CN105925956B - A method of oxide/metal magnetism hetero-junctions is prepared using atomic layer deposition method - Google Patents
A method of oxide/metal magnetism hetero-junctions is prepared using atomic layer deposition method Download PDFInfo
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- CN105925956B CN105925956B CN201610352527.XA CN201610352527A CN105925956B CN 105925956 B CN105925956 B CN 105925956B CN 201610352527 A CN201610352527 A CN 201610352527A CN 105925956 B CN105925956 B CN 105925956B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
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- C23C16/406—Oxides of iron group metals
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
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Abstract
The present invention provides a kind of methods preparing oxide/metal magnetism hetero-junctions using atomic layer deposition method, this method uses atomic layer deposition method, using ferrocene as source of iron, oxygen is as oxygen source, ferroso-ferric oxide is deposited on the metallic substrate, ferrocene is replaced with oxygen by atomic layer deposition system and is passed through in the reaction chamber of atomic layer deposition system, realizes deposition of the ferroso-ferric oxide on different metal substrate, and then construct oxide/metal magnetism hetero-junctions.Oxide/metal magnetism hetero-junctions made from this method has the advantages that at low cost, thin film composition and thickness controllable precise, three-dimensional uniformly conformal good, can be used as the Primary Component of magneto-electric coupled regulation and control.
Description
Technical field
The invention belongs to electric thin material and devices field, it is related to a kind of preparing oxygen using atomic layer deposition method (ALD)
The method of compound/metal magnetic hetero-junctions.
Background technology
With the continuous development of science and technology, the size of electronic product is smaller and smaller, and the storage density of traditional devices and
The speed of service becomes closer to its physics limit, this is because traditional electronic device is using the charge of electronics as information carrier,
Do not consider electron spin.Spintronics is the Spin-Polarized Transport for studying electronics and the electronic device developed is in main
The subject held, as a new branch of science, development also faces lot of challenges.Ferroso-ferric oxide (Fe3O4) it is a kind of heavy
The 3d transistion metal compounds wanted, the spin polarizability of electronics is very high, is that spintronics aspect is possible to realize industrialization
One of material of application.The growing method of common ferriferrous oxide film includes：Pulsed laser deposition (pulsed
Laser deposition, PLD), laser molecular beam epitaxy (laser molecular beam epitaxy, LMBE), magnetic
Control sputtering (magnetron sputtering, including rf magnetron sputtering, magnetically controlled DC sputtering and excitation magnetron sputtering) and height
Energy ion beam evaporation (High-energy ion beam evaporation) etc..These methods are high-energy preparation process,
Iron complete oxidation would generally be become the Fe of trivalent by preparation process2O3, then obtained in the annealing by subsequent hydrogen atmosphere
Fe3O4.Since these methods can carry out at high temperature either in deposition process or in annealing process so that in flexibility
Polymeric substrates prepare Fe3O4Film can not be achieved.In addition it with the continuous promotion to performance requirement, needs in three-dimensional structure
It is several nanometers of film that (such as depth is than prodigious groove, 3D fin structures etc.) surface, which prepares thickness, and above-mentioned several method by
Cause it thickness and the highly controllable film of component can not be made in complex three-dimensional body structure surface in the limitation of deposition principle, to
Hinder the realization of practical application.
Invention content
The purpose of the present invention is to provide a kind of sides preparing oxide/metal magnetism hetero-junctions using atomic layer deposition method
Method, this method can deposit stoicheiometry and film by being accurately controlled to atomic layer deposition process on different metal substrate
The thin magnetic film of thickness controllable precise can be used for preparing in the metal substrate with complex three-dimensional nanostructure three-dimensional uniform
Conformal oxide/metal magnetism hetero-junctions.
