CN107177834A - A kind of method for regulating and controlling atomic layer deposition thin film magnetic using situ Magnetic Field - Google Patents

A kind of method for regulating and controlling atomic layer deposition thin film magnetic using situ Magnetic Field Download PDF

Info

Publication number
CN107177834A
CN107177834A CN201710405411.2A CN201710405411A CN107177834A CN 107177834 A CN107177834 A CN 107177834A CN 201710405411 A CN201710405411 A CN 201710405411A CN 107177834 A CN107177834 A CN 107177834A
Authority
CN
China
Prior art keywords
substrate
atomic layer
layer deposition
magnetic field
situ
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.)
Granted
Application number
CN201710405411.2A
Other languages
Chinese (zh)
Other versions
CN107177834B (en
Inventor
刘明
张易军
张乐
任巍
叶作光
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.)
Xian Jiaotong University
Original Assignee
Xian Jiaotong University
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 Xian Jiaotong University filed Critical Xian Jiaotong University
Priority to CN201710405411.2A priority Critical patent/CN107177834B/en
Publication of CN107177834A publication Critical patent/CN107177834A/en
Application granted granted Critical
Publication of CN107177834B publication Critical patent/CN107177834B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical 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
    • C23C16/455Chemical 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
    • C23C16/45523Pulsed gas flow or change of composition over time
    • C23C16/45525Atomic layer deposition [ALD]
    • C23C16/45527Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22Chemical 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
    • C23C16/30Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40Oxides
    • C23C16/406Oxides of iron group metals
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical 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
    • C23C16/455Chemical 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
    • C23C16/45523Pulsed gas flow or change of composition over time
    • C23C16/45525Atomic layer deposition [ALD]
    • C23C16/45553Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Thin Magnetic Films (AREA)
  • Hall/Mr Elements (AREA)

Abstract

The invention discloses a kind of method for regulating and controlling atomic layer deposition thin film magnetic using situ Magnetic Field, it is therefore intended that, the Fe of preparation3O4The magnetic anisotropy of film is obvious, with higher strong Wan, and Fe3O4Film surface appearance is uniform, and extra coarse degree is small, the technical scheme used for, including:1) clean substrate is placed on the magnetic pole of permanent magnet, and substrate and permanent magnet be placed in vacuum reaction cavity heat standby, and heating-up temperature is less than the Curie temperature of permanent magnet;2) using ferrocene steam as source of iron, using oxygen as oxygen source, ferrocene steam and oxygen ALT pulse is sent into vacuum reaction cavity, atomic layer deposition cycles several times are carried out to substrate, until uniform deposition has conformal Fe on the surface of substrate3O4Film;3) inert gas is filled with into vacuum reaction cavity, is taken out after substrate naturally cools to room temperature.

