagnetic transformation temperature Tc=15K of the material.
Figure 12 is the DC magnetic susceptibility of sample and the relation curve in magnetic field, from Figure 12 it can be observed that it is returned with magnetic hysteresis Line, coercivity 8680Oe.
Figure 13 is the resistivity of sample and the relation curve of temperature, as can be seen from Figure 13, (Ba0.8K0.2)F(Zn0.925Mn0.075) The resistivity of As increases with the reduction of temperature, the conduction property with semiconductor, and due to scattering of spinning, resistance exists Tc nearby sharply becomes larger.
Embodiment 4
The present embodiment provides a kind of preparation methods of ferromagnetic semiconductor material, including the following steps:
1) by 2.547 grams of BaAs powder, 3.506 grams of BaF in the glove box filled with argon gas2Powder, 2.486 grams of Zn powder, 1.498 Gram As powder, 0.11 gram of Mn powder and 0.912 gram of KAs powder uniformly mix that (wherein the atom content ratio of Ba:K:F:Zn:Mn:As is 0.8:0.2:1:0.95:0.05:1), and by reactant it is fitted into boron nitride (BN) pipe；
2) the BN pipe equipped with reactant is put into the quartz ampoule filled with an atmospheric pressure argon gas, and sealed silica envelope；
3) quartz ampoule is placed in high temperature furnace, 1000 DEG C at a temperature of be sintered 5 hours.
The blocky product that step 3) is obtained is ground into powder, and carries out X-ray diffraction analysis.Figure 14 is its X-ray Diffracting spectrum, it is seen from figure 14 that the product belongs to tetragonal crystal system, diffraction identical as the structure of ZrCuSiAs, all Peak all finds the corresponding indices of diffraction, and does not have miscellaneous peak, i.e., there is no the reactant for having neither part nor lot in solid phase reaction, illustrates the above method (the Ba of high-purity is prepared0.8K0.2)F(Zn0.95Mn0.05)As。
Figure 15 is the DC magnetic susceptibility of sample and the relation curve of temperature, and wherein ZFC is the cold curve of null field, and ZF is the cold song in field Line, as can be seen from Figure 15 (Ba0.8K0.2)F(Zn0.95Mn0.05) As ferromagnetic transformation temperature Tc=14K.
Figure 16 is the DC magnetic susceptibility of sample and the relation curve in magnetic field, from Figure 16 it can be observed that it has than wider Hysteresis loop, coercivity 6410Oe.
Figure 17 is the resistivity of sample and the relation curve of temperature, as can be seen from Figure 17, (Ba0.8K0.2)F(Zn0.95Mn0.05)As Resistivity increase with the reduction of temperature, with semiconductor conduction property, spin scattering due to, resistance is in Tc Nearby sharply become larger.
Figure 18 is the relation curve in sample differential resistivity at different temperatures and magnetic field.(Ba as can be seen from Figure 180.8K0.2)F (Zn0.95Mn0.05) As in 30~150K all have Negative magnetoresistance effect.
Figure 19 is the relation curve of Hall resistance and magnetic field of the sample at 250K, as can be seen from Figure 19 (Ba0.8K0.2)F (Zn0.95Mn0.05) As carrier concentration be 1.21 × 1017cm-3, the type of carrier is p-type.
Embodiment 5
The present embodiment provides a kind of preparation methods of ferromagnetic semiconductor material, including the following steps:
1) by 2.547 grams of BaAs powder, 3.506 grams of BaF in the glove box filled with argon gas2Powder, 2.551 grams of Zn powder, 1.498 Gram As powder, 0.055 gram of Mn powder and 0.912 gram of KAs powder uniformly mix that (wherein the atom content ratio of Ba:K:F:Zn:Mn:As is 0.8:0.2:1:0.975:0.025:1), and by reactant it is fitted into high pressure assembly；
2) high pressure assembly is put into the high-pressure installation filled with 20GPa argon gas, the temperature of high-pressure installation is added from room temperature Heat after sintering 0.5 hour, is down to room temperature and release to 800 DEG C；
3) bulk material for obtaining step 2) grinds mixing under the protection of argon gas, is again loaded into high pressure assembly；
4) high pressure assembly is put into the high-pressure installation filled with 20GPa argon gas, the temperature of high-pressure installation is added from room temperature Heat after sintering 1 hour, is down to room temperature and release to 800 DEG C.