In order to achieve the above objectives, the technical solution adopted by the present invention is：
A method of oxide/metal magnetism hetero-junctions is prepared using atomic layer deposition method, is included the following steps：
1) metal substrate pre-processes：By metal substrate in the washing lotion with oxidisability immersion treatment, then use deionization
Water is rinsed well and is dried up with nitrogen, spare；
2) using ferrocene as source of iron, oxygen is packed into atomic layer deposition system Solid Source steel cylinder as oxygen source, by ferrocene
In and be heated to 150~165 DEG C, it is spare in the reaction chamber by oxygen by piping connection to atomic layer deposition system；
3) metal substrate that step 1) is got ready is put into the reaction chamber of atomic layer deposition system, by the temperature liter of reaction chamber
It is kept the temperature after to 400~500 DEG C, makes metal substrate thermally equivalent；
4) deposition parameter is set：Be arranged ferrocene source carrier gas high flow capacity be 150~250sccm, the burst length be 2~
4s, scavenging period are 25~40s, and the carrier gas low discharge of ferrocene is 50~100sccm, the low discharge carrier gas duration is 20~
30s；The flow that source of oxygen is arranged is 200~300sccm, and the burst length is 6~12s, and scavenging period is 10~20s；Setting pipe
The flow on road is 250~350sccm, ensures that the pressure in the reaction chamber of atomic layer deposition system maintains 1500~2500Pa；
5) parameter being arranged according to step 4) carries out cyclic deposition on the metallic substrate, and it is different to obtain oxide/metal magnetism
Matter knot, and the thickness of the number regulation and control oxide/metal magnetism hetero-junctions deposited by control loop；Wherein one cycle deposits
First to carry out a ferrocene pulse in a steady stream, then detergent line after the end-of-pulsing of ferrocene source carries out a pulse of oxygen, oxygen
Detergent line after air source end-of-pulsing.
The metal substrate includes Cu substrates, Ni substrates and Al substrates.
It is 1 that the washing lotion with oxidisability, which is volume ratio, in the step 1):1~5:The mixing of 1 concentrated sulfuric acid and hydrogen peroxide
The processing time of solution, metal substrate is 1~10 minute.
With nitrogen as the carrier gas of ferrocene in deposition process, and first to the atom equipped with ferrocene before starting deposition
Layered deposition system Solid Source steel cylinder carries out pre- pumping process, to exclude air therein.
Soaking time in the step 3) is 1.5~2.5h.
Nitrogen detergent line is used during cyclic deposition.
The number of cyclic deposition is 200~1000 times.
Oxide/metal magnetism hetero-junctions obtained includes Fe3O4/ Cu hetero-junctions, Fe3O4/ Ni hetero-junctions and Fe3O4/Al
Hetero-junctions, and Fe3O4With ferromagnetism.
Compared with the existing technology, beneficial effects of the present invention are：
The method provided by the invention for preparing oxide/metal magnetism hetero-junctions using atomic layer deposition method, this method are adopted
With atomic layer deposition method, using ferrocene as source of iron, oxygen deposits ferroso-ferric oxide on the metallic substrate as oxygen source, passes through
Atomic layer deposition system, which replaces ferrocene with oxygen, to be passed through in the reaction chamber of atomic layer deposition system, realizes ferroso-ferric oxide
(Fe3O4) deposition on different metal substrate, and then construct oxide/metal magnetism hetero-junctions.Atomic layer deposition method conduct
A kind of novel film preparation means, deposition principle are that reaction source substance reacts to be formed by sorption chemical in substrate surface
Film, reaction characteristics be whole process include two it is complementary and from restrictive half-reaction process constitute, be a kind of low energy
Growth course, this is advantageously implemented prepares ferroso-ferric oxide at a lower temperature, to realize the system in some specialized substrates
It is standby to need.By the principle of atomic layer deposition it is recognised that can be realized on an atomic scale using this method to preparing film thickness
