CN102360710A - Zinc oxide (ZnO)-base diluted magnetic thin film and preparation method thereof - Google Patents
Zinc oxide (ZnO)-base diluted magnetic thin film and preparation method thereof Download PDFInfo
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- CN102360710A CN102360710A CN 201110166520 CN201110166520A CN102360710A CN 102360710 A CN102360710 A CN 102360710A CN 201110166520 CN201110166520 CN 201110166520 CN 201110166520 A CN201110166520 A CN 201110166520A CN 102360710 A CN102360710 A CN 102360710A
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Abstract
The invention discloses a zinc oxide (ZnO)-base diluted magnetic thin film and a preparation method thereof. The ZnO-base diluted magnetic thin film comprises a substrate, and a diluted magnetic thin film and an antiferromagnetic thin film which are positioned on the substrate, wherein the diluted magnetic thin film is made of Zn1-xTMxO; in the Zn1-xTMxO, x is 0.2 to 10.0 percent, preferably 3 to 5 percent; TM is a transition metal element; and the antiferromagnetic thin film is made of at least one of transition metal oxides. The room temperature ferromagnetism of the ZnO-base diluted magnetic thin film is improved by depositing a thin layer of antiferromagnetic thin film on the ZnO-base diluted magnetic thin film or depositing a layer of diluted magnetic thin film on the antiferromagnetic thin film; and the average atomic magnetic moment of a room temperature saturated average atomic magnetic moment (muB/Co) with a double-layer film structure relative to a single-layer diluted magnetic thin film structure is improved greatly by using an interface neighbor effect of the room temperature ferromagnetism TM: ZnO thin film and the antiferromagnetic thin film.
Description
Technical field
The invention belongs to the spintronics field, relate to rare magnetic thin film of a kind of zno-based and preparation method thereof.
Background technology
The important support material that rare magnetic oxide is a self-spining device of new generation; Magneto-optic, magnetic electricity performance with multiple excellence make it in high-density nonvolatile memory, magnetic inductor, optical isolator, semiconductor integrated circuit, semiconductor laser and spin quantum bit machine field boundless application prospect arranged.Preparation has rare magnetic oxide of room-temperature ferromagnetic, and to be applied to self-spining device be one of spintronics hot research fields.Compare with traditional semiconductor device, spin electric device has advantages such as speed is fast, volume is little, energy consumption is low, non-volatile, has bigger application potential.Yet up to the present, still not have the practicability that can reach real, one of the main reasons be that the low and Curie temperature of the saturation magnetization of rare magnetic material is lower than room temperature to rare magnetic material.Constantly occur though have rare magnetic material of room-temperature ferromagnetic in recent years, their saturation magnetization a little less than, performance is stable inadequately, has limited practicalization.Up to now, also there is not a kind of suitable way can effectively strengthen the magnetic of rare magnetic thin film material.The ZnO film material has excellent structure and physical property, and very wide in the application prospect of field of electronic devices, in recent years, the rare magnetic material of zno-based has obtained extensive studies, but performance is not ideal enough and poor repeatability.
Summary of the invention
The purpose of this invention is to provide rare magnetic thin film of a kind of zno-based and preparation method thereof.
The rare magnetic thin film of zno-based provided by the invention comprises substrate, is positioned at said on-chip rare magnetic thin film and antiferromagnet film;
Wherein, the material that constitutes said rare magnetic thin film is Zn
1-xTM
xO, said Zn
1-xTM
xAmong the O, x is 0.2%-10.0%, and TM is a transition metal;
The material that constitutes said antiferromagnet film is selected from least a in the transition metal oxide.
Said Zn
1-xTM
xAmong the O, the preferred 3%-5% of x, more preferably 4-5%, TM are selected from least a among Co, Ni and the Fe; Said transition metal oxide is selected from least a among NiO, CoO and the CuO.The material that constitutes said substrate is selected from LiNbO
3, Si, Al
2O
3And LiTaO
3In at least a, preferred LiNbO
3The thickness of said rare magnetic thin film is 10～400nm, preferred 15-120nm; The thickness of said antiferromagnet film is 10～400nm, preferred 10-60nm.
