CN100595851C - Oxidate magnetic semiconductor thin film capable of regulating electric transport property and method of preparing the same - Google Patents
Oxidate magnetic semiconductor thin film capable of regulating electric transport property and method of preparing the same Download PDFInfo
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- CN100595851C CN100595851C CN200710115811A CN200710115811A CN100595851C CN 100595851 C CN100595851 C CN 100595851C CN 200710115811 A CN200710115811 A CN 200710115811A CN 200710115811 A CN200710115811 A CN 200710115811A CN 100595851 C CN100595851 C CN 100595851C
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Abstract
The present invention provides oxide magnetic semiconductor film with adjustable electronic transport properties and manufacture method thereof, which belongs to information technology rotating electron material field. The series oxide magnetic semiconductor film displays common electric transport property: material with low electric resistivity being Mott range transition resistor, material withmiddle electric resistivity being hard Efros range transition resistor, material with high electric resistivity being hardgap resistor. The super thin iron magneto- metallic layer and the wide forbidden region oxide semiconductor layer are alternating deposited on substrate by using the method of magnetron sputtering or pulsed laser depositing through accurate control partial pressure of oxygen infilm preparation process to regulate electric transport property of material. Electric transport property of oxide magnetic semiconductor film is only related to concentration of oxygen vacancy in material.
Description
Technical field
The present invention relates to the regulatable broad stopband of electronic transport character ternary oxide magnetic semiconductor thin film and preparation method thereof, belong to information technology spin-electronic material field.
Background technology
The running of traditional microelectronic component is electric charge number and the energy based on electronics, and its restriction is being arranged aspect speed and the energy consumption; And the running of novel spin electric device is based on electronic spin direction and spin-orbit coupling, when low-down power the speed of service faster can be arranged.Scientist has proposed many spinning electron antetype devices, spinning LED for example, spin fet, magnetic random memory, quantum computer etc.And magnetic semiconductor also becomes the research focus in spintronics field in recent years as the very promising material of realizing these function elements.
The magnetic semiconductor of being studied at present is divided into containing transition metal () III-V family for example, Fe, Co, Ni, Mn, and Cr etc., IV family, II-VI family three classes.Wherein, the research of III-V family magnetic semiconductor film material is with GaAs, and nitride GaN is main, but the Curie temperature of this class material is low excessively, and the highest 173K that is reported as is far below the application of temperature (293K) of room temperature spintronics device.The research of IV family magnetic semiconductor film material is with Ge, and Si is main, Ge, and can Si and transition elements form compound easily, succeed in developing the magnetic semiconductor of intrinsic, are still the problem of research at present.The research of II-VI family magnetic semiconductor film material is with ZnO and TiO
2Be main, notional result shows, may realize the magnetic semiconductor of room temperature in these two kinds of material the insides.
Under this situation, people such as plum have proposed the method that inferior nano combined legal system is equipped with the zno-based semiconductor film material, utilize the non-equilibrium growing technology of low temperature, obtained the zno-based magnetic semiconductor material that transient metal doped amount is not subjected to the solid solubility restriction, referring to patent documentation publication number CN 1858862A (application number 200610043855.8).In addition, people such as face has proposed the highly doped Co of a kind of amorphous state
xTi
1-xThe preparation method of O ferromagnetic semiconductor film has obtained Curie temperature and has been higher than room temperature (300K), has the not ferromagnetism Co that leads of Loews (Efros) range transition electricity of good dust
xTi
1-xThe O semiconductive thin film is referring to patent documentation publication number CN 1697095A (application number 200510043640.1).
But up to the present, the reason that influences oxide magnetic semiconductor film material electronic transport character is also unclear, does not more know how electron transport character is regulated and control.Therefore, the inventor has carried out long term studies to the factor that influences material electronic transport character, proposes the application.
Summary of the invention
At the deficiencies in the prior art, the invention provides the regulatable broad stopband of a kind of electronic transport character ternary oxide magnetic semiconductor thin film and preparation method thereof.
The term explanation:
Partial pressure of oxygen, i.e. oxygen proportion in the mixing sputter gas of oxygen and argon gas,
Low-resistance material, R=5 * 10
-6Ω m-5 * 10
-4Ω m,
The material of interlaminated resistance, R=5 * 10
-4Ω m-5 * 10
-3Ω m,
High-resistance material, R=5 * 10
-3Ω m-5 * 10
1Ω m.