It spends and is accurately controlled with what is formed, prepare the thin-film material of high quality on substrate.Therefore atomic layer deposition is produced from rotation electronics
A kind of ideal method of oxide/metal hetero-junctions in.The present invention by the well-designed of atomic layer deposition process and
It accurately controls, realizes the thin magnetic film for depositing stoicheiometry and film thickness controllable precise on different metal substrate, to
To the purpose of oxide/metal magnetism hetero-junctions.Oxide/metal magnetism hetero-junctions produced by the present invention can be used as magneto-electric coupled
The Primary Component of regulation and control.Raw material in the present invention is using cheap and easy to get, nontoxic, and free of contamination ferrocene is with oxygen as precursor
Source, entire reaction process are disposably completed in atomic layer deposition system, and oxide/metal magnetism hetero-junctions quality obtained is high
Degree is controllable, and environmentally safe, is a kind of safe and efficient preparation method.This method can be used for receiving with complex three-dimensional
100% three-dimensional uniform conformal magnetic hetero-junctions is prepared in the metal substrate of rice structure, prepares three-dimensional magnetic hetero-junctions
Key technology and completely new approach, to realize large area, the preparation of inexpensive three-dimensional oxide/metal magnetic hetero-junctions and magnetoelectricity coupling
It closes regulation and control and provides a kind of optional new method.Oxide/metal magnetism hetero-junctions made from this method has at low cost, film
The advantages that ingredient and thickness controllable precise, three-dimensional is uniformly conformal good.Oxide/metal magnetism hetero-junctions produced by the present invention passes through
Raman spectrometer, field emission scanning electron microscope, transmission electron microscope, vibrations sample magnetometer, electronic paramagnetic resonance spectrometer etc.
Advanced test equipment is tested and is analyzed, and test result shows that oxide/metal magnetism hetero-junctions obtained has following property
Matter：1) by atomic layer deposition, film obtained is the ferroso-ferric oxide Fe of pure phase on different metal substrate3O4, rather than
Fe2O3.2) Fe made from3O4Film surface is smooth, homogeneous grain size, has good three-dimensional conformal and thickness accurately may be used
Control.3) Fe made from3O4Film is ferromagnetism.4) Fe made from3O4Magneto-electric coupled regulation and control can be achieved.
Further, oxide/metal magnetism produced by the present invention is heterogeneous becomes Fe3O4/ Cu hetero-junctions, Fe3O4/ Ni is different
Matter knot or Fe3O4/ Al hetero-junctions；Wherein Fe3O4It is ferromagnetic oxide for ferroso-ferric oxide, it is raw in situ by atomic layer deposition
In long metal substrate；Cu, Ni, Al are metal substrate.
Further, the present invention in deposition process using high pure nitrogen as carrier gas, and use high pure nitrogen detergent line, and
And pre- pumping process is carried out to ferrocene source steel cylinder before starting deposition, to exclude air remaining in pipeline and ferrocene source,
And ensures that ferrocene source has sufficient saturated vapour pressure to ensure the stabilization of pulse, while ensureing that ferrocene will not be heated
By oxygenolysis in journey.
Description of the drawings
Fig. 1 is the Raman collection of illustrative plates of oxide/metal magnetism hetero-junctions made from the embodiment of the present invention 1,2,3；
Fig. 2 is the field emission scanning electron microscope photo of oxide/metal magnetism hetero-junctions made from the embodiment of the present invention 1.
Fig. 3 is the field emission scanning electron microscope photo of oxide/metal magnetism hetero-junctions made from the embodiment of the present invention 2.
Fig. 4 is the electron paramagnetic resonance spectrum (EPR) figure of oxide/metal magnetism hetero-junctions made from the embodiment of the present invention 2.
Fig. 5 is the electron paramagnetic resonance spectrum (EPR) figure of oxide/metal magnetism hetero-junctions made from the embodiment of the present invention 3.
Specific implementation mode
The present invention is described in further details with reference to the present invention preferably embodiment and attached drawing.
