A kind of have oxide ferroelectric thin film of exchange bias effect and preparation method thereof
Technical field
The invention belongs to function film field and in particular to a kind of oxide ferroelectric thin film with exchange bias effect and its
Preparation method.
Background technology
The interface zone being formed in two kinds of thing phases, an of paramount importance feature is exactly symmetric broken scarce.Electric charge, from
The coupling condition between the free degree and the free degree such as rotation, track and lattice will accordingly change, and ultimately result in interface and novelty
Physical phenomenon, such as quantum hall effect, magneto-electric coupled, interface superconduction, exchange biased etc..Wherein, exchange bias effect is certainly
Rotation electronic device, Spin Valve, and the technical field such as magnetic tunnel-junction have a good application prospect, people it is expanded with system and
In-depth study.
At present, researcher has been found that exchange biased phenomenon is widely present in Ferromagnetic/Antiferromagnetic, Ferrimagnetic/antiferromagnetic etc.
In system.When system plus magnetic field are cooled to low temperature by the Ne&1&el temperature of antiferromagnet, the hysteresis curve of sample is along cooling field
Rightabout deviation from origin, and the increase of simultaneous coercive field, this phenomenon is exchange bias effect.Its physical mechanism is such as
Under: when system temperature is in the Ne&1&el temperature t of antiferromagnetnCurie temperature t with ferromagnetic materialc(tn< t < tc) between
When, in system, ferromagnet magnetic moment goes to the direction parallel to externally-applied magnetic field, is in magnetic order state;And antiferromagnet is in paramagnetic
State, the magnetic moment disorder distribution of inside.It is cooled to t under magnetic fieldsnWhen following, antiferromagnet is also into ordered magnetic state.By
In there is exchange interaction in Ferromagnetic/Antiferromagnetic interface, the antiferromagnet atomic magnetic moment of interface will be along ferromagnetic magnetic moment
Direction is parallel or anti-parallel arranges, here it is the spin pinning layer of interface.When externally-applied magnetic field inverts, ferromagnetic magnetic moment
With outer field reversal, and antiferromagnet is it is considered that it is respectively very big to different magnetic constant, and interface spin magnetic moment does not become with outfield
Change.Due to interface coupling effect, antiferromagnet attempts the direction allowing ferromagnetic magnetic moment still remain in cooling field.Therefore work as survey
When amount magnetic field is contrary with cooling down field direction, the more difficult upset of ferromagnetic magnetic moment, coercivity is larger.When measurement magnetic field and cooling field side
To consistent when, ferromagnetic magnetic moment is easy to turn to direction parallel with it, and coercivity is less;So macroscopically showing as magnetic
Hysteresis curves, along the rightabout skew of cooling field, present unidirectional anisotropy.
One quasi-representative material of research exchange bias effect is exactly ferriferous oxide.In the different oxides of iron, iron ion is in oxygen
Concentration in ion close-packed structure, distribution, and oxidation state are different.Wherein, magnetic iron ore ferroso-ferric oxide fe3o4It is
Ferrimagnet, has fe simultaneously2+And fe3+, fe3+Occupy eighth tetrahedral interstice, fe2+And fe3+Ratio with 1:1
Occupy the tetrahedral interstice of half;And the wustite ferrous oxide feo being formed under reducing atmosphere is antiferromagnet, fe2+Account for
According to octahedral interstice.Anti-ferromagnetism feo and ferrimagnetism fe3o4Between exchange-coupling interaction can show exchange biased effect
Should.2011, benoit p.pichon et al. delivered autograph on chemistry of materials
“microstructural and magnetic investigations of wüstite-spinel core-shell
The article of cubic-shaped nanoparticles " is it was recently reported that cube feo/fe3o4Compound of (antiferromagnetic/Ferrimagnetic) nucleocapsid
The exchange bias effect of grain.Xiaolian sun et al. reports in nano letters (volume 12,246-251 page, 2012)
Spherical feo/fe3o4Nucleocapsid composite particles, and the physical essence of exchange bias effect is have studied in nanoscale.