Reactant is subjected to high-pressure sinter, substantially reduces sintering time, and improve sample consistency.
The blocky product that step 4) is obtained is ground into powder, and carries out X-ray diffraction analysis.Figure 20 is its X-ray Diffracting spectrum, as can be drawn from Figure 20, the reactant belong to tetragonal crystal system, diffraction identical as the structure of ZrCuSiAs, all Peak all finds the corresponding indices of diffraction, and does not have miscellaneous peak, i.e., there is no the reactant for having neither part nor lot in solid phase reaction, illustrates the above method (the Ba of high-purity is prepared0.8K0.2)F(Zn0.975Mn0.025)As。
Figure 21 is the DC magnetic susceptibility of sample and the relation curve of temperature, and wherein ZFC is the cold curve of null field, and ZF is the cold song in field Line, as can be seen from Figure 21 (Ba0.8K0.2)F(Zn0.975Mn0.025) As ferromagnetic transformation temperature Tc=10K.
Figure 22 is the DC magnetic susceptibility of sample and the relation curve in magnetic field, from Figure 22 it can be observed that it is returned with magnetic hysteresis Line, and coercivity is 1020Oe.
Figure 23 is the resistivity of sample and the relation curve of temperature, as can be seen from Figure 23, (Ba0.8K0.2)F(Zn0.975Mn0.025) The resistivity of As increases with the reduction of temperature, the conduction property with semiconductor, and due to scattering of spinning, resistance exists Tc nearby sharply becomes larger.
Embodiment 6
The present embodiment provides a kind of preparation methods of ferromagnetic semiconductor material, including the following steps:
1) by 2.971 grams of BaAs powder, 3.506 grams of BaF in the glove box filled with argon gas2Powder, 2.355 grams of Zn powder, 1.498 Gram As powder, 0.22 gram of Mn powder and 0.684 gram of KAs powder uniformly mix that (wherein the atom content ratio of Ba:K:F:Zn:Mn:As is 0.85:0.15:1:0.9:0.1:1), reactant is fitted into niobium pipe, and by the niobium seal of tube under the protection of argon gas；
2) the niobium pipe equipped with reactant is put into the quartz ampoule filled with an atmospheric pressure argon gas, and sealed silica envelope；
3) quartz ampoule is placed in high temperature furnace, 900 DEG C at a temperature of be sintered 20 hours.
The blocky product that step 3) is obtained is ground into powder, and carries out X-ray diffraction analysis.Figure 24 is its X-ray Diffracting spectrum, as can be drawn from Figure 24, the product belong to tetragonal crystal system, diffraction identical as the structure of ZrCuSiAs, all Peak all finds the corresponding indices of diffraction, and does not have miscellaneous peak, i.e., there is no the reactant for having neither part nor lot in solid phase reaction, illustrates the above method (the Ba of high-purity is prepared0.85K0.15)F(Zn0.9Mn0.1)As。
Figure 25 is the DC magnetic susceptibility of sample and the relation curve of temperature, and wherein ZFC is the cold curve of null field, and ZF is the cold song in field Line, as can be seen from Figure 25 (Ba0.85K0.15)F(Zn0.9Mn0.1) As ferromagnetic transformation temperature Tc=30K.
Figure 26 is the DC magnetic susceptibility of sample and the relation curve in magnetic field, from Figure 26 it can be observed that it is returned with magnetic hysteresis Line, coercivity 9067Oe.
Figure 27 is the resistivity of sample and the relation curve of temperature, as can be seen from Figure 27, (Ba0.85K0.15)F(Zn0.9Mn0.1)As Resistivity increase with the reduction of temperature, with semiconductor conduction property, spin scattering due to, resistance is in Tc Nearby sharply become larger.