Embodiment 1
1), substrate pre-treatment：It is dense H that required Cu substrates, which will be tested, in volume ratio2SO4:H2O2=1:In 1 washing lotion
Reason 3 minutes, then takes out substrate from washing lotion, is rinsed and is dried up with high pure nitrogen spare with a large amount of deionized waters；
2), using ferrocene as source of iron, oxygen deposits ferriferrous oxide film as oxygen source.Ferrocene is packed into atom
The special Solid Source steel cylinder of layered deposition system is simultaneously heated to 150 DEG C, and it is anti-that oxygen by dedicated pipeline is connected to atomic deposition system
Answer chamber spare.Pre- pumping process is carried out to ferrocene source steel cylinder before starting deposition, to exclude mixed air during loading of source,
And ensure the pulse of ferrocene source stabilization and will not be during heating by oxygenolysis；
3), the metal substrate for having pre-processed step 1) is sent into reaction cavity by vacuum robot loading system, will
Cavity temperature is set as 400 DEG C, and after cavity temperature reaches set temperature value, heat preservation 1.5h keeps substrate full and uniform heated；
4) deposition parameter, is set：Setting the carrier gas high flow capacity in ferrocene source to 150sccm, the burst length is set as 2s,
Scavenging period is set as 25s, and the carrier gas low discharge of ferrocene is set as 50sccm, and the low discharge duration is set as 20s, two cyclopentadienyls
The carrier gas of iron is high pure nitrogen；It is 200sccm by the flow set of source of oxygen, the burst length is set as 6s, scavenging period setting
For 10s；Piping flow is set as 250sccm and ensures that cavity reaction pressure maintains 1700Pa or so.
5), after completing setting of the step 3) with step 4), deposition is proceeded by.First subpulse is ferrocene source arteries and veins
Punching, system uses high pure nitrogen detergent line automatically after end-of-pulsing, and the second subpulse is pulse of oxygen, system after end-of-pulsing
Automatically high pure nitrogen detergent line is used, completes an ALD cycle deposition process at this time.Cyclic deposition 300 times repeatedly,
The uniform Fe of preset thickness is deposited on Cu substrates3O4Film is to get to Fe3O4/ Cu hetero-junctions.
Embodiment 2
1), substrate prepares：It is dense H that required Ni substrates, which will be tested, in volume ratio2SO4:H2O2=3:5 are handled in 1 washing lotion
Minute, substrate is taken out from washing lotion then, is rinsed and is dried up with nitrogen spare with a large amount of deionized waters；
2), using ferrocene as source of iron, oxygen deposits ferriferrous oxide film as oxygen source.Ferrocene is packed into atom
The special Solid Source steel cylinder of layered deposition system is simultaneously heated to 160 DEG C, and it is anti-that oxygen by dedicated pipeline is connected to atomic deposition system
Answer chamber spare.Pre- pumping process is carried out to ferrocene source steel cylinder before starting deposition, to exclude mixed air during loading of source,
And ensure the pulse of ferrocene source stabilization and will not be during heating by oxygenolysis；
3), the substrate for having pre-processed step 1) is sent into reaction cavity by mechanical arm, and the heating temperature of cavity is set
450 DEG C are set to, after cavity temperature reaches set temperature value, heat preservation 2h keeps substrate full and uniform heated；
4) deposition parameter, is set：Setting the carrier gas high flow capacity in ferrocene source to 200sccm, the burst length is set as 3s,
Scavenging period is set as 30s, and the carrier gas low discharge of ferrocene is set as 70sccm, and the low discharge duration is set as 25s, two cyclopentadienyls
The carrier gas of iron is high pure nitrogen；It is 250sccm by the flow set of source of oxygen, the burst length is set as 8s, scavenging period setting
For 12s；Piping flow is set as 300sccm and ensures that cavity reaction pressure maintains 1800Pa；
5), after completing setting of the step 3) with step 4), deposition is proceeded by.First subpulse is ferrocene source arteries and veins
It rushes, it is source of oxygen pulse, pulse knot to use high pure nitrogen detergent line, the second subpulse automatically by program setting after end-of-pulsing
High pure nitrogen detergent line is used automatically by program setting after beam, completes a cyclic deposition process at this time.It recycles repeatedly
Deposition 600 times, deposits the uniform Fe of preset thickness on Ni substrates3O4Film is to get to Fe3O4/ Ni hetero-junctions.