Description

A kind of method for regulating and controlling atomic layer deposition thin film magnetic using situ Magnetic Field
Technical field
Thin film technique field is prepared the invention belongs to atomic layer deposition method, and in particular to one kind is regulated and controled using situ Magnetic Field The method of atomic layer deposition thin film magnetic.
Background technology
In the late two decades, in order to which magneto-electronicses are applied in semiconductor industry highly developed till now, Hen Duoren Gradually concentrate on on semiconductor magnetoeletronic.The major advantage of this new branch of science is can be with traditional metal Oxide semiconductor technology is compatible, so that the addition spin free degree on traditional semiconductor based on electric charge, makes now The function of electronics device be expanded, performance is improved, and improves speed and integration density and the reduction of data processing Power consumption etc., makes now that very ripe microelectric technique has been expanded.Now, semiconductor magnetoeletronic is considered as magnetoelectricity Son learns the main flow direction of extensive practical most realistic approach and Future Development.Spintronics and microelectronics promote super The demand of the thin and high-quality magnetic oxide film of three-dimensional conformal so that the controllable growth of ultra-thin and three-dimensional conformal magnetic oxide As the key technique problem for being badly in need of solving, the magnetic controllable growth of especially magnetic oxide is the technology hardly possible of bottleneck Topic, such as high density data storage, sensor and spintronics.However, so far, preparing magnetic oxide film Method mainly has following several:(1) using pulsed laser deposition (PLD), the method technics comparing is simple, the crystalline of film Measure, but large-area uniformity and thickness accurately control poor, and can not realize three-dimensional uniform conformal covering.(2) magnetic control Sputtering is the most frequently used magnetic oxide film growth method, and the method has preferable planar uniformity and quality of forming film, so And the controllable precise of Subnano-class can not be realized in the accurate control aspect of film thickness, especially with complex three-dimensional nano junction Three-dimensional uniform conformal covering can not be realized on the substrate of structure.(3) it can be prepared with certain using chemical vapor deposition (CVD) method The Fe of three-dimensional uniformity3O4Film, but be due to that Fe has Fe2O3And Fe3O4Two kinds of stable oxides, so wanting to prepare pure The Fe of phase3O4Film is relatively difficult.In addition CVD accurately controlled in thickness and in the three-dimensional structure with larger depth-to-width ratio still Uniform conformal covering can not be realized.In summary, existing preparation Fe3O4The conventional method of film has thickness not control accurately With can not realize the bottleneck problem of three-dimensional uniform conformal covering.But current microelectric technique is developed rapidly, 22nm and with The microelectronic circuit of lower line width uses three-dimensional structure as Fin-FET or Tri-Get.This indicate microelectronic circuit from Flatness structural transition has been trend of the times to three-dimensional structure, how to solve from plane be transitioned into after three-dimensional structure tradition PVD and The technical bottleneck problem (three-dimensional conformal uniformity and magnetic controllability etc.) that CVD technology faces is key problem.
Ald (Atomic Layer Deposition, ALD) film deposition techniques are to be a kind of from limitation (self- Limiting superficial growth mode), with extraordinary three-dimensional uniformity.In fact in microelectronic ALD conducts One kind prepares the high-quality dielectric layer and CMOS transistor high-k of dynamic random access memory (DRAMs) trench capacitor The key technology of layer.ALD is a kind of can to realize the film deposition techniques of self limitation that monoatomic layer successively grows, its feature For can in the three-dimensional structure of any shape all deposit thickness controllable precise and 100% uniform conformal film, this satisfies system The active demand of standby three dimensional microelectronic device.But prepare Fe with ALD3O4Film generally has weaker magnetic anisotropic, and this is Because Fe prepared by ALD3O4Film crystal unity is low, and crystal grain is smaller, so Fe prepared by ALD3O4Typically to be isotropic Superparamagnetism, so we pass through in Fe in this invention3O4The growth course situ of film adds magnetic field to induce Fe3O4Film In magnetic moment orientation, and then induce magnetic anisotropic, have no using situ Magnetic Field to induce ALD to prepare Fe so far3O4It is thin The relevant report of magnetic anisotropy in film.
The content of the invention
In order to solve the problems of the prior art, it is thin that the present invention proposes that one kind regulates and controls ald using situ Magnetic Field The method of film magnetic, method is simple to operate, raw material is cheap and safety non-toxic, it is pollution-free, beneficial to volume production and with existing IC techniques Compatibility, Fe prepared by method3O4The magnetic anisotropy of film is obvious, with higher strong Wan, and Fe3O4Film surface appearance Uniformly, extra coarse degree is small.