The rare magnetic thin film of the zno-based that the invention described above provides can be said substrate, said rare magnetic thin film and said antiferromagnet film from the bottom to top successively;
Perhaps, the rare magnetic thin film of said zno-based is followed successively by said substrate, said antiferromagnet film and said rare magnetic thin film from the bottom to top.
Preferably, the rare magnetic thin film of zno-based provided by the invention is followed successively by said substrate, said rare magnetic thin film and said antiferromagnet film from the bottom to top; Wherein, the material that constitutes said substrate is LiNbO
3, the material that constitutes said rare magnetic thin film is Zn
0.96Co
0.04O, the material that constitutes said antiferromagnet film is NiO; Also promptly, the structure of the rare magnetic thin film of this zno-based is LiNbO
3/ Co:ZnO/NiO; Wherein, said Zn
0.96Co
0.04The thickness of the rare magnetic thin film of O is 30nm, and the thickness of said NiO antiferromagnet film is 10-60nm; The rare magnetic thin film LiNbO of said ZnO
3The saturated average atom magnetic moment of the room temperature of/Co:ZnO/NiO is 3.0 μ
B/ Co～3.6 μ
B/ Co.
Perhaps, preferred, the rare magnetic thin film of said zno-based is followed successively by said substrate, said antiferromagnet film and said rare magnetic thin film from the bottom to top; Wherein, the material that constitutes said substrate is LiNbO
3, the material that constitutes said antiferromagnet film is NiO; The material that constitutes said rare magnetic thin film is Zn
0.95Ni
0.05O; The thickness of said thin film is 80nm, and the thickness of said antiferromagnet film is 10-60nm; The saturated average atom magnetic moment of the room temperature of the rare magnetic thin film of said ZnO is 2.1 μ
B/ Co～2.5 μ
B/ Co.
The method of the rare magnetic thin film of the above-mentioned zno-based of preparation provided by the invention is following method one or method two, and wherein, said method one comprises the steps: on substrate, to prepare the rare magnetic thin film of one deck and one deck antiferromagnet film successively, obtains the rare magnetic thin film of said zno-based;
Said method two comprises the steps: on substrate, to prepare successively one deck antiferromagnet film and the rare magnetic thin film of one deck, obtains the rare magnetic thin film of said zno-based.
In above-mentioned two methods, the material that constitutes said rare magnetic thin film is Zn
1-xTM
xO, said Zn
1-xTM
xAmong the O, x is 0.2%-10.0%, preferred 3%-5%, and more preferably 4-5%, TM is transition metal, at least a among preferred Co, Ni and the Fe; The material that constitutes said antiferromagnet film all is selected from least a in the transition metal oxide, at least a among preferred NiO, CoO and the CuO;
The material that constitutes said substrate all is selected from LiNbO
3, Si, Al
2O
3And LiTaO
3In at least a, preferred LiNbO
3
The thickness of said rare magnetic thin film is 10～400nm, preferred 15-120nm; The thickness of said antiferromagnet film is 10～400nm, preferred 10-60nm.
The said method for preparing the rare magnetic thin film of one deck is the various methods that prepare film commonly used with the method for preparing one deck antiferromagnet film; As can be at least a in physical vaporous deposition, chemical vapour deposition technique, sol-gel process and the electrochemical method, preferred dc reactive sputtering sedimentation.Wherein, method therefor does, during preferred dc reactive sputtering method, this method can be carried out according to following steps: selecting argon gas (Ar) for use is sputter gas, oxygen (O
2) be reacting gas, the pressure of Ar is 0.24-0.3Pa, O
2Pressure be 0.06-0.8Pa, 200 ℃ of substrate temperatures, deposition rate is 3-7.2nm/min, sputtering current is 0.6A, sputtering voltage is 350V, in the sputter procedure, substrate temperature remains on 200 ℃.