Embodiment 3
1), substrate prepares：It is dense H that required Al substrates, which will be tested, in volume ratio2SO4:H2O2=5:It is handled in 1 washing lotion
10 minutes, then substrate took out from washing lotion, is rinsed and is dried up with nitrogen spare with a large amount of deionized waters；
2), using ferrocene as source of iron, oxygen deposits ferroso-ferric oxide as oxygen source.Ferrocene is packed into atomic layer deposition
Product system-specific Solid Source steel cylinder is simultaneously heated to 165 DEG C, and oxygen is connected to atomic deposition system response chamber by dedicated pipeline
It is spare.Pre- pumping process is carried out to ferrocene source steel cylinder before starting deposition, to exclude mixed air during loading of source, and
Ensure ferrocene source pulse stabilization and will not be during heating by oxygenolysis；
3), the substrate for having pre-processed step 1) is sent into reaction cavity by mechanical arm, and the heating temperature of cavity is set
500 DEG C are set to, after cavity temperature reaches set temperature value, heat preservation 2.5h keeps substrate full and uniform heated；
4) deposition parameter, is set：Setting the carrier gas high flow capacity in ferrocene source to 250sccm, the burst length is set as 4s,
Scavenging period is set as 40s, and the carrier gas low discharge of ferrocene is set as 100sccm, and the low discharge duration is set as 30s, and two
The carrier gas of luxuriant iron is high pure nitrogen；It is 300sccm by the flow set of source of oxygen, the burst length is set as 10s, and scavenging period is set
It is set to 14s；Piping flow is set as 350sccm and ensures that cavity reaction pressure maintains 1900Pa；
5), after completing setting of the step 3) with step 4), deposition is proceeded by.First subpulse is ferrocene source arteries and veins
It rushes, it is source of oxygen pulse, pulse knot to use high pure nitrogen detergent line, the second subpulse automatically by program setting after end-of-pulsing
High pure nitrogen detergent line is used automatically by program setting after beam, completes a cyclic deposition process at this time.It recycles repeatedly
Deposition 700 times, deposits the uniform Fe of preset thickness on Al substrates3O4Film is to get to Fe3O4/ Al hetero-junctions.
Embodiment 4
1), substrate pre-treatment：It is dense H that required Cu substrates, which will be tested, in volume ratio2SO4:H2O2=2:In 1 washing lotion
Reason 7 minutes, then takes out substrate from washing lotion, is rinsed and is dried up with high pure nitrogen spare with a large amount of deionized waters；
2), using ferrocene as source of iron, oxygen deposits ferriferrous oxide film as oxygen source.Ferrocene is packed into atom
The special Solid Source steel cylinder of layered deposition system is simultaneously heated to 155 DEG C, and it is anti-that oxygen by dedicated pipeline is connected to atomic deposition system
Answer chamber spare.Pre- pumping process is carried out to ferrocene source steel cylinder before starting deposition, to exclude mixed air during loading of source,
And ensure the pulse of ferrocene source stabilization and will not be during heating by oxygenolysis；
3), the metal substrate for having pre-processed step 1) is sent into reaction cavity by vacuum robot loading system, will
Cavity temperature is set as 420 DEG C, and after cavity temperature reaches set temperature value, heat preservation 1.8h keeps substrate full and uniform heated；
4) deposition parameter, is set：Set the carrier gas high flow capacity in ferrocene source to 180sccm, the burst length is set as
2.5s, scavenging period are set as 35s, and the carrier gas low discharge of ferrocene is set as 60sccm, and the low discharge duration is set as
The carrier gas of 22s, ferrocene are high pure nitrogen；It is 220sccm by the flow set of source of oxygen, the burst length is set as 9s, cleans
Time is set as 17s；Piping flow is set as 280sccm and ensures that cavity reaction pressure maintains 1500Pa or so.