Technical scheme of the present invention is as follows:
The regulatable oxide magnetic semiconductive thin film of electronic transport character is characterized in that it is as follows to have general molecular formula:
(A
1-xB
x)
aO
B-vWherein, x=0.2-0.8, a=1-2, b=1-3, v=0-0.4.
A represents the nonmagnetic metal element, is selected from Zn, Ti, Sn, In or Al;
B represents the magnetic metal element, is selected from Fe, Co, Ni or Mn;
V represents oxygen room content.
This series oxide magnetic semiconductive thin film shows general electronic transport character, and low-resistance material is not special (Mott) range transition, and the logarithm of film resiativity and the pass of temperature are that ln ρ is proportional to T
1/4The material of interlaminated resistance is not Loews (Efros) range transition of dust, and the logarithm of film resiativity and the pass of temperature are that ln ρ is proportional to T
1/2High-resistance material is hard band gap (hard gap) resistance, and the logarithm of film resiativity and the pass of temperature are ln ρ ∝ T
-1
This series oxide magnetic semiconductive thin film electronic transport character is regulated and control by the oxygen room that changes in the material.The oxygen room is a kind of defective of oxide semiconductor.The concentration in oxygen room generally can be regulated and control by following manner in the semiconductor film material: 1. change the oxygen atmosphere in the preparation process, 2. carry out annealing in process under certain oxygen atmosphere.Consider that the present invention need prepare under the low temperature non-equilibrium condition, annealing in process can cause and be separated, so the present invention adopts the oxygen atmosphere that changes in the preparation process to change the oxygen room of sample.
The preparation method of the regulatable oxide magnetic semiconductive thin film of electronic transport character is characterized in that, utilizes the method for magnetron sputtering or pulsed laser deposition, replaces deposited iron magnetic gold and oxide semiconductor layer on substrate, and ferromagnetic layer thickness is 2-10
, oxide skin(coating) thickness is 2-20
, the alternating deposit cycle is 30-120.
Above-mentioned feeromagnetic metal layer material is selected from Fe, Co, Ni or Mn.
Above-mentioned oxide skin(coating) material is selected from ZnO, TiO
2, SnO
2, In
2O
3Or Al
2O
3
When adopting the method for magnetron sputtering, the excursion 0-8% of control partial pressure of oxygen.
In order accurately to control the change of partial pressure of oxygen in the preparation process, preferably, the present invention adopts the regulation and control of two-stage oxygen content, one the tunnel is the pure argon original gas, another road is that the mist of the oxygen of certain oxygen content and argon gas is as original gas, enter the flow of sputtering chamber by mass flowmenter control two-way gas, thereby realize control oxygen proportion in last mixing sputter gas.
When adopting the method for pulsed laser deposition, vacuum reaches 10
-5During Pa, aerating oxygen, the excursion 10 that oxygen is pressed
5-10
-2Pa.
Above partial pressure of oxygen scope that the present invention is preferred is found can cause the appearance of other metal oxide especially when partial pressure of oxygen is too high.
The used backing material of the present invention is selected from the quartz glass substrate, single crystal quartz substrate, monocrystalline substrate, monocrystalline Al
2O
3Substrate, monocrystalline SrTiO
3Substrate or simple glass substrate.
The present invention goes into long-term experiment research, find the decisive role of the semi-conductive electronic transport character of oxygen double-void oxide magnetic, and, successfully prepared the regulatable oxide magnetic semiconductor of a series of transport properties by accurately controlling the partial pressure of oxygen in the film preparation process.The semi-conductive electronic transport character of this series oxide magnetic is insensitive for the doping of the kind of broad stopband oxide semiconductor material and magnetic transition metal element, and very sensitive to the concentration in oxygen room in the material.
The transition metal element doped amount that the present invention is high makes material that big magnetic be arranged, high Curie temperature.
The present invention selects wide bandgap semiconductor for use, because the wide band gap of material has good optical transmission.
The regulatable electronic transport character of the present invention in conjunction with last it magnetic and good optical transmission, make it at some multifunction devices, as the Spin Valve transistor, the spin light emitting diode, there is not the volatilization memory cell, ultrafast optical switch, and all there is potential using value aspect such as spin quantum device.
Description of drawings
(the In of Fig. 1-3 for preparing under the different partial of embodiment 1
0.26Co
0.74)
2O
3-vThe resistivity of oxide magnetic semiconductive thin film-temperature relation curve.