In order to realize the above object the technical solution adopted in the present invention is:Comprise the following steps:
1) clean substrate is placed on the magnetic pole of permanent magnet, and substrate and permanent magnet is placed in vacuum reaction cavity Heating is standby, and heating-up temperature is less than the Curie temperature of permanent magnet;
2) using ferrocene steam as source of iron, using oxygen as oxygen source, ferrocene steam and oxygen ALT pulse are sent into In vacuum reaction cavity, atomic layer deposition cycles several times are carried out to substrate, until uniform deposition has conformal on the surface of substrate Fe3O4Film;
3) inert gas is filled with into vacuum reaction cavity, is taken out after substrate naturally cools to room temperature.
The step 1) in the clean processing of substrate include:Substrate 10 is cleaned successively with acetone and absolute ethyl alcohol respectively first ~15 minutes;Then it is cleaned by ultrasonic repeatedly with deionized water 3~5 times, each 5~10 minutes every time;By base after the completion of finally cleaning The dry nitrogen drying of piece taking-up.
The step 1) in substrate and permanent magnet be heated to 350~450 DEG C under an inert atmosphere.
The substrate is Au/Si substrates or Pt/Si substrates, and the Curie temperature of the permanent magnet is more than 450 DEG C.
The permanent magnet is the cylindrical SnCo magnet that a diameter of 10mm-50mm, thickness are 5mm-10mm.
The step 2) in each atomic layer deposition cycles include:1~4s source of oxygen pulses are carried out first;Then nitrogen is used Clean 6-16s;Secondly the source pulse of 0.1~0.4s ferrocene is carried out;Finally 6~16s is cleaned with nitrogen.
The step 2) in ferrocene steam be by ferrocene in the Solid Source heater of atomic layer deposition apparatus plus Obtained after hot to 140~160 DEG C.
The ferrocene steam and oxygen use response speed to send into vacuum for the ALD pulse valves of Millisecond come ALT pulse In reaction cavity.
Compared with prior art, the present invention provides situ Magnetic Field to induce ALD former from the permanent magnet of high-curie temperature Position prepares Fe3O4The magnetic anisotropy of film, the precursor source used is used as iron and oxygen for cheap ferrocene and oxygen Precursor source, makes ferrocene be reacted with oxygen, in Au/Si or Pt/Si substrate surfaces by ald (ALD) equipment The Fe of depositing homogeneous3O4Film, film thickness and the composition all uniform, controllables deposited, surface is smooth.The inventive method not only may be used To prepare three-dimensional uniform conformal Fe3O4Film, can also induce obvious magnetic anisotropy and ferrous iron using situ Magnetic Field Magnetic.The inventive method is simple to operate, and advantages of nontoxic raw materials is pollution-free, and large area and batch production can be achieved.Through the inventive method system The Fe obtained3O4Film is tested and analyzed by electronic paramagnetic resonance spectrometer (ESR), it is determined that having the following properties that:1st, it is plus former The Fe of position magnetic field growth3O4Fe of the film than not adding situ Magnetic Field3O4Film has magnetic outside in stronger face and face each to different Property;2nd, the Fe of situ Magnetic Field growth is added3O4Fe of the film than not adding situ Magnetic Field3O4Film has higher strong Wan;3、 Fe3O4Film surface appearance is uniform, and extra coarse degree is small;4th, the Fe of situ Magnetic Field growth is added3O4Film is with and without adding situ Magnetic Field The Fe of growth3O4With identical surface topography.
Further, each atomic layer deposition cycles include following four step:1~4s source of oxygen pulses are carried out first;Then 6-16s is cleaned with nitrogen;Secondly the source pulse of 0.1~0.4s ferrocene is carried out;6~16s finally is cleaned with nitrogen, will not reacted Ferrocene drain, repeat above procedure for several times until the film thickness grown reaches the requirement of oneself, the thickness of film Controllable precise can be simply realized by setting ALD cycle number.
Brief description of the drawings
Fig. 1 plus under the conditions of situ Magnetic Field is not growing Fe using ALD3O4The FMR curve maps of/Au/Si samples;
Fig. 2 grows Fe using ALD under the conditions of added with situ Magnetic Field3O4The FMR curve maps of/Au/Si samples;
Fig. 3 plus under the conditions of situ Magnetic Field is not growing Fe using ALD3O4The FMR curve maps of/Pt/Si samples;
Fig. 4 grows Fe using ALD under the conditions of added with situ Magnetic Field3O4The FMR curve maps of/Pt/Si samples.
Embodiment
The present invention is further explained with reference to specific embodiment and Figure of description.
The present invention comprises the following steps:1) Au/Si or Pt/Si substrates are used into acetone and absolute ethyl alcohol successively respectively first Cleaning 10~15 minutes;Then it is cleaned by ultrasonic repeatedly with deionized water 3~5 times, each 5~10 minutes every time;Will after the completion of cleaning The dry nitrogen drying of Au/Si or Pt/Si substrates taking-up is standby.