Embodiment 7
The present embodiment provides a kind of preparation methods of ferromagnetic semiconductor material, including the following steps:
1) in the glove box filled with argon gas by 3.396 grams of BaAs powder, 3.506 grams of BaF2 powder, 2.224 grams of Zn powder, 1.498 Gram As powder, 0.33 gram of Mn powder and 0.456 gram of KAs powder are uniformly mixed, reactant are fitted into niobium pipe, and under the protection of argon gas By the niobium seal of tube；
2) the niobium pipe equipped with reactant is put into the quartz ampoule filled with an atmospheric pressure argon gas, and sealed silica envelope；
3) quartz ampoule is placed in high temperature furnace, 750 DEG C at a temperature of be sintered 20 hours；
4) bulk material obtained after the completion of sintering ground under the protection of argon gas mixing, tabletting, be fitted into niobium pipe simultaneously Sealing；
5) the niobium pipe of step 4) is put into the quartz ampoule filled with an atmospheric pressure argon gas, and sealed silica envelope；
6) quartz ampoule is placed in high temperature furnace, 750 DEG C at a temperature of be sintered 20 hours.
The blocky product that step 6) is obtained is ground into powder, and carries out X-ray diffraction analysis.Figure 28 is its X-ray Diffracting spectrum, as can be drawn from Figure 28, the product belong to tetragonal crystal system, diffraction identical as the structure of ZrCuSiAs, all Peak all finds the corresponding indices of diffraction, and does not have miscellaneous peak, i.e., there is no the reactant for having neither part nor lot in solid phase reaction, illustrates the above method (the Ba of high-purity is prepared0.9K0.1)F(Zn0.85Mn0.15)As。
Figure 29 is the DC magnetic susceptibility of sample and the relation curve of temperature, and wherein ZFC is the cold curve of null field, and ZF is the cold song in field Line, as can be seen from Figure 29 (Ba0.9K0.1)F(Zn0.85Mn0.15) As ferromagnetic transformation temperature Tc=27K.
The DC magnetic susceptibility of Figure 30 sample and the relation curve in magnetic field, from Figure 30 it can be observed that it is with hysteresis loop, Coercivity is 6166Oe.
Embodiment 8
The present embodiment provides a kind of preparation methods of ferromagnetic semiconductor material, including the following steps:
1) by 3.396 grams of BaAs powder, 3.506 grams of BaF in the glove box filled with argon gas2Powder, 2.355 grams of Zn powder, 1.498 Gram As powder, 0.22 gram of Mn powder and 0.456 gram of KAs powder uniformly mix that (wherein the atom content ratio of Ba:K:F:Zn:Mn:As is 0.9:0.1:1:0.9:0.1:1), reactant is fitted into niobium pipe, and by the niobium seal of tube under the protection of argon gas；
2) the niobium pipe equipped with reactant is put into the quartz ampoule filled with an atmospheric pressure argon gas, and sealed silica envelope；
3) quartz ampoule is placed in high temperature furnace, 750 DEG C at a temperature of be sintered 20 hours；
4) bulk material obtained after the completion of sintering ground under the protection of argon gas mixing, tabletting, be fitted into niobium pipe simultaneously Sealing；
5) niobium pipe is put into the quartz ampoule filled with an atmospheric pressure argon gas, and sealed silica envelope；
6) quartz ampoule is placed in high temperature furnace, 750 DEG C at a temperature of be sintered 20 hours.
The blocky product that step 6) is obtained is ground into powder, and carries out X-ray diffraction analysis.Figure 31 is its X-ray Diffracting spectrum, as can be drawn from Figure 31, the reactant belong to tetragonal crystal system, diffraction identical as the structure of ZrCuSiAs, all Peak all finds the corresponding indices of diffraction, and does not have miscellaneous peak, i.e., there is no the reactant for having neither part nor lot in solid phase reaction, illustrates the above method (the Ba of high-purity is prepared0.9K0.1)F(Zn0.9Mn0.1)As。
Figure 32 is the DC magnetic susceptibility of sample and the relation curve of temperature, and wherein ZFC is the cold curve of null field, and ZF is the cold song in field Line, as can be seen from Figure 32 (Ba0.9K0.1)F(Zn0.9Mn0.1) As ferromagnetic transformation temperature Tc=25K.