The invention provides rare magnetic thin film of a kind of zno-based and preparation method thereof.The rare magnetic thin film of this zno-based has a kind of simple double membrane structure, makes its room-temperature ferromagnetic have good control, and the structure of the rare magnetic thin film of this zno-based is: substrate/TM:ZnO/AF or substrate/AF/TM:ZnO.The present invention is through deposition skim antiferromagnet film on the rare magnetic thin film of zno-based or on antiferromagnet film, deposit the room-temperature ferromagnetic that the rare magnetic thin film of one deck improves the rare magnetic thin film of zno-based; Utilize interface neighbour's effect of room-temperature ferromagnetic TM:ZnO film and antiferromagnet film, make the saturated average atom magnetic moment of the room temperature (μ of double membrane structure
B/ Co) the average atom magnetic moment of the rare magnetic thin film structure of individual layer obviously increases relatively.Wherein can regulate and control the average atom magnetic moment of TM:ZnO through the variation of rare magnetosphere TM:ZnO and inverse ferric magnetosphere thickness.The rare magnetic thin film of zno-based provided by the invention will be accelerated the practicability of rare magnetic material aspect the spintronics device greatly, has important use and is worth.
Embodiment
Below in conjunction with specific embodiment the present invention is done further elaboration, but the present invention is not limited to following examples.Said method is conventional method if no special instructions.Said material all can get from open commercial sources if no special instructions.
Embodiment 1, preparation LiNbO
3The rare magnetic thin film of the zno-based of/Co:ZnO/NiO structure
At LiNbO
3Adopt the mode of dc reactive sputtering to deposit one deck Zn on the ferroelectric substrate
0.96Co
0.04O film (also being that Co is ZnO thin film doped), this Zn
0.96Co
0.04In the O film, the doping content of Co is 4.0at.%, and thickness is 30nm, and in this dc reactive sputtering deposition step, argon gas (Ar) is a sputter gas, oxygen (O
2) be reacting gas, the pressure of the two is respectively 0.3Pa and 0.5Pa, and sputtering current is 0.6A, and sputtering voltage is 350V, and deposition rate is 3nm/min, in the sputter procedure, substrate temperature remains on 200 ℃.
And then at this Zn
0.96Co
0.04Adopt the mode of dc reactive sputtering to deposit layer of Ni O film on the O film, in this dc reactive sputtering deposition step, argon gas (Ar) is a sputter gas, oxygen (O
2) be reacting gas, Ar and O
2Pressure be respectively 0.24Pa and 0.06Pa, sputtering current is 0.6A, sputtering voltage is 350V; 200 ℃ of substrate temperatures; Deposition rate is 7.2nm/min, and the NiO film thickness is set at 10nm, 20nm, 30nm, 40nm and 60nm respectively, obtains LiNbO provided by the invention
3The rare magnetic thin film of the zno-based of/Co:ZnO/NiO structure.
The rare magnetic thin film of this zno-based is followed successively by LiNbO from the bottom to top
3Ferroelectric substrate, Zn
0.96Co
0.04Rare magnetic thin film of O and NiO antiferromagnet film; Wherein, Zn
0.96Co
0.04The thickness of the rare magnetic thin film of O is 30nm, and the thickness of NiO antiferromagnet film is 10nm, 20nm, 30nm, 40nm or 60nm.
This embodiment prepares the rare magnetic thin film of gained zno-based and has well in the axial preferred orientation of c, and the interface is clear smooth, and adhesive force is better.Superconducting quantum magnetometer (SQUID) testing result shows LiNbO
3The saturated average atom magnetic moment of the room temperature of/Co:ZnO monofilm is 2.3 μ
B/ Co, and duplicature LiNbO provided by the invention
3The rare magnetic thin film of the zno-based of/Co:ZnO/NiO structure, when the NiO thickness range is 10nm～60nm, the saturated average atom magnetic moment of the room temperature of double membrane structure is 3.0 μ
B/ Co～3.6 μ
B/ Co, its magnetic moment size reduces along with the increase of NiO thickness.The inverse ferric magnetosphere NiO of different-thickness and the interface coupling of Co:ZnO film make the saturated average atom magnetic moment of room temperature of the rare magnetic thin film of Co:ZnO that raising in various degree arranged.