2) substrate of clean plane or three-dimensional structure is placed on to the magnetic of cylindrical permanent magnet of the Curie temperature more than 450 DEG C On pole and ALD vacuum reaction cavitys are sent into, then in N2Be heated under atmosphere 350~450 DEG C it is standby;
4) using ferrocene as source of iron, ferrocene is heated to 140 in the Solid Source heater of atomic layer deposition system Ferrocene steam is obtained after~160 DEG C, using oxygen as oxygen source, ferrocene steam and oxygen are passed through atomic layer deposition apparatus Carrier gas system, is then sent into vacuum reaction cavity by carrier gas system, is controlled by the ALD pulse valves of Millisecond response speed Ferrocene steam and oxygen enter the amount of vacuum reaction cavity, and atomic layer deposition cycles, each atom are opened in nitrogen atmosphere Layer deposition cycle be:1~4s source of oxygen pulses are first carried out, and 6~16s is cleaned with nitrogen;Then 0.1~0.4s ferrocene is carried out Source pulse, finally cleans 6~16s with nitrogen, until Au/Si the or Pt/Si substrate surfaces in plane or three-dimensional structure sink Uniform conformal Fe in product3O4Film;
4)Fe3O4After the completion of thin film deposition, a certain amount of N is filled with toward vacuum reaction cavity the inside2And allow sample natural cooling Sample is taken out from cavity after to room temperature;
Embodiment 1
The present invention comprises the following steps:
A, Au/Si substrate prepare:Au/Si substrates needed for experiment are taken turns doing into following cleaning:Acetone and anhydrous second are used respectively Alcohol is cleaned 10~15 minutes successively;Then it is cleaned by ultrasonic repeatedly with deionized water 3~5 times, each 5~10 minutes every time;Clean Vacuum reaction cavity is immediately fed into after the taking-up of Au/Si or Pt/Si substrates is dried up with dry nitrogen after to use;
B, ferrocene source loaded in the Solid Source heating source bottle of ALD equipment, source bottle is carried out taking out processing in advance, to take dress away The air introduced in source procedure in source capsule line, setting source bottle heater strip temperature is heated to source, until the steaming of every subpulse Untill vapour pressure is stable, to ensure that ferrocene there are enough vapour pressure pulses to enter carrier gas system, reaction chamber is finally brought into by carrier gas Body;
C, by ready Au/Si substrates by vacuum mechanical-arm send into reaction cavity after start to heat substrate, In order to ensure that gas is pure N inside reaction cavity2Gas, need to be by the N of every source capsule line2Carrier gas flux is set to 2000sccm, And simultaneously close off vavuum pump extraction valve V6, until the pressure of reaction cavity reaches that system can close carrier gas automatically after an atmospheric pressure And open vavuum pump extraction valve V6Pumping, the gas in reaction cavity is taken away, repeats above step 3 times, can both ensure anti- It is the pure N of comparison to answer inside cavity2, maintain every pipe source line 50sccm nitrogen flow all the time in heating process in addition, with Ensure that reaction cavity pressure maintains stove silk temperature in 800Pa or so, heating process and is set to 500~600 DEG C, substrate temperature is set to 350~450 DEG C, after base reservoir temperature is stable, the ALD deposition program set is performed, specific procedure is as follows:
First pulse is pulse of oxygen, and the pulse of oxygen time is 1~4 second;The nitrogen cleaning burst length is 6~16 seconds;Two The luxuriant iron burst length is 0.1~0.4 second;Nitrogen is cleaned 6~16 seconds, and the carrier gas flux of ferrocene and oxygen is set to 150sccm and 200sccm, the N of other source capsule lines2Carrier gas flux is set to 80sccm, and growth thickness is above-mentioned to perform 400 ALD cycle;
D, by ALD Fe in situ obtained3O4Film is in N2Room temperature is naturally cooled under atmosphere and is taken out.
Fe is grown under the conditions of without situ Magnetic Field referring to Fig. 1 utilization ALD3O4The electron paramagnetic resonance ripple of/Au/Si samples Spectrometer (ESR) test result shows, in the Fe plus under the conditions of situ Magnetic Field not prepared on Au/Si substrates3O4Film has very It is magnetic beach axle (resonant fields are up to 5580Oe) outside strong magnetic anisotropy, face, is magnetic easy axis (resonant fields are 1753Oe), face in face Interior and face external resonance difference 3827Oe.Comparison diagram 2 grows Fe using ALD under the conditions of added with situ Magnetic Field3O4/ Au/Si samples Electronic paramagnetic resonance spectrometer (ESR) test result, it can be clearly seen that plus after situ Magnetic Field, Fe3O4The magnetic of film is each to different Property weakens significantly.Remained as outside face in magnetic beach axle (but face external resonance is reduced to 3297 Oe), face and remain as magnetic easy axis (face Internal resonance increase is 2710 Oe), the difference of in face and face external resonance field is reduced to 587Oe.Situ Magnetic Field allows Fe3O4The face of film Magnetic anisotropy reduces 3240 Oe (3827-587=3240 Oe) outside interior and face, and this is fully demonstrated in ALD growing films During, add in-place magnetic field can effectively change the magnetic anisotropy of film.