Figure 33 is the DC magnetic susceptibility of sample and the relation curve in magnetic field, from Figure 33 it can be observed that it is returned with magnetic hysteresis Line, and coercivity is 9060Oe.
Figure 34 is the resistivity of sample and the relation curve of temperature, as can be seen from Figure 34, (Ba0.9K0.1)F(Zn0.9Mn0.1)As Resistivity increase with the reduction of temperature, with semiconductor conduction property, spin scattering due to, resistance is in Tc Nearby sharply become larger.
Embodiment 9
The present embodiment provides a kind of preparation methods of ferromagnetic semiconductor material, including the following steps:
1) by 3.82 grams of BaAs powder, 3.506 grams of BaF in the glove box filled with argon gas2Powder, 2.224 grams of Zn powder, 1.498 Gram As powder, 0.33 gram of Mn powder and 0.228 gram of KAs powder uniformly mix, and reactant is fitted into high pressure assembly；
2) high pressure assembly is put into the high-pressure installation filled with 1GPa argon gas, the temperature of high-pressure installation is heated from room temperature To 1000 DEG C, after sintering 2 hours, it is down to room temperature and release.
The blocky product that step 2) is obtained is ground into powder, and carries out X-ray diffraction analysis.Figure 35 is its X-ray Diffracting spectrum, as can be drawn from Figure 35, the reactant belong to tetragonal crystal system, diffraction identical as the structure of ZrCuSiAs, all Peak all finds the corresponding indices of diffraction, and does not have miscellaneous peak, i.e., there is no the reactant for having neither part nor lot in solid phase reaction, illustrates the above method (the Ba of high-purity is prepared0.95K0.05)F(Zn0.975Mn0.15)As。
Figure 36 is the DC magnetic susceptibility of sample and the relation curve of temperature, and wherein ZFC is the cold curve of null field, and ZF is the cold song in field Line, as can be seen from Figure 36 (Ba0.95K0.05)F(Zn0.975Mn0.15) As ferromagnetic transformation temperature Tc=22K.
Figure 37 is the DC magnetic susceptibility of sample and the relation curve in magnetic field, from Figure 37 it can be observed that it is returned with magnetic hysteresis Line, and coercivity is 8590Oe.
Figure 38 is the resistivity of sample and the relation curve of temperature, as can be seen from Figure 38, (Ba0.95K0.05)F(Zn0.975Mn0.15) The resistivity of As increases with the reduction of temperature, the conduction property with semiconductor, and due to scattering of spinning, resistance exists Tc nearby sharply becomes larger.
Embodiment 10
The present embodiment provides a kind of preparation methods of ferromagnetic semiconductor material, including the following steps:
1) by 3.82 grams of BaAs powder, 3.506 grams of BaF in the glove box filled with argon gas2Powder, 2.355 grams of Zn powder, 1.498 Gram As powder, 0.22 gram of Mn powder and 0.228 gram of KAs powder uniformly mix, and aluminium oxide ceramics examination will be packed into after reactant compression moulding Guan Zhong；
2) by the ceramic test tube Vacuum Package equipped with reactant in quartz ampoule；
3) quartz ampoule is placed in high temperature furnace, 700 DEG C at a temperature of be sintered 30 hours.
The blocky product that step 3) is obtained is ground into powder, and carries out X-ray diffraction analysis.Figure 39 is its X-ray Diffracting spectrum, as can be drawn from Figure 39, the product belong to tetragonal crystal system, diffraction identical as the structure of ZrCuSiAs, all Peak all finds the corresponding indices of diffraction, and does not have miscellaneous peak, i.e., there is no the reactant for having neither part nor lot in solid phase reaction, illustrates the above method (the Ba of high-purity is prepared0.95K0.05)F(Zn0.9Mn0.1)As。
Figure 40 is the DC magnetic susceptibility of sample and the relation curve of temperature, and wherein ZFC is the cold curve of null field, and ZF is the cold song in field Line, as can be seen from Figure 40 (Ba0.95K0.05)F(Zn0.9Mn0.1) As ferromagnetic transformation temperature Tc=19K.