Embodiment
The present invention will be further described below in conjunction with embodiment, but be not limited thereto.
Embodiment 1:(In
0.26Co
0.74)
2O
3-vThe preparation of oxide magnetic semiconductive thin film reaches the regulation and control to its electronic transport character
Utilize the method for magnetron sputtering,, the sputtering chamber vacuum is evacuated to 5 * 10
-5Pa is with the In of purity more than 99.99%
2O
3Pottery and the Co metal of purity more than 99.99% are target, with In
2O
3Place the radio frequency target, Co places the direct current target.With the high-purity Ar gas of purity more than 99.99% with contain O
2Mol ratio be 2% Ar gas as sputtering atmosphere, two kinds of gases are entered mixing chamber via mass-flow gas meter respectively, after mixing chamber fully mixes, enter sputtering chamber.Sputtering chamber pressure is stabilized in 1Pa.Control partial pressure of oxygen by mass flowmenter, in this example, partial pressure of oxygen is respectively 0%, 0.096%, and 0.136%.On the simple glass substrate of water-cooled, the In of alternating deposit one deck 0.5nm
2O
3, the Co of one deck 0.5nm, alternate cycle is 60.
(the In of the different electronic transport character of demonstration that Fig. 1-3 expression embodiment 1 makes
0.26Co
0.74)
2O
3-vThe resistivity of film-temperature relation curve.As shown in Figure 1, (the In for preparing under 0% partial pressure of oxygen
0.26Co
0.74)
2O
3-vThe logarithm ln ρ ∝ T of the resistivity of film
-1/4, show not special (Mott) range transition resistance.As shown in Figure 2, (the In for preparing under 0.096% partial pressure of oxygen
0.26Co
0.74)
2O
3-vThe logarithm ln ρ ∝ T of the resistivity of film
-1/2, demonstration dust not Loews (Efros) range transition electricity is led.As shown in Figure 3, (the In for preparing under 0.136% partial pressure of oxygen
0.26Co
0.74)
2O
3-vThe logarithm ln ρ ∝ T of the resistivity of film
-1, show hard band gap (hard gap) resistance.
| Sample number into spectrum | Partial pressure of oxygen | Resistivity | Electronic transport character |
| I | 0％ | 5.19×10 -5Ωm | lnρ∝T -1/4 |
| II | 0.096％ | 2.72×10 4Ωm | lnρ∝T 1/2 |
| III | 0.136％ | 4.22×10 -3Ωm | lnρ∝T -1 |
Embodiment 2:Sn
0.34Fe
0.66O
2-vThe preparation of oxide magnetic semiconductive thin film is to the regulation and control of its electronic transport character
Utilizing the method for pulsed laser deposition, is substrate with (111) silicon single crystal, with the SnO of purity more than 99.99%
2Pottery and the Fe metal of purity more than 99.99% are target, when vacuum is evacuated to 5 * 10
-5During Pa,, press by the flow control vacuum indoor oxygen of regulating oxygen via the mass-flow gas meter aerating oxygen.In this example, partial pressure of oxygen is respectively 5 * 10
-5Pa, 1 * 10
-5Pa, 5 * 10
-4Pa.After system's stable gas pressure, begin to deposit.On (111) silicon monocrystalline substrate, the SnO of alternating deposit one deck 0.6nm
2, the Fe of one deck 0.4nm, alternate cycle is 90.
Claims (2)
1, the preparation method of the regulatable oxide magnetic semiconductive thin film of electronic transport character is characterized in that it is as follows that film has molecular formula:
(Sn
1-xFe
x)
aO
B-vPerhaps (In
1-xCo
x)
aO
B-v, wherein, x=0.2-0.8, a=1-2, b=1-3, v=0-0.4,
Sn, In are the nonmagnetic metal element, and Fe, Co are the magnetic metal element, and v represents oxygen room content;
Low-resistance film is not special range transition, and the logarithm of its film resiativity and the pass of temperature are that ln ρ is proportional to T
-1/4The film of interlaminated resistance is not Loews range transition of dust, and the logarithm of its film resiativity and the pass of temperature are that ln ρ is proportional to T
-1/2High-resistance film is hard band gap resistance, and the logarithm of its film resiativity and the pass of temperature are that ln ρ is proportional to T
-1
Utilize the method for magnetron sputtering or pulsed laser deposition, on substrate, replace deposited iron magnetic metal layer material Fe and oxide semiconductor layer material SnO
2, perhaps on substrate, replace deposited iron magnetic metal layer material Co and oxide semiconductor layer material In
2O
3, the feeromagnetic metal layer thickness is 2-
Oxide semiconductor layer thickness is 2-
The alternating deposit cycle is 30-120;
When adopting the method for magnetron sputtering, the excursion 0-8% of control partial pressure of oxygen; Described control partial pressure of oxygen adopts the regulation and control of two-stage oxygen content, one the tunnel is the pure argon original gas, another road is that the mist of the oxygen of certain oxygen content and argon gas is as original gas, enter the flow of sputtering chamber by mass flowmenter control two-way gas, thereby realize control oxygen proportion in last mixing sputter gas;
When adopting the method for pulsed laser deposition, vacuum reaches 10
-5During Pa, aerating oxygen, the excursion 10 that oxygen is pressed
-5-10
-2Pa.