Although with regard to feo/fe3o4The exchange bias effect of nano core-shell composite particles studied, but there is presently no
Report with regard to two-dimentional oxide ferroelectric thin film system exchange bias effect.Compare nano composite structure, two-dimensional film material cost
Cheap, preparation is simple, and and magnetic memory, Spin Valve, tunnel knot, sensor etc. has more preferable compatibility.Therefore, develop
The new technology preparing the oxide ferroelectric thin film with exchange bias effect has important scientific meaning and wide market prospects.
Content of the invention
It is contemplated that filling up the not blank with regard to two-dimentional oxide ferroelectric thin film system exchange bias effect, the present invention carries
Supply a kind of there is oxide ferroelectric thin film of exchange bias effect and preparation method thereof.
The invention provides a kind of oxide ferroelectric thin film with exchange bias effect, described oxide ferroelectric thin film comprises instead
Ferromagnetism ferrous oxide thin layer and ferrimagnetism four oxidation three in described anti-ferromagnetism ferrous oxide thin layer Epitaxial growth
Iron thin layer.
It is preferred that the thickness of described oxide ferroelectric thin film is 15 60nm.
It is preferred that the thickness of described anti-ferromagnetism ferrous oxide thin layer is 3 10nm, described ferrimagnetism ferroso-ferric oxide
The thickness of thin layer is 5 55nm.
It is preferred that described oxide ferroelectric thin film is deposited on strontium titanate layer surface or strontium titanate monocrystal surface, described anti-iron
Magnetic oxygenated ferrous iron thin layer is in strontium titanate layer surface or the epitaxial growth of strontium titanate monocrystal surface.
It is preferred that the thickness of described strontium titanate layer is 5-25nm.
Also, present invention also offers a kind of preparation method of above-mentioned oxide ferroelectric thin film, methods described includes:
1) with strontium titanates as target, obtain strontium titanate layer in base material enterprising horizontal pulse laser deposition, or pretreatment metatitanic acid
Strontium single crystalline substrate;
2) with iron oxide as target, in step 1) strontium titanate layer prepared or strontium titanate monocrystal substrate enterprising horizontal pulse laser
Deposition, obtains described oxide ferroelectric thin film, wherein, the parameter of pulsed laser deposition technique is: first by impulse laser deposition system
Background be evacuated to 5 × 10-4Pa, and heated substrate or strontium titanates substrate be to 350~550 DEG C, then reative cell vacuum is taken out
To 3 × 10-4Pa is deposited, 300~600 DEG C of depositing temperature, laser energy density 3~7j/cm2, sedimentation rate 1.5~2nm/
Minute.
It is preferred that step 1) in, base material is lead magnesio-niobate lead titanate monocrystal or magnesium aluminate spinel monocrystalline.In addition, it is preferred that
Step 1) in, the parameter of pulsed laser deposition technique is: 500~800 DEG C of depositing temperature, and deposition oxygen presses 0.01~1pa, laser energy
Metric density 3~7j/cm2, sedimentation rate 1~1.5nm/ minute.
It is preferred that step 2) in, the heating rate of heated substrate or strontium titanate monocrystal substrate is 1-10 DEG C/min.
It is preferred that step 2) in, deposit after terminating in air pressure 3 × 10-4Under conditions of pa, with 1-10 DEG C/min of fall
Prepared oxide ferroelectric thin film is cooled to room temperature by warm speed.
Beneficial effects of the present invention:
The present invention is ingenious and effectively utilizes srtio3After high vacuum annealing, surface forms ti at interface3+- vo, in film
Early growth period, due to redox reaction, interface generates extension ferrous oxide (feo) reduction phase, ferrimagnetism four oxidation three
Iron (fe3o4) thin layer subsequently epitaxial growing.Anti-ferromagnetism feo layer and ferrimagnetism fe3o4Exchange-coupling interaction between layer makes
System shows stronger exchange bias effect.The oxide ferroelectric thin film with exchange bias effect that the present invention provides, it shows
Show the characteristic value exchange bias field h of exchange bias effect sizeebCan be adjusted by changing film thickness.