Embodiment 2
The present invention comprises the following steps:
A, Pt/Si substrate prepare:Pt/Si substrates needed for experiment are taken turns doing into following cleaning:Acetone and anhydrous second are used respectively Alcohol is cleaned 10~15 minutes successively;Then it is cleaned by ultrasonic repeatedly with deionized water 3~5 times, each 5~10 minutes every time;Clean Vacuum reaction cavity is immediately fed into after the taking-up of Pt/Si substrates is dried up with dry nitrogen after to use;
B, ferrocene source loaded in the Solid Source heating source bottle of ALD equipment, source bottle is carried out taking out processing in advance, to take dress away The air introduced in source procedure in source capsule line, setting source bottle heating-up temperature is heated to source, until the steam of every subpulse Untill pressure is stable, to ensure that ferrocene there are enough vapour pressure pulses to enter carrier gas system, reaction cavity is finally brought into by carrier gas;
C, by ready Pt/Si substrates by vacuum mechanical-arm send into reaction cavity after start to heat substrate, In order to ensure that gas is pure N inside reaction cavity2Gas, need to be by the N of every source capsule line2Carrier gas flux is set to 2000sccm, And simultaneously close off vavuum pump extraction valve V6, until the pressure of reaction cavity reaches that system can close carrier gas automatically after an atmospheric pressure And open vavuum pump extraction valve V6Pumping, the gas in reaction cavity is taken away, repeats above step 3 times, can both ensure anti- It is the pure N of comparison to answer inside cavity2, maintain every pipe source line 50sccm nitrogen flow all the time in heating process in addition, with Ensure that reaction cavity pressure maintains stove silk temperature in 800Pa or so, heating process and is set to 500~600 DEG C, substrate temperature is set to 350~450 DEG C, after base reservoir temperature is stable, the ALD deposition program set is performed, specific procedure is as follows:
First pulse is pulse of oxygen, and the pulse of oxygen time is 1~4 second;The nitrogen cleaning burst length is 6~16 seconds;Two The luxuriant iron burst length is 0.1~0.4 second;Nitrogen is cleaned 6~16 seconds, and the carrier gas flux of ferrocene and oxygen is set to 150sccm and 200sccm, the N of other source capsule lines2Carrier gas flux is set to 80sccm, and growth thickness is above-mentioned to perform 400 ALD cycle;
D, by ALD Fe in situ obtained3O4Film is in N2Room temperature is naturally cooled under atmosphere and is taken out.
Fe is grown under the conditions of without situ Magnetic Field referring to Fig. 3 utilization ALD3O4The electron paramagnetic resonance ripple of/Pt/Si samples Spectrometer (ESR) test result shows, in the Fe plus under the conditions of situ Magnetic Field not prepared on Pt/Si substrates3O4Film has very It is magnetic beach axle (resonant fields are up to 5915Oe) outside strong magnetic anisotropy, face, is magnetic easy axis (resonant fields are 1890Oe), face in face Interior and face external resonance difference 4025Oe.Comparison diagram 4 grows Fe using ALD under the conditions of added with situ Magnetic Field3O4/ Pt/Si samples Electronic paramagnetic resonance spectrometer (ESR) test result, it can be clearly seen that plus after situ Magnetic Field, Fe3O4The magnetic of film is each to different Property weakens significantly.Plus remained as outside behind situ Magnetic Field in magnetic beach axle (but face external resonance is reduced to 3350Oe), face still For magnetic easy axis (face internal resonance increase be 2603Oe), the difference in face with face external resonance field is reduced to 747Oe.Situ Magnetic Field allows The Fe that Pt/Si substrates grow above3O4Magnetic anisotropy reduces 3278Oe (4025-747=outside in the face of film and face 3278Oe), this again demonstrate during ALD growing films, add in-place magnetic field can effectively change film magnetic it is each to The opposite sex.
In summary, the inventive method proposes one kind during ALD growth in situ thin magnetic films plus situ Magnetic Field The method of growth thin magnetic film magnetic anisotropy to regulate and control, by contrast plus situ Magnetic Field and is not added with institute under the conditions of situ Magnetic Field Grow the magnetic anisotropy in thin magnetic film face and outside face, discovery is in various substrates (Au/Si and Pt/Si) grown magnetic above The magnetic anisotropy of film is all largely regulated and controled by situ Magnetic Field.
The method have the advantages that can by ALD grow thin magnetic film during by add in-place magnetic field come Regulate and control ALD just in the magnetic of thin magnetic film.The thickness of thin magnetic film can also be accurately controlled by controlling ALD cycle number of times Degree, preparation process is simple and easy to apply, compatible with existing semiconductor preparing process.