Embodiment 2, preparation LiNbO
3The rare magnetic thin film of the zno-based of/NiO/Ni:ZnO structure
At LiNbO
3Adopt the mode of dc reactive sputtering to deposit the NiO film on the ferroelectric substrate, in this dc reactive sputtering deposition step, argon gas (Ar) is a sputter gas, oxygen (O
2) be reacting gas, the pressure of the two is respectively 0.24Pa and 0.06Pa, and 200 ℃ of substrate temperatures, sputtering current are 0.6A, and sputtering voltage is 350V, and deposition rate is 7.2nm/min, the NiO film thickness is set at 10nm, 20nm, 30nm, 40nm and 60nm respectively.
And then on the NiO film, adopt the mode of dc reactive sputtering to deposit one deck Zn
0.95Ni
0.05O film (also being that Ni is ZnO thin film doped), doping content is 5.0at.%, and thickness is 80nm, and in this dc reactive sputtering deposition step, argon gas (Ar) is a sputter gas, oxygen (O
2) be reacting gas, Ar and O
2Pressure be respectively 0.3Pa and 0.5Pa, sputtering current is 0.6A, sputtering voltage is 350V, deposition rate is 3nm/min, in the sputter procedure, substrate temperature remains on 200 ℃, obtains LiNbO provided by the invention
3The rare magnetic thin film of the zno-based of/NiO/Ni:ZnO structure.
This LiNbO
3The rare magnetic thin film of the zno-based of/NiO/Ni:ZnO structure is followed successively by LiNbO from the bottom to top
3Ferroelectric substrate, NiO antiferromagnet film and Zn
0.95Ni
0.05The rare magnetic thin film of O.Wherein, Zn
0.95Ni
0.05The thickness of the rare magnetic thin film of O is 80nm, and the thickness of NiO antiferromagnet film is 10nm, 20nm, 30nm, 40nm or 60nm.
This embodiment prepares the rare magnetic thin film of gained zno-based and has well in the axial preferred orientation of c, and the interface is clear smooth, and adhesive force is better.Superconducting quantum magnetometer (SQUID) testing result shows LiNbO
3The saturated average atom magnetic moment of the room temperature of/Ni:ZnO monofilm is 1.6 μ
B/ Co, duplicature LiNbO
3/ NiO/Ni:ZnO structure, when the NiO thickness range is 10nm～60nm, and the LiNbO of double membrane structure provided by the invention
3The saturated average atom magnetic moment of the room temperature of the rare magnetic thin film of zno-based of/NiO/Ni:ZnO structure is 2.1 μ
B/ Co～2.5 μ
B/ Co, its magnetic moment size reduces along with the increase of NiO thickness.The inverse ferric magnetosphere NiO of different-thickness and the interface coupling of Ni:ZnO film make the saturated average atom magnetic moment of room temperature of the rare magnetic thin film of Ni:ZnO that raising in various degree arranged.
Claims (10)
1. the rare magnetic thin film of zno-based comprises substrate, is positioned at said on-chip rare magnetic thin film and antiferromagnet film;
Wherein, the material that constitutes said rare magnetic thin film is Zn
1-xTM
xO, said Zn
1-xTM
xAmong the O, x is 0.2%-10.0%, and TM is a transition metal;
The material that constitutes said antiferromagnet film is selected from least a in the transition metal oxide.
2. film according to claim 1 is characterized in that: said Zn
1-xTM
xAmong the O, TM is selected from least a among Co, Ni and the Fe, and x is 3%-5%, preferred 4-5%; Said transition metal oxide is selected from least a among NiO, CoO and the CuO.
3. film according to claim 1 and 2 is characterized in that: the material that constitutes said substrate is selected from LiNbO
3, Si, Al
2O
3And LiTaO
3In at least a, preferred LiNbO
3
4. according to the arbitrary described film of claim 1-3, it is characterized in that: the thickness of said rare magnetic thin film is 10～400nm, preferred 15-120nm; The thickness of said antiferromagnet film is 10～400nm, preferred 10-60nm.
5. according to the arbitrary described film of claim 1-4, it is characterized in that: the rare magnetic thin film of said zno-based is followed successively by said substrate, said rare magnetic thin film and said antiferromagnet film from the bottom to top;
Perhaps, the rare magnetic thin film of said zno-based is followed successively by said substrate, said antiferromagnet film and said rare magnetic thin film from the bottom to top.