Figure 41 is the DC magnetic susceptibility of sample and the relation curve in magnetic field, from Figure 41 it can be observed that it is returned with magnetic hysteresis Line, coercivity 8293Oe.
Figure 42 is the resistivity of sample and the relation curve of temperature, as can be seen from Figure 42 (Ba0.95K0.05)F(Zn0.9Mn0.1)As Resistivity increase with the reduction of temperature, with semiconductor conduction property, spin scattering due to, resistance is in Tc Nearby sharply become larger.
Figure 43 is the relation curve of the resistivity and temperature under sample different magnetic field, and Figure 44 is the partial enlargement of low-temperature space Figure.From Figure 43-44 it is found that at the same temperature, with the increase in magnetic field, resistance is gradually reduced, illustrate that sample has negative magnetoresistance Effect.
Embodiment 11
The present embodiment provides a kind of preparation methods of ferromagnetic semiconductor material, including the following steps:
1) by 3.82 grams of BaAs powder, 3.506 grams of BaF in the glove box filled with argon gas2Powder, 2.551 grams of Zn powder, 1.498 Gram As powder, 0.055 gram of Mn powder and 0.228 gram of KAs powder uniformly mix that (wherein the atom content ratio of Ba:K:F:Zn:Mn:As is 0.95:0.05:1:0.975:0.025:1), reactant is fitted into niobium pipe, and by the niobium seal of tube under the protection of argon gas；
2) the niobium pipe equipped with reactant is put into the quartz ampoule filled with an atmospheric pressure argon gas, and sealed silica envelope；
3) quartz ampoule is placed in high temperature furnace, 850 DEG C at a temperature of be sintered 25 hours；
4) bulk material obtained after the completion of sintering ground under the protection of argon gas mixing, tabletting, be fitted into niobium pipe simultaneously Sealing；
5) the niobium pipe of step 4) is put into the quartz ampoule filled with an atmospheric pressure argon gas, and sealed silica envelope；
6) quartz ampoule is placed in high temperature furnace, 850 DEG C at a temperature of be sintered 20 hours.
The blocky product that step 6) is obtained is ground into powder, and carries out X-ray diffraction analysis.Figure 45 is its X-ray Diffracting spectrum, from Figure 45, it can be concluded that, which belongs to tetragonal crystal system, diffraction identical as the structure of ZrCuSiAs, all Peak all finds the corresponding indices of diffraction, and does not have miscellaneous peak, i.e., there is no the reactant for having neither part nor lot in solid phase reaction, illustrates the above method (the Ba of high-purity is prepared0.95K0.05)F(Zn0.975Mn0.025)As。
Figure 46 is the DC magnetic susceptibility of sample and the relation curve of temperature, and wherein ZFC is the cold curve of null field, and ZF is the cold song in field Line, as can be seen from Figure 46 (Ba0.95K0.05)F(Zn0.975Mn0.025) As ferromagnetic transformation temperature Tc=16K.
Figure 47 is the DC magnetic susceptibility of sample and the relation curve in magnetic field, from Figure 47 it can be observed that it is returned with magnetic hysteresis Line, coercivity 3588Oe.
In summary, the present invention is prepared for a kind of novel fluorine-based ferromagnetic semiconductor material, belongs to tetragonal crystal system, with The structure of ZrCuSiAs is identical, and chemical formula is (Ba1-xKx)F(Zn1-yMny) As, wherein x and y indicates atom content, and 0.05≤x ≤ 0.2,0.025≤y≤0.15.Prepared fluorine-based ferromagnetic semiconductor material (Ba1-xKx)F(Zn1-yMny) As is block shape, pure Degree is high, stability is good；Carrier type is cavity type (i.e. p-type), has Electric transport properties abundant；And there is negative magnetoresistance effect It answers.