Claims (8)

1. a kind of method for regulating and controlling atomic layer deposition thin film magnetic using situ Magnetic Field, it is characterised in that comprise the following steps:
1) clean substrate is placed on the magnetic pole of permanent magnet, and substrate and permanent magnet is placed in heating in vacuum reaction cavity It is standby, and heating-up temperature is less than the Curie temperature of permanent magnet;
2) using ferrocene steam as source of iron, using oxygen as oxygen source, ferrocene steam and oxygen ALT pulse are sent into vacuum In reaction cavity, atomic layer deposition cycles several times are carried out to substrate, until conformal on uniform deposition on the surface of substrate Fe3O4Film;
3) inert gas is filled with into vacuum reaction cavity, is taken out after substrate naturally cools to room temperature.
2. a kind of method for regulating and controlling atomic layer deposition thin film magnetic using situ Magnetic Field according to claim 1, it is special Levy and be, the step 1) in the clean processing of substrate include:Substrate 10 is cleaned successively with acetone and absolute ethyl alcohol respectively first ~15 minutes;Then it is cleaned by ultrasonic repeatedly with deionized water 3~5 times, each 5~10 minutes every time;By base after the completion of finally cleaning The dry nitrogen drying of piece taking-up.
3. a kind of method for regulating and controlling atomic layer deposition thin film magnetic using situ Magnetic Field according to claim 1 or 2, its Be characterised by, the step 1) in substrate and permanent magnet be heated to 350~450 DEG C under an inert atmosphere.
4. a kind of method for regulating and controlling atomic layer deposition thin film magnetic using situ Magnetic Field according to claim 3, it is special Levy and be, the substrate is Au/Si substrates or Pt/Si substrates, the Curie temperature of the permanent magnet is more than 450 DEG C.
5. a kind of method for regulating and controlling atomic layer deposition thin film magnetic using situ Magnetic Field according to claim 4, it is special Levy and be, the permanent magnet is the cylindrical SnCo magnet that a diameter of 10mm-50mm, thickness are 5mm-10mm.
6. a kind of method for regulating and controlling atomic layer deposition thin film magnetic using situ Magnetic Field according to claim 1, it is special Levy and be, the step 2) in each atomic layer deposition cycles include:1~4s source of oxygen pulses are carried out first;Then nitrogen is used Clean 6-16s;Secondly the source pulse of 0.1~0.4s ferrocene is carried out;Finally 6~16s is cleaned with nitrogen.
7. a kind of use situ Magnetic Field according to claim 1 or 6 regulates and controls the method for atomic layer deposition thin film magnetic, its Be characterised by, the step 2) in ferrocene steam be by ferrocene in the Solid Source heater of atomic layer deposition apparatus plus Obtained after hot to 140~160 DEG C.
8. a kind of method for regulating and controlling atomic layer deposition thin film magnetic using situ Magnetic Field according to claim 7, it is special Levy and be, the ferrocene steam and oxygen use response speed for the ALD pulse valves of Millisecond to control two introduces a collection alternating pulses In punching feeding vacuum reaction cavity.
CN201710405411.2A 2017-05-31 2017-05-31 A method of regulating and controlling atomic layer deposition thin film magnetism using situ Magnetic Field Active CN107177834B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710405411.2A CN107177834B (en) 2017-05-31 2017-05-31 A method of regulating and controlling atomic layer deposition thin film magnetism using situ Magnetic Field