6. according to the arbitrary described film of claim 1-5, it is characterized in that: the rare magnetic thin film of said zno-based is followed successively by said substrate, said rare magnetic thin film and said antiferromagnet film from the bottom to top; Wherein, the material that constitutes said substrate is LiNbO
3, the material that constitutes said rare magnetic thin film is Zn
0.96Co
0.04O, the material that constitutes said antiferromagnet film is NiO; The thickness of said rare magnetic thin film is 30nm, and the thickness of said antiferromagnet film is 10-60nm; The saturated average atom magnetic moment of the room temperature of the rare magnetic thin film of said zno-based is 3.0 μ
B/ Co～3.6 μ
B/ Co;
Perhaps, the rare magnetic thin film of said zno-based is followed successively by said substrate, said antiferromagnet film and said rare magnetic thin film from the bottom to top; Wherein, the material that constitutes said substrate is LiNbO
3, the material that constitutes said antiferromagnet film is NiO; The material that constitutes said rare magnetic thin film is Zn
0.95Ni
0.05O; The thickness of said thin film is 80nm, and the thickness of said antiferromagnet film is 10-60nm; The saturated average atom magnetic moment of the room temperature of the rare magnetic thin film of said zno-based is 2.1 μ
B/ Co～2.5 μ
B/ Co.
7. according to the arbitrary described film of claim 1-6, it is characterized in that: said film is to get according to the arbitrary said method preparation of claim 8-10.
8. method for preparing the rare magnetic thin film of the arbitrary said zno-based of claim 1-6; Be following method one or method two; Wherein, said method one comprises the steps: on substrate, to prepare the rare magnetic thin film of one deck and one deck antiferromagnet film successively, obtains the rare magnetic thin film of said zno-based;
Said method two comprises people's following steps: on substrate, prepare one deck antiferromagnet film and the rare magnetic thin film of one deck successively, obtain the rare magnetic thin film of said zno-based.
9. method according to claim 8 is characterized in that: the material that constitutes said rare magnetic thin film is Zn
1-xTM
xO, said Zn
1-xTM
xAmong the O, x is 0.2%-10.0%, preferred 3%-5%, more preferably 4-5%; TM is transition metal, at least a among preferred Co, Ni and the Fe; The material that constitutes said antiferromagnet film all is selected from least a in the transition metal oxide, at least a among preferred NiO, CoO and the CuO;
The material that constitutes said substrate all is selected from LiNbO
3, Si, Al
2O
3And LiTaO
3In at least a, preferred LiNbO
3
The thickness of said rare magnetic thin film is 10～400nm, preferred 15-120nm; The thickness of said antiferromagnet film is 10～400nm, preferred 10-60nm.
10. according to Claim 8 or 9 described methods; It is characterized in that: the said method for preparing the rare magnetic thin film of one deck and the method that prepare one deck antiferromagnet film are at least a in physical vaporous deposition, chemical vapour deposition technique, sol-gel process and the electrochemical method, preferably dc reactive sputtering sedimentation.
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107604408A (en) * | 2017-08-25 | 2018-01-19 | 洛阳师范学院 | A kind of bismuth ferrite thin film and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100521273C (en) * | 2007-07-11 | 2009-07-29 | 清华大学 | ZnO thin membrane with large piezoelectric constant and high resistivity |
| CN101820047A (en) * | 2010-05-06 | 2010-09-01 | 清华大学 | Method for improving piezoelectric constant of ZnO film material |
-
2011
- 2011-06-20 CN CN 201110166520 patent/CN102360710B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100521273C (en) * | 2007-07-11 | 2009-07-29 | 清华大学 | ZnO thin membrane with large piezoelectric constant and high resistivity |
| CN101820047A (en) * | 2010-05-06 | 2010-09-01 | 清华大学 | Method for improving piezoelectric constant of ZnO film material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107604408A (en) * | 2017-08-25 | 2018-01-19 | 洛阳师范学院 | A kind of bismuth ferrite thin film and preparation method thereof |
| CN107604408B (en) * | 2017-08-25 | 2019-11-08 | 洛阳师范学院 | A kind of bismuth ferrite thin film and preparation method thereof |
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