Brief description
Fig. 1 shows the oxide ferroelectric thin film body with exchange bias effect of preparation in an embodiment of the invention
The structural representation of system, wherein, (a) represents in non-srtio3One layer of srtio is first deposited on single crystalline substrate3Thin layer, redeposited iron oxygen
Compound film, (b) represents in srtio3Direct precipitation oxide ferroelectric thin film in single crystalline substrate;
Fig. 2 shows the oxide ferroelectric thin film prepared in two embodiments of the present invention in h=1t and h=-1t magnetic field
Under cooling, the hysteresis curve of temperature t=10k;
Fig. 3 shows the xrd diffracting spectrum of the oxide ferroelectric thin film/strontium titanates of preparation in an embodiment of the invention
And high resolution transmission electron microscopy (tem) photo;
Fig. 4 shows the oxide ferroelectric thin film of preparation in an embodiment of the invention in h=1t and h=-1t magnetic field
Under cooling, the hysteresis curve of temperature t=10k.
Specific embodiment
Further illustrate the present invention below in conjunction with accompanying drawing and following embodiment it should be appreciated that accompanying drawing and following embodiment
It is merely to illustrate the present invention, and the unrestricted present invention.
It is contemplated that filling up the existing report not blank with regard to two-dimentional oxide ferroelectric thin film system exchange bias effect,
A kind of oxide ferroelectric thin film with exchange bias effect is provided.The present invention also aims to it is exchange biased to provide one kind to have
The preparation method of the two-dimentional oxide ferroelectric thin film of effect.The object of the present invention is achieved like this: one kind has exchange biased effect
The two-dimentional oxide ferroelectric thin film answered, it is deposited on the strontium titanates (srtio of high vacuum annealing3) surface.
The present invention relates to a kind of oxide ferroelectric thin film with stronger exchange bias effect and preparation method thereof, wherein iron oxygen
The structure of compound film (not removing strontium titanate layer or strontium titanates substrate) is: ferroso-ferric oxide (fe3o4)/ferrous oxide (feo)/
Strontium titanates (srtio3) transition zone/single crystalline substrate, or fe3o4/feo/srtio3Single crystalline substrate.srtio3Interface is that system produces friendship
Change the key of bias effect: vacuum (≤3 × 10-4Pa) after (300~600 DEG C) annealing of high temperature, srtio3Surface Creation ti3+- vo,
Thus generate ferrous oxide (feo) epitaxial layer, extension fe in film early growth period interface3o4Thin layer subsequent growth.Anti-ferromagnetism
Feo and ferrimagnetism fe3o4Between exchange-coupling interaction make system show stronger exchange bias effect.The present invention passes through
The control of film growth interface, based on srtio3The two-dimentional oxide ferroelectric thin film system (fe at interface3o4/feo/srtio3) in
Obtain stronger exchange bias effect, compare the feo/fe of report in document3o4Nano composite granules, two-dimensional film system low cost
Honest and clean, preparation is simple, and and magnetic memory, Spin Valve, tunnel knot, sensor etc. has more preferable compatibility.
Described thin film deposition is in strontium titanates (srtio3) surface, such as with srtio3Monocrystalline, has deposited a thin layer srtio3Niobium
Magnesium lead plumbate lead titanates (0.72pb (mg1/3nb2/3)o3-0.28pbtio3, pmn-pt) and magnesium aluminate spinel (mgal2o4) monocrystalline is
Substrate.
Using srtio3Surface high vacuum annealing forms ti3+- vo, interface generates antiferromagnetic oxygen due to redox reaction
Change ferrous (feo) layer, Ferrimagnetic ferroso-ferric oxide (fe3o4) layer subsequent growth, thus forming fe3o4/feo/srtio3Structure.
Interface feo thin layer and the fe of subsequent growth3o4Layer is epitaxial growth.