5), after completing setting of the step 3) with step 4), deposition is proceeded by.First subpulse is ferrocene source arteries and veins
Punching, system uses high pure nitrogen detergent line automatically after end-of-pulsing, and the second subpulse is pulse of oxygen, system after end-of-pulsing
Automatically high pure nitrogen detergent line is used, completes an ALD cycle deposition process at this time.Cyclic deposition 200 times repeatedly,
The uniform Fe of preset thickness is deposited on Cu substrates3O4Film is to get to Fe3O4/ Cu hetero-junctions.
Embodiment 5
1), substrate prepares：It is dense H that required Ni substrates, which will be tested, in volume ratio2SO4:H2O2=4:1 is handled in 1 washing lotion
Minute, substrate is taken out from washing lotion then, is rinsed and is dried up with nitrogen spare with a large amount of deionized waters；
2), using ferrocene as source of iron, oxygen deposits ferriferrous oxide film as oxygen source.Ferrocene is packed into atom
The special Solid Source steel cylinder of layered deposition system is simultaneously heated to 158 DEG C, and it is anti-that oxygen by dedicated pipeline is connected to atomic deposition system
Answer chamber spare.Pre- pumping process is carried out to ferrocene source steel cylinder before starting deposition, to exclude mixed air during loading of source,
And ensure the pulse of ferrocene source stabilization and will not be during heating by oxygenolysis；
3), the substrate for having pre-processed step 1) is sent into reaction cavity by mechanical arm, and the heating temperature of cavity is set
480 DEG C are set to, after cavity temperature reaches set temperature value, heat preservation 2.2h keeps substrate full and uniform heated；
4) deposition parameter, is set：Set the carrier gas high flow capacity in ferrocene source to 220sccm, the burst length is set as
3.5s, scavenging period are set as 28s, and the carrier gas low discharge of ferrocene is set as 80sccm, and the low discharge duration is set as
The carrier gas of 28s, ferrocene are high pure nitrogen；It is 280sccm by the flow set of source of oxygen, the burst length is set as 12s, cleans
Time is set as 20s；Piping flow is set as 320sccm and ensures that cavity reaction pressure maintains 2500Pa；
5), after completing setting of the step 3) with step 4), deposition is proceeded by.First subpulse is ferrocene source arteries and veins
It rushes, it is source of oxygen pulse, pulse knot to use high pure nitrogen detergent line, the second subpulse automatically by program setting after end-of-pulsing
High pure nitrogen detergent line is used automatically by program setting after beam, completes a cyclic deposition process at this time.It recycles repeatedly
Deposition 1000 times, deposits the uniform Fe of preset thickness on Ni substrates3O4Film is to get to Fe3O4/ Ni hetero-junctions.
Fig. 1 is the Raman collection of illustrative plates of oxide/metal magnetism hetero-junctions made from the embodiment of the present invention 1,2,3, can from Fig. 1
To find out, the present invention is using atomic layer deposition method in Cu, and Al, the phase composition of film obtained is Fe on Ni substrates3O4。
Fig. 2 is the field emission scanning electron microscope photo of oxide/metal magnetism hetero-junctions made from the embodiment of the present invention 1, from
As can be seen that the present invention utilizes atomic layer deposition method Fe obtained on Cu substrates in Fig. 23O4Surfacing, consistency is high, protects
Type is good.
Fig. 3 is the field emission scanning electron microscope photo of oxide/metal magnetism hetero-junctions made from the embodiment of the present invention 2, from
As can be seen that the present invention utilizes atomic layer deposition method Fe obtained on Ni substrates in Fig. 33O4Surfacing, consistency is high, protects
Type is good.
Fig. 4 is the electron paramagnetic resonance spectrum (EPR) figure of oxide/metal magnetism hetero-junctions made from the embodiment of the present invention 2, from
As can be seen that the present invention utilizes atomic layer deposition method Fe obtained on Cu substrates in Fig. 43O4For ferromagnetism, face internal resonance field
Knead dough external resonance field is respectively 215Oe and 443Oe.