The reactant and its weight chosen in preparation method provided by the above embodiment are exemplary only, according to the present invention Other embodiments, reactant can selected from following substance constitute group: BaAs, BaF2, Zn, Mn, KAs, ZnAs, MnAs and As, preferably powdered BaAs, BaF2, Zn, As, Mn and KAs, it is only necessary to meet the original of Ba:K:F:Zn:Mn:As in reactant Sub- content ratio is (1-x): x:1:(1-y): y:1, wherein 0.05≤x≤0.2,0.025≤y≤0.15；It is preferred that 0.1≤x≤ 0.2,0.1≤y≤0.15.Therefore the atom percentage content of K and Mn be can be controlled separately, to regulate and control fluorine-based ferromagnetic half respectively Conductor material (Ba1-xKx)F(Zn1-yMny) As electrical property and magnetism.
The present invention improves the purity of product using secondary high-temperature sintering.It, can be right in the other embodiment of the present invention Reactant be sintered more than secondary high-temperature, and the temperature of each high temperature sintering is 700 DEG C~1000 DEG C.
The present invention is not limited to carry out solid phase reaction to reactant in ar gas environment or vacuum environment, in order to avoid reaction Object is oxidized, as long as the sintering reaction object in the environment of oxygen isolation.
Although the present invention has been described by means of preferred embodiments, the present invention is not limited to described here Embodiment, without departing from the present invention further include made various changes and variation.

Claims (11)

1. a kind of fluorine-based ferromagnetic semiconductor material, which is characterized in that the chemical formula of the fluorine-based ferromagnetic semiconductor material is (Ba1- xKx)F(Zn1-yMny) As, wherein x and y indicates atom content, and 0.05≤x≤0.2,0.025≤y≤0.15.
2. fluorine-based ferromagnetic semiconductor material according to claim 1, which is characterized in that 0.1≤x≤0.2,0.1≤y≤ 0.15。
3. fluorine-based ferromagnetic semiconductor material according to claim 1 or 2, which is characterized in that the fluorine-based ferromagnetic semiconductor The crystal structure of material is tetragonal crystal system.
4. a kind of preparation method of fluorine-based ferromagnetic semiconductor material, characterized in that it comprises the following steps:
1) it weighs reactant and is uniformly mixed, the atom content ratio of Ba:K:F:Zn:Mn:As is (1-x): x in the reactant: 1:(1-y): y:1, wherein 0.05≤x≤0.2,0.025≤y≤0.15；
2) uniformly mixed reactant is subjected to solid phase reaction.
5. the preparation method according to claim 4, which is characterized in that further include the following steps:
3) block materials for generating the step 2) are ground；
4) powder for obtaining the step 3) carries out solid phase reaction.
6. preparation method according to claim 4 or 5, which is characterized in that the temperature of the solid phase reaction be 700 DEG C~ 1000℃。
7. preparation method according to claim 6, which is characterized in that the pressure of the solid phase reaction is an atmospheric pressure, Time is 5~30 hours.
8. preparation method according to claim 6, which is characterized in that the pressure of the solid phase reaction is 1~20GPa, when Between be 1~2 hour.
9. preparation method according to claim 4 or 5, which is characterized in that 0.1≤x≤0.2,0.1≤y≤0.15.
10. preparation method according to claim 4 or 5, which is characterized in that the reactant is selected from what following substance was constituted Group: BaAs, BaF2, Zn, Mn, KAs, ZnAs, MnAs and As.
11. preparation method according to claim 10, which is characterized in that the reactant is powdered BaAs, BaF2、 Zn, As, Mn and KAs.