Described preparation method is to adopt pulsed laser deposition technique, and the ferriferous oxide with stronger exchange bias effect is obtained
The method of film, comprising:
Step (1): srtio3Prepared by transition zone
Technology using pulsed laser deposition prepares srtio3Layer, target is more than 99.99% srtio for purity3Pottery
Block, substrate is (001) pmn-pt monocrystalline and (001) mgal of single-sided polishing2o4Monocrystalline, 500~800 DEG C of depositing temperature, deposit oxygen
Pressure 0.01~1pa, laser energy density 3~7j/cm2, sedimentation rate 1~1.5nm/min;
Step (2): oxide ferroelectric thin film deposition
Technology using pulsed laser deposition prepares oxide ferroelectric thin film, by (001) srtio of single-sided polishing3Monocrystalline, with
And prepared srtio in step (1)3(001) pmn-pt monocrystalline of film layer and (001) mgal2o4Monocrystalline is put into pulse laser and is sunk
In the reative cell of long-pending system, the background of impulse laser deposition system is evacuated to≤5 × 10-4Pa, heating substrate to 350~
550 DEG C, then reative cell vacuum is evacuated to≤3 × 10-4Pa deposits oxide ferroelectric thin film;Technological parameter is more than 99.99% for purity
Fe2o3Block is as corresponding target, 300~600 DEG C of depositing temperature, laser energy density 3~7j/cm2, sedimentation rate 1.5
~2nm/min.After oxide ferroelectric thin film preparation terminates, in high vacuum conditions, room is cooled to the speed of 1~10 DEG C/min
Temperature, then takes out and carries out microstructure and electromagnetic performance sign.
Impulse laser deposition system described in step (1) and step (2) is using German lambda physik lpx
Compex201 krf excimer laser (excimer-laser, λ=248 nm), laser frequency 1~10hz.
Srtio described in step (1)3The deposit thickness of thin layer is 5~25nm.
In step (2), heating rate during oxide ferroelectric thin film preparation is 1~10 DEG C/min, prepares after terminating in high vacuum
Condition (3 × 10-4Pa under), room temperature is cooled to the speed of 1~10 DEG C/min.
In step (2), the thickness of the oxide ferroelectric thin film of preparation is 15~60nm.
The present invention obtain beneficial effect be: the present invention is ingenious and effectively utilize srtio3Anneal in high vacuum in interface
Afterwards, surface forms ti3+- vo, in film early growth period, due to redox reaction, interface generates extension ferrous oxide (feo)
Reduction phase, ferrimagnetism ferroso-ferric oxide (fe3o4) thin layer subsequently epitaxial growing.Anti-ferromagnetism feo layer and ferrimagnetism fe3o4
Exchange-coupling interaction between layer makes system show stronger exchange bias effect.Having that the present invention provides is exchange biased
The oxide ferroelectric thin film of effect, the characteristic value exchange bias field h of its display exchange bias effect sizeebCan be thick by changing film
Degree is adjusted.
Include some exemplary embodiments further below so that the present invention is better described.It should be understood that the present invention is detailed
The above-mentioned embodiment stated, and following examples are only illustrative of the invention and is not intended to limit the scope of the invention, this area
Technical staff made according to the above of the present invention some nonessential improve and adjustment belongs to the protection of the present invention
Scope.In addition, concrete proportioning in following technological parameters, time, temperature etc. are also only exemplary, those skilled in the art are permissible
Suitable value is selected in the range of above-mentioned restriction.