Fig. 5 is the electron paramagnetic resonance spectrum (EPR) figure of oxide/metal magnetism hetero-junctions made from the embodiment of the present invention 3, from
As can be seen that the present invention utilizes atomic layer deposition method Fe obtained on Al substrates in Fig. 53O4For ferromagnetism, face internal resonance field
Knead dough external resonance field is respectively 215Oe and 464Oe.
Claims (7)
1. a kind of method preparing oxide/metal magnetism hetero-junctions using atomic layer deposition method, which is characterized in that including following
Step：
1) metal substrate pre-processes：By metal substrate in the washing lotion with oxidisability immersion treatment, then rushed with deionized water
Wash clean is simultaneously dried up with nitrogen, spare；The metal substrate includes Cu substrates, Ni substrates or Al substrates；
2) using ferrocene as source of iron, ferrocene is fitted into atomic layer deposition system Solid Source steel cylinder simultaneously by oxygen as oxygen source
150~165 DEG C are heated to, it is spare in the reaction chamber by oxygen by piping connection to atomic layer deposition system；
3) metal substrate that step 1) is got ready is put into the reaction chamber of atomic layer deposition system, the temperature of reaction chamber is risen to
It is kept the temperature after 400~500 DEG C, makes metal substrate thermally equivalent；
4) deposition parameter is set：The carrier gas high flow capacity that ferrocene source is arranged is 150~250sccm, and the burst length is 2~4s, clearly
It is 25~40s to wash the time, and the carrier gas low discharge of ferrocene is 50~100sccm, and the low discharge carrier gas duration is 20~30s；
The flow that source of oxygen is arranged is 200~300sccm, and the burst length is 6~12s, and scavenging period is 10~20s；Pipeline is set
Flow is 250~350sccm, ensures that the pressure in the reaction chamber of atomic layer deposition system maintains 1500~2500Pa；
5) parameter being arranged according to step 4) carries out cyclic deposition on the metallic substrate, obtains oxide/metal magnetism hetero-junctions,
And regulate and control the thickness of oxide/metal magnetism hetero-junctions by the number that control loop deposits；Wherein one cycle is deposited as elder generation
A ferrocene pulse in a steady stream is carried out, then detergent line after the end-of-pulsing of ferrocene source carries out a pulse of oxygen, source of oxygen
Detergent line after end-of-pulsing.
2. the method according to claim 1 for preparing oxide/metal magnetism hetero-junctions using atomic layer deposition method, special
Sign is：It is 1 that the washing lotion with oxidisability, which is volume ratio, in the step 1):1~5:The mixing of 1 concentrated sulfuric acid and hydrogen peroxide is molten
The processing time of liquid, metal substrate is 1~10 minute.
3. the method according to claim 1 for preparing oxide/metal magnetism hetero-junctions using atomic layer deposition method, special
Sign is：With nitrogen as the carrier gas of ferrocene in deposition process, and first to the atom equipped with ferrocene before starting deposition
Layered deposition system Solid Source steel cylinder carries out pre- pumping process, to exclude air therein.
4. the method according to claim 1 for preparing oxide/metal magnetism hetero-junctions using atomic layer deposition method, special
Sign is：Soaking time in the step 3) is 1.5~2.5h.
5. the method according to claim 1 for preparing oxide/metal magnetism hetero-junctions using atomic layer deposition method, special
Sign is：Nitrogen detergent line is used during cyclic deposition.
6. the method according to claim 1 for preparing oxide/metal magnetism hetero-junctions using atomic layer deposition method, special
Sign is：The number of cyclic deposition is 200~1000 times.
7. the method according to claim 1 for preparing oxide/metal magnetism hetero-junctions using atomic layer deposition method, special
Sign is：Oxide/metal magnetism hetero-junctions obtained includes Fe3O4/ Cu hetero-junctions, Fe3O4/ Ni hetero-junctions or Fe3O4/ Al is different
Matter knot, and Fe3O4With ferromagnetism.
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