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710405411.2A CN107177834B (en) 2017-05-31 2017-05-31 A method of regulating and controlling atomic layer deposition thin film magnetism using situ Magnetic Field

Publications (2)

Publication Number Publication Date
CN107177834A true CN107177834A (en) 2017-09-19
CN107177834B CN107177834B (en) 2019-05-03

Family

ID=59835956

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710405411.2A Active CN107177834B (en) 2017-05-31 2017-05-31 A method of regulating and controlling atomic layer deposition thin film magnetism using situ Magnetic Field

Country Status (1)

Country Link
CN (1) CN107177834B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104630742A (en) * 2015-01-27 2015-05-20 西安交通大学 Method for in-situ preparing super-paramagnetic Fe3O4 nanotube arrays by atomic layer deposition
CN105925956A (en) * 2016-05-24 2016-09-07 西安交通大学 Method of preparing oxide/metal magnetic heterojunction through atomic layer deposition
CN105925955A (en) * 2016-05-24 2016-09-07 西安交通大学 Method for in-situ preparationof oxide/metal ferromagnetic heterojunction through atomic layer deposition method
CN106086815A (en) * 2016-08-05 2016-11-09 西安交通大学 A kind of method using ald to prepare metal Fe thin film

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104630742A (en) * 2015-01-27 2015-05-20 西安交通大学 Method for in-situ preparing super-paramagnetic Fe3O4 nanotube arrays by atomic layer deposition
CN105925956A (en) * 2016-05-24 2016-09-07 西安交通大学 Method of preparing oxide/metal magnetic heterojunction through atomic layer deposition
CN105925955A (en) * 2016-05-24 2016-09-07 西安交通大学 Method for in-situ preparationof oxide/metal ferromagnetic heterojunction through atomic layer deposition method
CN106086815A (en) * 2016-08-05 2016-11-09 西安交通大学 A kind of method using ald to prepare metal Fe thin film

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
樊希安等: "一维铁磁金属纳米材料的制备、结构调控及其磁性能", 《化学进展》 *

Also Published As

Publication number Publication date
CN107177834B (en) 2019-05-03

Similar Documents

Publication Publication Date Title
CN106086815B (en) A method of metal Fe films are prepared using atomic layer deposition
CN101960631B (en) Process for producing magnetoresistive element and apparatus for producing magnetoresistive element
CN110165053A (en) A kind of ALD preparation Hf towards ferroelectric memory application0.5Zr0.5O2The method of ferroelectric thin film
CN111312898B (en) HfO 2 Ferroelectric thin film material and preparation method and application thereof
CN104193316B (en) Yttrium iron garnet film and preparation method thereof
CN101429646B (en) Production method for film generating in-plane uniaxial magnetic anisotropy in non-inducement magnetic field
CN104630742B (en) Method for in-situ preparing super-paramagnetic Fe3O4 nanotube arrays by atomic layer deposition
CN106591781B (en) A kind of ameliorative way of ultra-thin lanthanum-strontium-manganese-oxygen film interface dead layer
CN112410880B (en) Flexible self-supporting single crystal Fe with self-regulating growth orientation3O4Preparation of thin film material, thin film material and single crystal structure
CN109440081B (en) Method for preparing magnetic graphene film based on chemical vapor deposition method
CN108493102A (en) Method and the application of hafnium oxide based ferroelectric film are prepared using full-inorganic precursor solution
CN110289349B (en) Magnetic adjustable composite metal phthalocyanine film and preparation method thereof
CN107177834B (en) A method of regulating and controlling atomic layer deposition thin film magnetism using situ Magnetic Field
JPH02212320A (en) Production of iron nitride having high magnetism
CN105925955B (en) A method of oxide/metal ferromagnetism hetero-junctions is prepared in situ using atomic layer deposition method
CN102157262B (en) Method for preparing capacitor with Ta205 thin film as dielectric film
CN108831741B (en) Method for increasing interface magnetic anisotropy energy of ferromagnetic metal/oxide double-layer film
CN101665911A (en) Method for preparing giant magnetoresistance films by vacuum vapor deposition method
CN108930017A (en) A kind of La0.7Sr0.3MnO3The preparation method of ferromagnetic thin film
CN107134524B (en) Method for preparing fin type three-dimensional multiferroic heterojunction by adopting atomic layer deposition method
CN108004592A (en) A kind of Bi6Ti3Fe2O18More epitaxial ferroelectric films of stratiform and preparation method thereof
RU2655507C1 (en) METHOD FOR OBTAINING FILMS WITH Mn5Ge3OX FERROMAGNETIC CLUSTERS ON THE SUBSTRATE IN THE GeO2 MATRIX
CN111243816A (en) Magnetized material, preparation method, perpendicular magnetized film structure and electron spin device
Jang et al. Interfacial structure of ferromagnetic Fe-Pt thin films grown on a Si substrate
CN113046709B (en) Cobalt-based multilayer film and preparation method 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