Embodiment 1:
In impulse laser deposition system, the srtio that is orientated with (001)3Monocrystalline is substrate, prepares thickness and is about 26nm's
Oxide ferroelectric thin film;
1) by (001) srtio of single-sided polishing3Single crystalline substrate is put in the reative cell of impulse laser deposition system, by arteries and veins
The background rushing laser deposition system is evacuated to≤5 × 10-4Pa, heating substrate is to 400 DEG C, then reative cell vacuum is evacuated to≤3
×10-4pa;It is more than 99.99% fine and close fe with purity2o3Ceramic block is as target, laser energy 7j/cm2, sedimentation rate 1.5
~2nm/min.Deposit after terminating in high vacuum (≤3 × 10-4Pa) in environment, room temperature is down to the speed of 6 DEG C/min, thus making
Obtain as the oxide ferroelectric thin film of (b) structure in Fig. 1;
2) superconducting quantum interference device (SQUID) (squid) is adopted to measure the prepared sample of embodiment 1 cold in h=1t and h=-1t magnetic field
But under the conditions of, the hysteresis curve (as accompanying drawing 2 (b)) of temperature t=10k, the hysteresis curve finding sample is along the contrary side in cooling field
To shifting, there is exchange bias effect, exchange bias field heb=360oe, coercive field hc=520oe.Wherein hc=| hl-hr
|/2, heb=| hl+hr|/2, hlFor the intersection point of hysteresis curve and the left side of abscissa, hrThe right for hysteresis curve and abscissa
Intersection point.Separately, the hysteresis curve recording under the conditions of positive and negative magnetic-field cooling also there occurs skew along ordinate, furtherly light field
Unidirectional anisotropy is created in this system when cold;
3) accompanying drawing 3 gives the x-ray diffraction collection of illustrative plates of oxide ferroelectric thin film prepared according to embodiment 1 and transmitted electron shows
Micro mirror photo.As can be seen that having had to the ferroso-ferric oxide along c-axis orientation in the analysis limit of x-ray diffraction technology
(fe3o4) diffraction maximum, but high resolution transmission electron microscopy photo is shown in interface and defines the feo phase that (001) is orientated,
(001) fe being orientated3o4Epitaxial film subsequent growth.In high vacuum environment, srtio3The ti on surface4+It is reduced to ti3+, ti3+
Feo can be promoted to reduce the generation of phase, antiferromagnetic feo phase and Ferrimagnetic fe3o4Exchange-coupling interaction between phase result in above-mentioned friendship
Change bias effect.
Embodiment 2:
In impulse laser deposition system, with srtio3Pmn-pt and mgal for transition zone2o4Monocrystalline is substrate, preparation
Thickness is about the oxide ferroelectric thin film of 26nm;
1) in impulse laser deposition system, pmn-pt and mgal that be orientated with (001)2o4Monocrystalline is substrate, prepares thickness
It is about the srtio of 10nm3Layer.Preparation technology parameter: base reservoir temperature t=700 DEG C, deposition oxygen pressure 0.1pa, laser energy is 5j/
cm2;
2) in impulse laser deposition system, the srtio that prepared with step (1)3/ pmn-pt, srtio3/mgal2o4And
pmn-pt、mgal2o4Monocrystalline is substrate, prepares the oxide ferroelectric thin film that thickness is about 26nm.Preparation technology is with embodiment 1;
3) use superconducting quantum interference device (SQUID) (squid) to measure sample magnetic property, measure sample in external magnetic field h=1t and h=-
Under 1t cooling condition, the m-h curve map (as accompanying drawing 4) of temperature t=10k.As can be seen that fe3o4/ pmn-pt and fe3o4/
mgal2o4Exchange bias effect inconspicuous;Increase a thin layer srtio in the interface of this two systems3Obtained fe3o4/
srtio3/ pmn-pt and fe3o4/srtio3/mgal2o4Heterojunction structure has obvious exchange bias effect, thus illustrating
srtio3Interface is most important to the growth of oxide ferroelectric thin film and magnetic property.
Embodiment 3:
In impulse laser deposition system, the srtio that is orientated with (001)3Monocrystalline is substrate, three different-thickness of preparation
Oxide ferroelectric thin film;
1) with embodiment 1, the thickness of film is controlled preparation technology by sedimentation time, and thickness is respectively 17nm, 35nm
And 43nm;
2) superconducting quantum interference device (SQUID) (squid) is adopted to measure the prepared sample of embodiment 3 cold in h=1t and h=-1t magnetic field
But under the conditions of, the hysteresis curve (as Fig. 2 (a), (c) and (d)) of temperature t=10k.1 sample Magnetic Measurement is obtained in conjunction with the embodiments
As a result, it is possible to find, exchange bias effect is obviously reduced with the increase of film thickness, this is because for thicker film
System, the relative amount of interface antiferromagnetic feo layer reduces, and exchange bias effect comes from interfacial interaction thus also can phase
Should weaken.