2, the preparation method of the regulatable oxide magnetic semiconductive thin film of electronic transport character as claimed in claim 1 is characterized in that used backing material is selected from the quartz glass substrate, single crystal quartz substrate, monocrystalline substrate, monocrystalline Al
2O
3Substrate, monocrystalline SrTiO
3Substrate or simple glass substrate.
Priority Applications (1)
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|---|---|---|---|
| CN200710115811A CN100595851C (en) | 2007-12-20 | 2007-12-20 | Oxidate magnetic semiconductor thin film capable of regulating electric transport property and method of preparing the same |
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|---|---|---|---|
| CN200710115811A CN100595851C (en) | 2007-12-20 | 2007-12-20 | Oxidate magnetic semiconductor thin film capable of regulating electric transport property and method of preparing the same |
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| CN100595851C true CN100595851C (en) | 2010-03-24 |
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|---|---|---|---|---|
| US9960278B2 (en) * | 2011-04-06 | 2018-05-01 | Yuhei Sato | Manufacturing method of semiconductor device |
| CN102931341B (en) * | 2012-11-09 | 2014-09-10 | 山东大学 | Magnetic tunnel junction spin battery with spin electromotive force and giant magnetoresistance (GMR) and preparation method thereof |
| CN104614654B (en) * | 2013-11-04 | 2017-09-19 | 华东师范大学 | A kind of automatization test system of multichip semiconductor electrical parameter |
| CN103956261B (en) * | 2014-04-22 | 2016-03-30 | 河北大学 | The multi-functional ferromagnetic composite film material of nanostructure and preparation method |
| CN107326326B (en) * | 2017-06-15 | 2019-06-21 | 郑州科技学院 | A kind of method for preparing zinc oxide thin film that electricity device is adulterated with Al |
| CN107354440B (en) * | 2017-06-23 | 2019-07-02 | 郑州科技学院 | A kind of preparation method of the tin oxide transparent conductive film of Sb doped |
| CN108190941B (en) * | 2017-12-31 | 2020-05-12 | 乐清海创智能科技有限公司 | Diluted magnetic semiconductor and preparation method thereof |
| CN113061990A (en) * | 2021-03-18 | 2021-07-02 | 中国科学院物理研究所 | Cobalt oxide-based magnetic oxide thin film and preparation method and application thereof |
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Non-Patent Citations (5)
| Title |
|---|
| Electrical transport properties of (CoxAl1-x)2O3-v oxidemagnetic semiconductor and corresponding Co-Al2O3granular films. Y. F. Tian et al.Applied Physics Letters,Vol.91 . 2007 |
| Electrical transport properties of (CoxAl1-x)2O3-v oxidemagnetic semiconductor and corresponding Co-Al2O3granular films.Y.F.Tian et al.Applied Physics Letters,Vol.91. 2007 * |
| Electronic transport of (In1-xFex)2O3-v magneticsemiconductor and Fe-In2O3 granular films in the presence ofelectronic screening. Y. F. Tian et al.J. phys.: Condens. Matter,Vol.19 . 2007 |
| Electronic transport of (In1-xFex)2O3-v magneticsemiconductor and Fe-In2O3 granular films in the presence ofelectronic screening. Y.F.Tian et al.J.phys.:Condens. Matter,Vol.19. 2007 * |
| Transformation of electrical transport from variable rangehopping to hard gap resistance in Zn1-xFexO1-v magneticsemiconductor films. Y. F. Tian et al.Journal of applied physics,Vol.100 . 2006 |
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