CN201610157611.6A 2016-03-18 2016-03-18 Fluorine-based ferromagnetic semiconductor material and preparation method thereof Active CN107204225B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610157611.6A CN107204225B (en) 2016-03-18 2016-03-18 Fluorine-based ferromagnetic semiconductor material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610157611.6A CN107204225B (en) 2016-03-18 2016-03-18 Fluorine-based ferromagnetic semiconductor material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN107204225A CN107204225A (en) 2017-09-26
CN107204225B true CN107204225B (en) 2019-04-05

Family

ID=59904584

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610157611.6A Active CN107204225B (en) 2016-03-18 2016-03-18 Fluorine-based ferromagnetic semiconductor material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN107204225B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103911660A (en) * 2012-12-31 2014-07-09 中国科学院物理研究所 Diluted magnetic semiconductor material and preparation method thereof
CN104099664A (en) * 2013-04-08 2014-10-15 中国科学院物理研究所 Semi-conducting material BaFxZnAs and preparation method thereof
CN105097173A (en) * 2014-05-14 2015-11-25 中国科学院物理研究所 A ferromagnetic semiconductor material (Sr, na) (Zn, mn)2As2and its prepn

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2224056C1 (en) * 2002-05-13 2004-02-20 Институт общей и неорганической химии им. Н.С.Курнакова РАН Ferromagnetic semiconducting material with high curie temperature
SE528394C2 (en) * 2004-05-18 2006-11-07 Nm Spintronics Ab Manganese doped magnetic semiconductors
US8357309B2 (en) * 2007-04-03 2013-01-22 University Of Kentucky Research Foundation Class of ferromagnetic semiconductors

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103911660A (en) * 2012-12-31 2014-07-09 中国科学院物理研究所 Diluted magnetic semiconductor material and preparation method thereof
CN104099664A (en) * 2013-04-08 2014-10-15 中国科学院物理研究所 Semi-conducting material BaFxZnAs and preparation method thereof
CN105097173A (en) * 2014-05-14 2015-11-25 中国科学院物理研究所 A ferromagnetic semiconductor material (Sr, na) (Zn, mn)2As2and its prepn

Also Published As

Publication number Publication date
CN107204225A (en) 2017-09-26

Similar Documents

Publication Publication Date Title
Streule et al. Effect of oxygen ordering on the structural and magnetic properties of the layered perovskites PrBaCo2O5+ δ
CN112010270B (en) FeBi (Te, Se) polycrystalline superconducting material and preparation method and application thereof
CN103911660B (en) A kind of dilute magnetic semiconductor material and preparation method thereof
Muro et al. Crystalline electric field effect and magnetic properties of CeRhSi3 single crystal
CN101993247A (en) Perovskite structure-based single-phase iron-based superconductive material and preparation method thereof
CN107204225B (en) Fluorine-based ferromagnetic semiconductor material and preparation method thereof
CN102683168B (en) A kind of method preparing magnetic germanium quantum point
CN106395913A (en) Ferromagnetic nano alpha-Fe2O3 with iron defects, and preparation method thereof
Rodgers et al. Suppression of the superconducting transition of R FeAsO 1− x F x (R= Tb, Dy, and Ho)
CN102659166B (en) Method for preparing CuO/Cu2O block composite material with room-temperature ferromagnetism
CN105097173B (en) A kind of ferromagnetic semiconductor material (Sr, Na) (Zn, Mn)2As2And preparation method thereof
CN107146676B (en) Cadmium base ferromagnetic semiconductor material and preparation method thereof
Hu et al. Characterization of the magnetic entropy of double perovskite (Sr1. 55Gd0. 15Ba0. 3) FeMoO6
CN107099845A (en) A kind of HfTe with huge magneto-resistor5‑δ Crystal and its growing method
CN105296785A (en) A diluted magnetic semiconductor material (Ca, na) (Zn, mn)2As2and its prepn
CN108505109B (en) Single crystal growth method of ferromagnetic semiconductor material
CN102839354A (en) Preparation method for component-controlled ZrOx thin film
Lin et al. Extremely low temperature coefficient of resistivity in antiperovskite compounds MσGa1− σCFe3 (M= Cu, Ag)
CN110459377A (en) A kind of ferromagnetic material and preparation method thereof with huge Negative magnetoresistance effect
CN112647129B (en) NbGe2Single crystal, method for producing the same and use thereof
RU2256618C1 (en) Method for producing ferromagnetic iron-manganese sulfide with giant magnetic resistance
Jia et al. Emergence of 1/3 magnetization plateau and successive magnetic transitions in Zintl phase Eu 3 InAs 3
CN108511595B (en) A kind of An Deliefu reflection knot and its preparation method and application
CN109873077B (en) Method for adjusting exchange bias field of intermetallic compound
CN113149642B (en) Intermetallic oxide superconducting material and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant