CN105859152A - High magnetic Bi0.96Sr0.04FeO3 base / CoFe2O4 composite film and preparation method thereof - Google Patents
High magnetic Bi0.96Sr0.04FeO3 base / CoFe2O4 composite film and preparation method thereof Download PDFInfo
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- CN105859152A CN105859152A CN201610201240.7A CN201610201240A CN105859152A CN 105859152 A CN105859152 A CN 105859152A CN 201610201240 A CN201610201240 A CN 201610201240A CN 105859152 A CN105859152 A CN 105859152A
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- C03—GLASS; MINERAL OR SLAG WOOL
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Abstract
The present invention provides a high magnetic Bi0.96Sr0.04FeO3 base / CoFe2O4 composite film and a preparation method thereof. The film includes CoFe2O4 and Bi0.96Sr0.04Fe1-x-yMnxCoyO3, which are compounded together, wherein x equals to 0-0.04, y equals to 0-0.02, and x, y are not both 0. The method is as below: first preparing a CoFe2O4 precursor solution and a Bi0.96Sr0.04FeO3 base film precursor solution; then preparing a magnetic CoFe2O4 magnetic thin film on an FTO substrate by a spinning coating method and an annealing process; then preparing a Bi0.96Sr0.04FeO3 base film on CoFe2O4 to form a high magnetic Bi0.96Sr0.04FeO3 base / CoFe2O4 composite film. By ion doping and magnetic CoFe2O4 thin film compounding, the method greatly improves dielectric, ferroelectric and ferromagnetic properties of the film, but also effectively reduces the current leakage density of the film.
Description
Technical field
The invention belongs to field of functional materials, be specifically related to a kind of high magnetic Bi0.96Sr0.04FeO3Base/CoFe2O4Laminated film and
Preparation method.
Background technology
BiFeO3It is a kind of typical single phase multi-iron material, is one of current active material studied.It has far above room temperature
Ferroelectrie Curie temperature (830 DEG C) and antiferromagnetic Neel temperature (370 DEG C), therefore, have ferroelectricity and anti-ferromagnetism the most simultaneously.
BiFeO3Iron electric polarization intensity be common Pt (ZrTi) O3(PZT) about 3 times of ferroelectric material, it is a kind of unleaded and has
Ferroelectricity and anti-ferromagnetism, be one of the focus of current multi-iron material research.BiFeO3The intensity of magnetization (M) and electric polarization (P)
Electromagnetic coupled can occur, can be produced magnetic field by electric field induction, magnetic field again can be with evoked electrode simultaneously, i.e. magnetoelectric effect.And
BiFeO3Magnetic come from Fe ion, each Fe3+All by the six of arest neighbors antiparallel Fe that spin3+Surround, form G type anti-
Ferromagnetic structure.BiFeO3Bi in system3+6s and 6p orbital hybridization, 6s2Electronics is filled with one of them hybrid orbital.This
Kind hydridization causes lone pair electrons and loses Sphere symmetry and be inclined to cation side, forms the lattice structure of a kind of distortion.BiFeO3
In material, the magnetic motion of Fe ion is ferromagnetic coupling in [111] face, and the magnetic moment in adjacent two [111] faces constitutes antiferromagnetic
Coupling, spin coupling causes the inclination of magnetic sublattice in the case, thus produces macroscopical weak magnetic.
In order to improve BiFeO3Weak magnetic, BiFeO3Can be combined from the magnetic material of different systems, such as CoFe2O4、
Na0.5K0.5NbO3、SrTiO3, improve the dielectric properties of system, ferroelectric properties and ferromagnetic property etc..Use at present and CoFe2O4
Compound research gets more and more, and becomes people and studies BiFeO3Compound focus.CoFe2O4Crystal belongs to cubic system, cubic plane
Heart grid, Fd3m space group.The normal spinel structure material being made up of Co-Fe-O ternary system is the magnetisable material of function admirable,
There is high saturation and magnetic intensity, high-coercive force, high magnetic permeability, big magnetocrystalline anisotropy, big magnetostriction and high change
Learning stability, be a kind of well magnetic recording material and magneto-optic recording material, prominent advantage is that resistivity is high, and magnetic spectrum characteristic is good,
It is also suitable under high frequency and hyperfrequency application.Therefore, use ion doping and be combined with thin magnetic film and improve BiFeO3Dielectric
The correlational study of performance, ferroelectric properties and ferromagnetic property etc. is significant.
Summary of the invention
It is an object of the invention to provide a kind of high magnetic Bi0.96Sr0.04FeO3Base/CoFe2O4Laminated film and preparation method thereof, should
Method can make the leakage current of the laminated film prepared reduce, ferroelectric properties improves.
To achieve these goals, the present invention adopts the following technical scheme that
A kind of high magnetic Bi0.96Sr0.04FeO3Base/CoFe2O4Laminated film, including the upper layer film being combined with each other and lower membrane, its
Middle lower membrane is CoFe2O4Crystalline state film, upper layer film is Bi0.96Sr0.04FeO3Base crystalline state film, its structural formula is
Bi0.96Sr0.04Fe1-x-yMnxCoyO3, x=0～0.04, y=0～0.02, and be 0 during x, y difference.
Described Bi0.96Sr0.04FeO3Base crystalline state film belongs to R3c:H space group, has trigonal crystal structure；CoFe2O4Crystalline state film belongs to
R3c:H space group, has trigonal crystal structure, cell parameter a=b=c=8.3763.
Described high magnetic Bi0.96Sr0.04FeO3Base/CoFe2O4Laminated film includes Bi0.96Sr0.04Fe0.98Co0.02O3/CoFe2O4Multiple
Close thin film, Bi0.96Sr0.04Fe0.96Mn0.04O3/CoFe2O4Laminated film and Bi0.96Sr0.04Fe0.94Mn0.04Co0.02O3/CoFe2O4Multiple
Close thin film；
Wherein Bi0.96Sr0.04Fe0.98Co0.02O3/CoFe2O4Saturation magnetisation value under laminated film room temperature is 74emu/cm3, remanence
Change value is 47emu/cm3；Under 1kHz test frequency, its dielectric constant is 435；Under 200kV/cm electric field, its electric leakage
Current density is 1.83 × 10-5A/cm2；When full test electric field is 500kV/cm, its saturated polarization is 100 μ C/cm2,
Remanent polarization is 84 μ C/cm2, coercive field is 376kV/cm；
Bi0.96Sr0.04Fe0.96Mn0.04O3/CoFe2O4Saturation magnetisation value under laminated film room temperature is 71emu/cm3, remanent magnetization value
For 46emu/cm3；Under 1kHz test frequency, its dielectric constant is 750；Under 200kV/cm electric field, its leakage current is close
Degree is 4.46 × 10-6A/cm2；When full test electric field is 500kV/cm, its saturated polarization is 123 μ C/cm2, residue
Polarization intensity is 104 μ C/cm2, coercive field is 326kV/cm；
Bi0.96Sr0.04Fe0.94Mn0.04Co0.02O3/CoFe2O4Saturation magnetisation value under laminated film room temperature is 108emu/cm3, residue
Magnetization value is 60emu/cm3；Under 1kHz test frequency, its dielectric constant is 800；Under 200kV/cm electric field, its leakage
Electric current density is 1.37 × 10-5A/cm2；When full test electric field is 500kV/cm, its saturated polarization is 167 μ C/cm2,
Remanent polarization is 150 μ C/cm2, coercive field is 324kV/cm.
A kind of high magnetic Bi0.96Sr0.04FeO3Base/CoFe2O4The preparation method of laminated film, comprises the following steps:
Step 1: by Co (NO3)2·6H2O and Fe (NO3)3·9H2O is dissolved in ethylene glycol monomethyl ether for 1:2 in molar ratio, and stirring is all
Add acetic anhydride after even, obtain CoFe2O4Precursor liquid；Wherein CoFe2O4In precursor liquid, the concentration of Co ion is 0.15～0.3
mol/L；
Step 2: be that 1.01:0.04:1-x-y:x:y is by Bi (NO in molar ratio3)3·5H2O、Sr(NO3)2、Fe(NO3)3·9H2O、
C6H9MnO6·2H2O、Co(NO3)2·6H2O is dissolved in solvent, obtains Bi0.96Sr0.04FeO3Base film precursor liquid, wherein
X=0～0.04, y=0～0.02, and be 0, Bi during x, y difference0.96Sr0.04FeO3The total concentration of metal ion in base film precursor liquid
Being 0.25～0.35mol/L, solvent is the mixed liquor of ethylene glycol monomethyl ether and acetic anhydride；
Step 3: use spin-coating method spin coating CoFe on substrate2O4Precursor liquid, obtains CoFe2O4Wet film, CoFe2O4Wet film warp
At 180～210 DEG C, toast to obtain dry film after spin coating, anneal in atmosphere at 580～600 DEG C, obtain crystalline state CoFe2O4Thin film；
Step 4: treat crystalline state CoFe2O4After film cooling, in crystalline state CoFe2O4Step 3 is repeated, until it reaches required on thin film
Thickness, obtains CoFe2O4Crystalline state film；
Step 5: at CoFe2O4Spin coating Bi on crystalline state film0.96Sr0.04FeO3Base film precursor liquid, obtains Bi0.96Sr0.04FeO3Base is wet
Film, Bi0.96Sr0.04FeO3Base wet film toasts to obtain dry film after spin coating at 180～210 DEG C, then anneals in atmosphere, obtains crystalline state
Bi0.96Sr0.04FeO3Base film；Wherein annealing temperature is 540～550 DEG C；
Step 6: treat crystalline state Bi0.96Sr0.04FeO3After base film cooling, repeat step 5 thereon, until it reaches desired thickness,
I.e. obtain high magnetic Bi0.96Sr0.04FeO3Base/CoFe2O4Laminated film.
Described CoFe2O4In precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is (2.5～3.5): 1；The solvent of described step 2
The volume ratio of middle ethylene glycol monomethyl ether and acetic anhydride is (2.5～3.5): 1.
Substrate, before carrying out, is first carried out by described step 3, the most under ultraviolet light treatment with irradiation, makes substrate surface reach former
Sub-cleannes, then spin coating CoFe2O4Precursor liquid；
Described step 5 is before carrying out, first to CoFe2O4Crystalline state film carries out ultraviolet light treatment with irradiation, makes CoFe2O4Crystalline state film surface
Reach atomic cleanliness degree, then spin coating Bi0.96Sr0.04FeO3Base film precursor liquid.
In described step 3 and step 5, spin coating rotating speed during spin coating is 3600～4000r/min, and spin coating time is 10～15s.
In described step 3 and step 5, the baking time after spin coating is 6～10min.
Annealing time in described step 3 is 7～annealing time in 15min, step 5 is 6～12min.
Described high magnetic Bi0.96Sr0.04FeO3Base/CoFe2O4Laminated film is by 4～8 layer crystal states CoFe2O4Thin film and 8～15 layers
Crystalline state Bi0.96Sr0.04FeO3Base film is constituted.
Relative to prior art, the invention have the advantages that
1, high magnetic Bi that the present invention provides0.96Sr0.04FeO3Base/CoFe2O4The preparation method of laminated film, with BiFeO3For base
Plinth, the diatomic base metal Sr that adulterates on A position, to replace part Bi, can compensate the charge unbalance that Lacking oxygen causes, effectively
Suppression Fe3+The valence state fluctuation of ion；One or both in doping Mn, Co on B position, it is possible to reduce in annealing process
Fe3+To Fe2+Conversion, suppresses Fe effectively3+The valence state fluctuation of ion, thus preferably reduce the leakage current density of thin film,
Improve the ferroelectricity of thin film.
2、CoFe2O4Be that a kind of good dispersion, magnetic is strong, chemical property and the stable ferrimagnet of crystalline phase.The present invention is with tool
Magnetic CoFe2O4Crystalline state film is as lower membrane, and makes CoFe2O4Crystalline state film and Bi0.96Sr0.04FeO3Base film is closely tied
It is combined, improves Bi to a great extent0.96Sr0.04FeO3Base/CoFe2O4The ferromagnetic property of laminated film.
3, the present invention uses sol-gel process to prepare Bi0.96Sr0.04FeO3Base/CoFe2O4Laminated film, experimental facilities requires simple,
Experiment condition easily reaches, the Bi of preparation0.96Sr0.04FeO3Base/CoFe2O4Laminated film uniformity is preferable, and doping is easily controlled,
And by doping and with magnetic CoFe2O4The compound of crystalline state film improves BiFeO3The dielectric of thin film, ferroelectricity and ferromagnetic property.
4, high magnetic Bi that the present invention provides0.96Sr0.04FeO3Base/CoFe2O4Laminated film, by the upper layer film being combined with each other and
Lower membrane is constituted, and wherein lower membrane is CoFe2O4Crystalline state film, belongs to R3c:H space group, has trigonal crystal structure, cell parameter
A=b=c=8.3763；Upper layer film is Bi0.96Sr0.04FeO3Base crystalline state film, belongs to R3c:H space group, has trigonal crystal structure, its knot
Structure formula is Bi0.96Sr0.04Fe1-x-yMnxCoyO3, x=0～0.04, y=0～0.02, and be 0 during x, y difference.By A/B position
Doping and with CoFe2O4Compound so that high magnetic Bi of the present invention0.96Sr0.04FeO3Base/CoFe2O4The electric leakage of laminated film
Current density reduces, and dielectric, ferroelectricity and ferromagnetic property improve.
Accompanying drawing explanation
Fig. 1 is high magnetic Bi prepared by the present invention0.96Sr0.04FeO3Base/CoFe2O4The XRD figure of laminated film；
Fig. 2 is high magnetic Bi prepared by the present invention0.96Sr0.04FeO3Base/CoFe2O4The SEM figure of laminated film；
Fig. 3 is high magnetic Bi prepared by the present invention0.96Sr0.04FeO3Base/CoFe2O4The dielectric constant of laminated film and dielectric loss with
The graph of a relation of test frequency；
Fig. 4 is high magnetic Bi prepared by the present invention0.96Sr0.04FeO3Base/CoFe2O4The leakage current density of laminated film；
Fig. 5 is high magnetic Bi prepared by the present invention0.96Sr0.04FeO3Base/CoFe2O4The ferroelectric hysteresis loop of laminated film；
Fig. 6 is high magnetic Bi prepared by the present invention0.96Sr0.04FeO3Base/CoFe2O4The hysteresis curve of laminated film.
Detailed description of the invention
Below in conjunction with the present invention preferably embodiment and accompanying drawing, the present invention is described in further details.
Embodiment 1
Step 1: by Co (NO3)2·6H2O and Fe (NO3)3·9H2O is dissolved in ethylene glycol monomethyl ether stirring 30min for 1:2 in molar ratio,
Add acetic anhydride stirring 90min, obtain the CoFe that Co ion concentration is 0.15mol/L mix homogeneously2O4Precursor liquid, wherein
Ethylene glycol monomethyl ether is 3:1 with the volume ratio of acetic anhydride；
Step 2: by Bi (NO3)3·5H2O、Sr(NO3)2、Fe(NO3)3·9H2O、Co(NO3)2·6H2O according to mol ratio is
1.01:0.04:0.98:0.02 (Bi excess 5%, x=0, y=0.02) is dissolved in ethylene glycol monomethyl ether, stirs 30min, adds acetic acid
Acid anhydride stirring 90min, obtains the Bi of the mix homogeneously that metal ion total concentration is 0.3mol/L0.96Sr0.04FeO3Base film precursor liquid,
Wherein ethylene glycol monomethyl ether is 3:1 with the volume ratio of acetic anhydride；
Step 3: select FTO/glass substrate, the FTO/glass substrate of well cutting is sequentially placed in detergent, acetone, ethanol
Ultrasonic waves for cleaning, with a large amount of distilled water flushing substrates after each ultrasonic waves for cleaning 10min, finally dries up with nitrogen.Then will
60 DEG C of baking oven baking 5min put into by FTO/glass substrate, take out and stand to room temperature.Again clean FTO/glass substrate is placed in
Ultraviolet radiation instrument irradiates 40min, makes substrate surface reach " atomic cleanliness degree ".Use spin-coating method on FTO/glass substrate
Spin coating CoFe2O4Precursor liquid, obtains CoFe2O4Wet film, to CoFe2O4Wet film spin coating, spin coating rotating speed is 3800r/min, even
The glue time is 15s, after spin coating terminates, toasts 8min and obtain dry film, then the 10min that anneals layer by layer in air at 600 DEG C at 200 DEG C,
Obtain crystalline state CoFe2O4Thin film；
Step 4: treat crystalline state CoFe2O4After film cooling, in crystalline state CoFe2O4Repeat step 3 on thin film, be repeated 7 times,
To CoFe2O4Crystalline state film；
Step 5: by CoFe2O4Crystalline state film is placed in ultraviolet radiation instrument irradiation 40min so that it is surface reaches atomic cleanliness degree；
Then at CoFe2O4Spin coating Bi on crystalline state film0.96Sr0.04FeO3Base film precursor liquid, obtains Bi0.96Sr0.04FeO3Base wet film, right
Bi0.96Sr0.04FeO3Base wet film spin coating, spin coating rotating speed is 3800r/min, and spin coating time is 15s, after spin coating terminates, at 200 DEG C
Lower baking 8min obtains dry film, then the 12min that anneals layer by layer in air at 540 DEG C, obtains crystalline state Bi0.96Sr0.04FeO3Base film；
Step 6: treat crystalline state Bi0.96Sr0.04FeO3After base film cooling, in crystalline state Bi0.96Sr0.04FeO3Step 5 is repeated on base film,
It is repeated 13 times, obtains high magnetic Bi0.96Sr0.04Fe0.98Co0.02O3/CoFe2O4Laminated film.
High magnetic Bi is tested with XRD0.96Sr0.04Fe0.98Co0.02O3/CoFe2O4The thing phase composition structure of laminated film.Survey with SEM
Fixed high magnetic Bi0.96Sr0.04Fe0.98Co0.02O3/CoFe2O4The microscopic appearance of laminated film and interracial contact situation.With
High magnetic Bi tested by P-PMF1114-372 ferroelectricity analyser0.96Sr0.04Fe0.98Co0.02O3/CoFe2O4The ferroelectric properties of laminated film,
Test frequency is 1kHz, when full test electric field is 500kV/cm, and high magnetic Bi0.96Sr0.04Fe0.98Co0.02O3/CoFe2O4Multiple
The saturated polarization closing thin film is 100 μ C/cm2, remanent polarization is 84 μ C/cm2, coercive field is 376kV/cm.With
High magnetic Bi tested by Agilent E4980A precision LCR table0.96Sr0.04Fe0.98Co0.02O3/CoFe2O4The dielectric properties of laminated film,
When test frequency is 1kHz, high magnetic Bi0.96Sr0.04Fe0.98Co0.02O3/CoFe2O4The dielectric constant of laminated film is 435.With
Agilent B2900 tests high magnetic Bi0.96Sr0.04Fe0.98Co0.02O3/CoFe2O4The leakage conductance current characteristics of laminated film, test electricity
When field is 200kV/cm, high magnetic Bi0.96Sr0.04Fe0.98Co0.02O3/CoFe2O4The leakage current density of laminated film is 1.83 × 10-5
A/cm2.High magnetic Bi is tested with SQUID MPMS-XL-70.96Sr0.04Fe0.98Co0.02O3/CoFe2O4Under laminated film room temperature
Ferromagnetic property, under room temperature, high magnetic Bi0.96Sr0.04Fe0.98Co0.02O3/CoFe2O4The saturation magnetisation value of laminated film is 74
emu/cm3, remanent magnetization value is 47emu/cm3。
Embodiment 2
Step 1: by Co (NO3)2·6H2O and Fe (NO3)3·9H2O is dissolved in ethylene glycol monomethyl ether stirring 30min for 1:2 in molar ratio,
Add acetic anhydride stirring 90min, obtain the CoFe that Co ion concentration is 0.2mol/L mix homogeneously2O4Precursor liquid, wherein
Ethylene glycol monomethyl ether is 3:1 with the volume ratio of acetic anhydride；
Step 2: by Bi (NO3)3·5H2O、Sr(NO3)2、Fe(NO3)3·9H2O、C6H9MnO6·2H2O according to mol ratio is
1.01:0.04:0.96:0.04 (Bi excess 5%, x=0.04, y=0) is dissolved in ethylene glycol monomethyl ether, stirs 30min, adds acetic acid
Acid anhydride stirring 90min, obtains the Bi of the mix homogeneously that metal ion total concentration is 0.3mol/L0.96Sr0.04FeO3Base film precursor liquid,
Wherein ethylene glycol monomethyl ether is 3:1 with the volume ratio of acetic anhydride；
Step 3: select FTO/glass substrate, the FTO/glass substrate of well cutting is sequentially placed in detergent, acetone, ethanol
Ultrasonic waves for cleaning, with a large amount of distilled water flushing substrates after each ultrasonic waves for cleaning 10min, finally dries up with nitrogen.Then will
60 DEG C of baking oven baking 5min put into by FTO/glass substrate, take out and stand to room temperature.Again clean FTO/glass substrate is placed in
Ultraviolet radiation instrument irradiates 40min, makes substrate surface reach " atomic cleanliness degree ".Use spin-coating method on FTO/glass substrate
Spin coating CoFe2O4Precursor liquid, obtains CoFe2O4Wet film, to CoFe2O4Wet film spin coating, spin coating rotating speed is 3800r/min, even
The glue time is 15s, after spin coating terminates, toasts 8min and obtain dry film, then the 10min that anneals layer by layer in air at 600 DEG C at 200 DEG C,
Obtain crystalline state CoFe2O4Thin film；
Step 4: treat crystalline state CoFe2O4After film cooling, in crystalline state CoFe2O4Repeat step 3 on thin film, be repeated 7 times,
To CoFe2O4Crystalline state film；
Step 5: by CoFe2O4Crystalline state film is placed in ultraviolet radiation instrument irradiation 40min so that it is surface reaches atomic cleanliness degree；
Then at CoFe2O4Spin coating Bi on crystalline state film0.96Sr0.04FeO3Base film precursor liquid, obtains Bi0.96Sr0.04FeO3Base wet film, right
Bi0.96Sr0.04FeO3Base wet film spin coating, spin coating rotating speed is 3800r/min, and spin coating time is 15s, after spin coating terminates, at 200 DEG C
Lower baking 8min obtains dry film, then the 12min that anneals layer by layer in air at 540 DEG C, obtains crystalline state Bi0.96Sr0.04FeO3Base film；
Step 6: treat crystalline state Bi0.96Sr0.04FeO3After base film cooling, in crystalline state Bi0.96Sr0.04FeO3Step 5 is repeated on base film,
It is repeated 13 times, obtains high magnetic Bi0.96Sr0.04Fe0.96Mn0.04O3/CoFe2O4Laminated film.
High magnetic Bi is tested with XRD0.96Sr0.04Fe0.96Mn0.04O3/CoFe2O4The thing phase composition structure of laminated film.Use SEM
Measure high magnetic Bi0.96Sr0.04Fe0.96Mn0.04O3/CoFe2O4The microscopic appearance interracial contact situation of laminated film.With
High magnetic Bi tested by P-PMF1114-372 ferroelectricity analyser0.96Sr0.04Fe0.96Mn0.04O3/CoFe2O4The ferroelectric properties of laminated film,
Test frequency is 1kHz, when full test electric field is 500kV/cm, and high magnetic Bi0.96Sr0.04Fe0.96Mn0.04O3/CoFe2O4Multiple
The saturated polarization closing thin film is 123 μ C/cm2, remanent polarization is 104 μ C/cm2, coercive field is 326kV/cm.With
High magnetic Bi tested by Agilent E4980A precision LCR table0.96Sr0.04Fe0.96Mn0.04O3/CoFe2O4The dielectric properties of laminated film,
When test frequency is 1kHz, high magnetic Bi0.96Sr0.04Fe0.96Mn0.04O3/CoFe2O4The dielectric constant of laminated film is 750.With
Agilent B2900 tests high magnetic Bi0.96Sr0.04Fe0.96Mn0.04O3/CoFe2O4The leakage conductance current characteristics of laminated film, test electricity
When field is 200kV/cm, high magnetic Bi0.96Sr0.04Fe0.96Mn0.04O3/CoFe2O4The leakage current density of laminated film is 4.46 × 10-6
A/cm2.High magnetic Bi is tested with SQUID MPMS-XL-70.96Sr0.04Fe0.96Mn0.04O3/CoFe2O4Under laminated film room temperature
Ferromagnetic property, under room temperature, high magnetic Bi0.96Sr0.04Fe0.96Mn0.04O3/CoFe2O4The saturation magnetisation value of laminated film is 71
emu/cm3, remanent magnetization value is 46emu/cm3。
Embodiment 3
Step 1: by Co (NO3)2·6H2O and Fe (NO3)3·9H2O is dissolved in ethylene glycol monomethyl ether stirring 30min for 1:2 in molar ratio,
Add acetic anhydride stirring 90min, obtain the CoFe that Co ion concentration is 0.25mol/L mix homogeneously2O4Precursor liquid, wherein
Ethylene glycol monomethyl ether is 3:1 with the volume ratio of acetic anhydride；
Step 2: by Bi (NO3)3·5H2O、Sr(NO3)2、Fe(NO3)3·9H2O、C6H9MnO6·2H2O、Co(NO3)2·6H2O
It is that 1.01:0.04:0.94:0.04:0.02 (Bi excess 5%, x=0.04, y=0.02) is dissolved in ethylene glycol monomethyl ether according to mol ratio, stirs
Mix 30min, add acetic anhydride stirring 90min, obtain the mix homogeneously that metal ion total concentration is 0.3mol/L
Bi0.96Sr0.04FeO3Base film precursor liquid, wherein ethylene glycol monomethyl ether is 3:1 with the volume ratio of acetic anhydride；
Step 3: select FTO/glass substrate, the FTO/glass substrate of well cutting is sequentially placed in detergent, acetone, ethanol
Ultrasonic waves for cleaning, with a large amount of distilled water flushing substrates after each ultrasonic waves for cleaning 10min, finally dries up with nitrogen.Then will
60 DEG C of baking oven baking 5min put into by FTO/glass substrate, take out and stand to room temperature.Again clean FTO/glass substrate is placed in
Ultraviolet radiation instrument irradiates 40min, makes substrate surface reach " atomic cleanliness degree ".Use spin-coating method on FTO/glass substrate
Spin coating CoFe2O4Precursor liquid, obtains CoFe2O4Wet film, to CoFe2O4Wet film spin coating, spin coating rotating speed is 3800r/min, even
The glue time is 15s, after spin coating terminates, toasts 8min and obtain dry film, then the 10min that anneals layer by layer in air at 600 DEG C at 200 DEG C,
Obtain crystalline state CoFe2O4Thin film；
Step 4: treat crystalline state CoFe2O4After film cooling, in crystalline state CoFe2O4Repeat step 3 on thin film, be repeated 7 times,
To CoFe2O4Crystalline state film；
Step 5: by CoFe2O4Crystalline state film is placed in ultraviolet radiation instrument irradiation 40min so that it is surface reaches atomic cleanliness degree；
Then at CoFe2O4Spin coating Bi on crystalline state film0.96Sr0.04FeO3Base film precursor liquid, obtains Bi0.96Sr0.04FeO3Base wet film, right
Bi0.96Sr0.04FeO3Base wet film spin coating, spin coating rotating speed is 3800r/min, and spin coating time is 15s, after spin coating terminates, at 200 DEG C
Lower baking 8min obtains dry film, then the 12min that anneals layer by layer in air at 540 DEG C, obtains crystalline state Bi0.96Sr0.04FeO3Base film；
Step 6: treat crystalline state Bi0.96Sr0.04FeO3After base film cooling, in crystalline state Bi0.96Sr0.04FeO3Step 5 is repeated on base film,
It is repeated 13 times, obtains high magnetic Bi0.96Sr0.04Fe0.94Mn0.04Co0.02O3/CoFe2O4Laminated film.
High magnetic Bi is tested with XRD0.96Sr0.04Fe0.94Mn0.04Co0.02O3/CoFe2O4The thing phase composition structure of laminated film.With
SEM measures high magnetic Bi0.96Sr0.04Fe0.94Mn0.04Co0.02O3/CoFe2O4The microscopic appearance interracial contact situation of laminated film.With
High magnetic Bi tested by P-PMF1114-372 ferroelectricity analyser0.96Sr0.04Fe0.94Mn0.04Co0.02O3/CoFe2O4The ferroelectricity of laminated film
Performance, test frequency is 1kHz, when full test electric field is 500kV/cm, Bi0.96Sr0.04Fe0.94Mn0.04Co0.02O3/CoFe2O4
The saturated polarization of laminated film is 167 μ C/cm2, remanent polarization is 150 μ C/cm2, coercive field is 324kV/cm.
High magnetic Bi is tested with Agilent E4980A precision LCR table0.96Sr0.04Fe0.94Mn0.04Co0.02O3/CoFe2O4Jie of laminated film
Electrical property, when test frequency is 1kHz, high magnetic Bi0.96Sr0.04Fe0.94Mn0.04Co0.02O3/CoFe2O4The dielectric of laminated film
Constant is 800.High magnetic Bi is tested with Agilent B29000.96Sr0.04Fe0.94Mn0.04Co0.02O3/CoFe2O4The leakage of laminated film
Electrical conduction current characteristic, when test electric field is 200kV/cm, high magnetic Bi0.96Sr0.04Fe0.94Mn0.04Co0.02O3/CoFe2O4THIN COMPOSITE
The leakage current density of film is 1.37 × 10-5A/cm2.High magnetic is tested with SQUID MPMS-XL-7
Bi0.96Sr0.04Fe0.94Mn0.04Co0.02O3/CoFe2O4Ferromagnetic property under laminated film room temperature, under room temperature, high magnetic
Bi0.96Sr0.04Fe0.94Mn0.04Co0.02O3/CoFe2O4The saturation magnetisation value of laminated film is 108emu/cm3, remanent magnetization value is 60
emu/cm3。
Embodiment 4
Step 1: by Co (NO3)2·6H2O and Fe (NO3)3·9H2O is dissolved in ethylene glycol monomethyl ether stirring 30min for 1:2 in molar ratio,
Add acetic anhydride stirring 90min, obtain the CoFe that Co ion concentration is 0.3mol/L mix homogeneously2O4Precursor liquid, wherein
Ethylene glycol monomethyl ether is 2.5:1 with the volume ratio of acetic anhydride；
Step 2: by Bi (NO3)3·5H2O、Sr(NO3)2、Fe(NO3)3·9H2O、C6H9MnO6·2H2O、Co(NO3)2·6H2O
It is that 1.01:0.04:0.98:0.01:0.01 (Bi excess 5%, x=0.01, y=0.01) is dissolved in ethylene glycol monomethyl ether according to mol ratio, stirs
Mix 30min, add acetic anhydride stirring 90min, obtain the mix homogeneously that metal ion total concentration is 0.25mol/L
Bi0.96Sr0.04FeO3Base film precursor liquid, wherein ethylene glycol monomethyl ether is 2.5:1 with the volume ratio of acetic anhydride；
Step 3: select FTO/glass substrate, the FTO/glass substrate of well cutting is sequentially placed in detergent, acetone, ethanol
Ultrasonic waves for cleaning, with a large amount of distilled water flushing substrates after each ultrasonic waves for cleaning 10min, finally dries up with nitrogen.Then will
60 DEG C of baking oven baking 5min put into by FTO/glass substrate, take out and stand to room temperature.Again clean FTO/glass substrate is placed in
Ultraviolet radiation instrument irradiates 40min, makes substrate surface reach " atomic cleanliness degree ".Use spin-coating method on FTO/glass substrate
Spin coating CoFe2O4Precursor liquid, obtains CoFe2O4Wet film, to CoFe2O4Wet film spin coating, spin coating rotating speed is 3600r/min, even
The glue time is 14s, after spin coating terminates, toasts 10min and obtain dry film at 180 DEG C, then anneals 15 at 580 DEG C in air layer by layer
Min, obtains crystalline state CoFe2O4Thin film；
Step 4: treat crystalline state CoFe2O4After film cooling, in crystalline state CoFe2O4Repeat step 3 on thin film, be repeated 3 times,
To CoFe2O4Crystalline state film；
Step 5: by CoFe2O4Crystalline state film is placed in ultraviolet radiation instrument irradiation 40min so that it is surface reaches atomic cleanliness degree；
Then at CoFe2O4Spin coating Bi on crystalline state film0.96Sr0.04FeO3Base film precursor liquid, obtains Bi0.96Sr0.04FeO3Base wet film, right
Bi0.96Sr0.04FeO3Base wet film spin coating, spin coating rotating speed is 3600r/min, and spin coating time is 14s, after spin coating terminates, at 180 DEG C
Lower baking 10min obtains dry film, then the 10min that anneals layer by layer in air at 542 DEG C, obtains crystalline state Bi0.96Sr0.04FeO3Base film；
Step 6: treat crystalline state Bi0.96Sr0.04FeO3After base film cooling, in crystalline state Bi0.96Sr0.04FeO3Step 5 is repeated on base film,
It is repeated 7 times, obtains high magnetic Bi0.96Sr0.04Fe0.98Mn0.01Co0.01O3/CoFe2O4Laminated film.
Embodiment 5
Step 1: by Co (NO3)2·6H2O and Fe (NO3)3·9H2O is dissolved in ethylene glycol monomethyl ether stirring 30min for 1:2 in molar ratio,
Add acetic anhydride stirring 90min, obtain the CoFe that Co ion concentration is 0.18mol/L mix homogeneously2O4Precursor liquid, wherein
Ethylene glycol monomethyl ether is 3.5:1 with the volume ratio of acetic anhydride；
Step 2: by Bi (NO3)3·5H2O、Sr(NO3)2、Fe(NO3)3·9H2O、C6H9MnO6·2H2O、Co(NO3)2·6H2O
It is that 1.01:0.04:0.975:0.02:0.005 (Bi excess 5%, x=0.02, y=0.005) is dissolved in ethylene glycol monomethyl ether according to mol ratio,
Stirring 30min, adds acetic anhydride stirring 90min, obtains the mix homogeneously that metal ion total concentration is 0.35mol/L
Bi0.96Sr0.04FeO3Base film precursor liquid, wherein ethylene glycol monomethyl ether is 3.5:1 with the volume ratio of acetic anhydride；
Step 3: select FTO/glass substrate, the FTO/glass substrate of well cutting is sequentially placed in detergent, acetone, ethanol
Ultrasonic waves for cleaning, with a large amount of distilled water flushing substrates after each ultrasonic waves for cleaning 10min, finally dries up with nitrogen.Then will
60 DEG C of baking oven baking 5min put into by FTO/glass substrate, take out and stand to room temperature.Again clean FTO/glass substrate is placed in
Ultraviolet radiation instrument irradiates 40min, makes substrate surface reach " atomic cleanliness degree ".Use spin-coating method on FTO/glass substrate
Spin coating CoFe2O4Precursor liquid, obtains CoFe2O4Wet film, to CoFe2O4Wet film spin coating, spin coating rotating speed is 4000r/min, even
The glue time is 10s, after spin coating terminates, toasts 9min and obtain dry film, then the 12min that anneals layer by layer in air at 590 DEG C at 190 DEG C,
Obtain crystalline state CoFe2O4Thin film；
Step 4: treat crystalline state CoFe2O4After film cooling, in crystalline state CoFe2O4Repeat step 3 on thin film, be repeated 5 times,
To CoFe2O4Crystalline state film；
Step 5: by CoFe2O4Crystalline state film is placed in ultraviolet radiation instrument irradiation 40min so that it is surface reaches atomic cleanliness degree；
Then at CoFe2O4Spin coating Bi on crystalline state film0.96Sr0.04FeO3Base film precursor liquid, obtains Bi0.96Sr0.04FeO3Base wet film, right
Bi0.96Sr0.04FeO3Base wet film spin coating, spin coating rotating speed is 4000r/min, and spin coating time is 10s, after spin coating terminates, at 190 DEG C
Lower baking 9min obtains dry film, then the 6min that anneals layer by layer in air at 550 DEG C, obtains crystalline state Bi0.96Sr0.04FeO3Base film；
Step 6: treat crystalline state Bi0.96Sr0.04FeO3After base film cooling, in crystalline state Bi0.96Sr0.04FeO3Step 5 is repeated on base film,
It is repeated 14 times, obtains high magnetic Bi0.96Sr0.04Fe0.975Mn0.02Co0.005O3/CoFe2O4Laminated film.
Embodiment 6
Step 1: by Co (NO3)2·6H2O and Fe (NO3)3·9H2O is dissolved in ethylene glycol monomethyl ether stirring 30min for 1:2 in molar ratio,
Add acetic anhydride stirring 90min, obtain the CoFe that Co ion concentration is 0.22mol/L mix homogeneously2O4Precursor liquid, wherein
Ethylene glycol monomethyl ether is 2.8:1 with the volume ratio of acetic anhydride；
Step 2: by Bi (NO3)3·5H2O、Sr(NO3)2、Fe(NO3)3·9H2O、C6H9MnO6·2H2O、Co(NO3)2·6H2O
It is that 1.01:0.04:0.955:0.03:0.015 (Bi excess 5%, x=0.03, y=0.015) is dissolved in ethylene glycol monomethyl ether according to mol ratio,
Stirring 30min, adds acetic anhydride stirring 90min, obtains the mix homogeneously that metal ion total concentration is 0.28mol/L
Bi0.96Sr0.04FeO3Base film precursor liquid, wherein ethylene glycol monomethyl ether is 2.8:1 with the volume ratio of acetic anhydride；
Step 3: select FTO/glass substrate, the FTO/glass substrate of well cutting is sequentially placed in detergent, acetone, ethanol
Ultrasonic waves for cleaning, with a large amount of distilled water flushing substrates after each ultrasonic waves for cleaning 10min, finally dries up with nitrogen.Then will
60 DEG C of baking oven baking 5min put into by FTO/glass substrate, take out and stand to room temperature.Again clean FTO/glass substrate is placed in
Ultraviolet radiation instrument irradiates 40min, makes substrate surface reach " atomic cleanliness degree ".Use spin-coating method on FTO/glass substrate
Spin coating CoFe2O4Precursor liquid, obtains CoFe2O4Wet film, to CoFe2O4Wet film spin coating, spin coating rotating speed is 3900r/min, even
The glue time is 12s, after spin coating terminates, toasts 6min and obtain dry film, then the 7min that anneals layer by layer in air at 595 DEG C at 210 DEG C,
Obtain crystalline state CoFe2O4Thin film；
Step 4: treat crystalline state CoFe2O4After film cooling, in crystalline state CoFe2O4Repeat step 3 on thin film, be repeated 6 times,
To CoFe2O4Crystalline state film；
Step 5: by CoFe2O4Crystalline state film is placed in ultraviolet radiation instrument irradiation 40min so that it is surface reaches atomic cleanliness degree；
Then at CoFe2O4Spin coating Bi on crystalline state film0.96Sr0.04FeO3Base film precursor liquid, obtains Bi0.96Sr0.04FeO3Base wet film, right
Bi0.96Sr0.04FeO3Base wet film spin coating, spin coating rotating speed is 3900r/min, and spin coating time is 12s, after spin coating terminates, at 210 DEG C
Lower baking 6min obtains dry film, then the 9min that anneals layer by layer in air at 545 DEG C, obtains crystalline state Bi0.96Sr0.04FeO3Base film；
Step 6: treat crystalline state Bi0.96Sr0.04FeO3After base film cooling, in crystalline state Bi0.96Sr0.04FeO3Step 5 is repeated on base film,
It is repeated 10 times, obtains high magnetic Bi0.96Sr0.04Fe0.955Mn0.03Co0.015O3/CoFe2O4Laminated film.
High magnetic Bi is tested with XRD0.96Sr0.04FeO3Base/CoFe2O4The thing phase composition structure of laminated film.Height is measured with SEM
Magnetic Bi0.96Sr0.04FeO3Base/CoFe2O4The microscopic appearance of laminated film and interracial contact situation.Use P-PMF1114-372 ferrum
Electroanalysis apparatus tests high magnetic Bi0.96Sr0.04FeO3Base/CoFe2O4The ferroelectric properties of laminated film.Accurate with Agilent E4980A
High magnetic Bi tested by LCR table0.96Sr0.04FeO3Base/CoFe2O4The dielectric properties of laminated film.With Agilent B2900 test height
Magnetic Bi0.96Sr0.04FeO3Base/CoFe2O4The leakage conductance current characteristics of laminated film.High magnetic is tested with SQUID MPMS-XL-7
Bi0.96Sr0.04FeO3Base/CoFe2O4Ferromagnetic property under laminated film room temperature.By high magnetic prepared by the present invention
Bi0.96Sr0.04FeO3Base/CoFe2O4Laminated film carries out above test, and result is as shown in figs. 1 to 6.
Fig. 1 is high magnetic Bi prepared by the present invention0.96Sr0.04FeO3Base/CoFe2O4The XRD figure of laminated film；Can from Fig. 1
Know, Bi0.96Sr0.04FeO3Base crystalline state film belongs to R3c:H space group, has trigonal crystal structure；CoFe2O4Crystalline state film belongs to R3c:H
Space group, has trigonal crystal structure, cell parameter a=b=c=8.3763, does not has impurity to occur.
Fig. 2 is high magnetic Bi prepared by the present invention0.96Sr0.04FeO3Base/CoFe2O4Laminated film SEM figure, wherein (a), (b),
C () is respectively high magnetic Bi that embodiment 1-3 prepares0.96Sr0.04FeO3Base/CoFe2O4The surface SEM figure of laminated film, (d)
For high magnetic Bi0.96Sr0.04FeO3Base/CoFe2O4The section SEM figure of laminated film；As can be seen from Figure 2 prepared by the present invention
High magnetic Bi0.96Sr0.04FeO3Base/CoFe2O4Laminated film surfacing, even grain size, wherein Bi0.96Sr0.04FeO3
The thickness of base film is about 500nm, CoFe2O4The thickness of thin film is about 200nm, high magnetic Bi0.96Sr0.04FeO3Base/CoFe2O4
The gross thickness of laminated film is about 700nm.
Fig. 3 is high magnetic Bi prepared by the present invention0.96Sr0.04FeO3Base/CoFe2O4The dielectric constant of laminated film and dielectric loss with
The graph of a relation of test frequency；From figure 3, it can be seen that when testing frequency and being 1kHz, Bi0.96Sr0.04Fe0.98Co0.02O3/CoFe2O4
The dielectric constant of laminated film is 435, Bi0.96Sr0.04Fe0.96Mn0.04O3/CoFe2O4The dielectric constant of laminated film is 750,
Bi0.96Sr0.04Fe0.94Mn0.04Co0.02O3/CoFe2O4The dielectric constant of laminated film is 800.
Fig. 4 is high magnetic Bi prepared by the present invention0.96Sr0.04FeO3Base/CoFe2O4The leakage current density of laminated film；From Fig. 4
It can be seen that when electric field is 200kV/cm, Bi0.96Sr0.04Fe0.98Co0.02O3/CoFe2O4The leakage current density of laminated film is
1.83×10-5A/cm2, Bi0.96Sr0.04Fe0.96Mn0.04O3/CoFe2O4The leakage current density of laminated film is 4.46 × 10-6A/cm2,
Bi0.96Sr0.04Fe0.94Mn0.04Co0.02O3/CoFe2O4The leakage current density of laminated film is 1.37 × 10-5。
Fig. 5 is high magnetic Bi prepared by the present invention0.96Sr0.04FeO3Base/CoFe2O4The ferroelectric hysteresis loop of laminated film；Can from Fig. 5
To find out, when full test electric field is 500kV/cm, high magnetic Bi0.96Sr0.04Fe0.98Co0.02O3/CoFe2O4Laminated film
Saturated polarization is 100 μ C/cm2, remanent polarization is 84 μ C/cm2, coercive field is 376kV/cm；High magnetic
Bi0.96Sr0.04Fe0.96Mn0.04O3/CoFe2O4The saturated polarization of laminated film is 123 μ C/cm2, remanent polarization is 104
μC/cm2, coercive field is 326kV/cm；High magnetic Bi0.96Sr0.04Fe0.94Mn0.04Co0.02O3/CoFe2O4Laminated film saturated
Polarization intensity is 167 μ C/cm2, remanent polarization is 150 μ C/cm2, coercive field is 324kV/cm.It addition, from Fig. 5
Can be seen that high magnetic Bi that the present invention prepares0.96Sr0.04FeO3Base/CoFe2O4Laminated film occur in that directric relaxation phenomenon, and
Directric relaxation peak gradually moves to high frequency direction along with the increase of doped chemical kind.
Fig. 6 is high magnetic Bi prepared by the present invention0.96Sr0.04FeO3Base/CoFe2O4The hysteresis curve of laminated film, can from Fig. 6
To find out, under room temperature, Bi0.96Sr0.04Fe0.98Co0.02O3/CoFe2O4The saturation magnetisation value of laminated film is 74emu/cm3, residue
Magnetization value is 47emu/cm3；Bi0.96Sr0.04Fe0.96Mn0.04O3/CoFe2O4The saturation magnetisation value of laminated film is 71emu/cm3,
Remanent magnetization value is 46emu/cm3；Bi0.96Sr0.04Fe0.94Mn0.04Co0.02O3/CoFe2O4The saturation magnetisation value of laminated film is 108
emu/cm3, remanent magnetization value is 60emu/cm3。
The invention provides a kind of sol-gel process and prepare high magnetic Bi0.96Sr0.04FeO3Base/CoFe2O4The method of laminated film,
The method equipment requirements is simple, suitably prepares thin film on big surface and surface in irregular shape, and the uniformity of film of preparation is relatively
Good, and chemical constituent controllable precise.By ion doping and with magnetic CoFe2O4Thin film is combined, and thin film is greatly improved
Dielectric, ferroelectricity and ferromagnetic property, also effectively reduce the leakage current density of thin film.
The foregoing is only one embodiment of the present invention, be not all of or unique embodiment, those of ordinary skill in the art
The conversion of any equivalence taked technical solution of the present invention by reading description of the invention, is the claim institute of the present invention
Contain.
Claims (10)
1. high magnetic Bi0.96Sr0.04FeO3Base/CoFe2O4Laminated film, it is characterised in that: include being combined with each other is upper
Tunic and lower membrane, wherein lower membrane is CoFe2O4Crystalline state film, upper layer film is Bi0.96Sr0.04FeO3Base crystalline state film, its structural formula
For Bi0.96Sr0.04Fe1-x-yMnxCoyO3, x=0～0.04, y=0～0.02, and be 0 during x, y difference.
High magnetic Bi the most according to claim 10.96Sr0.04FeO3Base/CoFe2O4Laminated film, it is characterised in that: institute
The Bi stated0.96Sr0.04FeO3Base crystalline state film belongs to R3c:H space group, has trigonal crystal structure；CoFe2O4Crystalline state film belongs to R3c:H
Space group, has trigonal crystal structure, cell parameter a=b=c=8.3763.
High magnetic Bi the most according to claim 10.96Sr0.04FeO3Base/CoFe2O4Laminated film, it is characterised in that: institute
High magnetic Bi stated0.96Sr0.04FeO3Base/CoFe2O4Laminated film includes Bi0.96Sr0.04Fe0.98Co0.02O3/CoFe2O4THIN COMPOSITE
Film, Bi0.96Sr0.04Fe0.96Mn0.04O3/CoFe2O4Laminated film and Bi0.96Sr0.04Fe0.94Mn0.04Co0.02O3/CoFe2O4THIN COMPOSITE
Film；
Wherein Bi0.96Sr0.04Fe0.98Co0.02O3/CoFe2O4Saturation magnetisation value under laminated film room temperature is 74emu/cm3, remanence
Change value is 47emu/cm3；Under 1kHz test frequency, its dielectric constant is 435；Under 200kV/cm electric field, its electric leakage
Current density is 1.83 × 10-5A/cm2；When full test electric field is 500kV/cm, its saturated polarization is 100 μ C/cm2,
Remanent polarization is 84 μ C/cm2, coercive field is 376kV/cm；
Bi0.96Sr0.04Fe0.96Mn0.04O3/CoFe2O4Saturation magnetisation value under laminated film room temperature is 71emu/cm3, remanent magnetization value
For 46emu/cm3；Under 1kHz test frequency, its dielectric constant is 750；Under 200kV/cm electric field, its leakage current is close
Degree is 4.46 × 10-6A/cm2；When full test electric field is 500kV/cm, its saturated polarization is 123 μ C/cm2, residue
Polarization intensity is 104 μ C/cm2, coercive field is 326kV/cm；
Bi0.96Sr0.04Fe0.94Mn0.04Co0.02O3/CoFe2O4Saturation magnetisation value under laminated film room temperature is 108emu/cm3, residue
Magnetization value is 60emu/cm3；Under 1kHz test frequency, its dielectric constant is 800；Under 200kV/cm electric field, its leakage
Electric current density is 1.37 × 10-5A/cm2；When full test electric field is 500kV/cm, its saturated polarization is 167 μ C/cm2,
Remanent polarization is 150 μ C/cm2, coercive field is 324kV/cm.
4. high magnetic Bi0.96Sr0.04FeO3Base/CoFe2O4The preparation method of laminated film, it is characterised in that include following
Step:
Step 1: by Co (NO3)2·6H2O and Fe (NO3)3·9H2O is dissolved in ethylene glycol monomethyl ether for 1:2 in molar ratio, and stirring is all
Add acetic anhydride after even, obtain CoFe2O4Precursor liquid；Wherein CoFe2O4In precursor liquid, the concentration of Co ion is 0.15～0.3
mol/L；
Step 2: be that 1.01:0.04:1-x-y:x:y is by Bi (NO in molar ratio3)3·5H2O、Sr(NO3)2、Fe(NO3)3·9H2O、
C6H9MnO6·2H2O、Co(NO3)2·6H2O is dissolved in solvent, obtains Bi0.96Sr0.04FeO3Base film precursor liquid, wherein
X=0～0.04, y=0～0.02, and be 0, Bi during x, y difference0.96Sr0.04FeO3The total concentration of metal ion in base film precursor liquid
Being 0.25～0.35mol/L, solvent is the mixed liquor of ethylene glycol monomethyl ether and acetic anhydride；
Step 3: use spin-coating method spin coating CoFe on substrate2O4Precursor liquid, obtains CoFe2O4Wet film, CoFe2O4Wet film warp
At 180～210 DEG C, toast to obtain dry film after spin coating, anneal in atmosphere at 580～600 DEG C, obtain crystalline state CoFe2O4Thin film；
Step 4: treat crystalline state CoFe2O4After film cooling, in crystalline state CoFe2O4Step 3 is repeated, until it reaches required on thin film
Thickness, obtains CoFe2O4Crystalline state film；
Step 5: at CoFe2O4Spin coating Bi on crystalline state film0.96Sr0.04FeO3Base film precursor liquid, obtains Bi0.96Sr0.04FeO3Base is wet
Film, Bi0.96Sr0.04FeO3Base wet film toasts to obtain dry film after spin coating at 180～210 DEG C, then anneals in atmosphere, obtains crystalline state
Bi0.96Sr0.04FeO3Base film；Wherein annealing temperature is 540～550 DEG C；
Step 6: treat crystalline state Bi0.96Sr0.04FeO3After base film cooling, repeat step 5 thereon, until it reaches desired thickness,
I.e. obtain high magnetic Bi0.96Sr0.04FeO3Base/CoFe2O4Laminated film.
High magnetic Bi the most according to claim 40.96Sr0.04FeO3Base/CoFe2O4The preparation method of laminated film, it is special
Levy and be: described CoFe2O4In precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is (2.5～3.5): 1；Described step 2
In solvent, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is (2.5～3.5): 1.
High magnetic Bi the most according to claim 40.96Sr0.04FeO3Base/CoFe2O4The preparation method of laminated film, it is special
Levy and be: substrate, before carrying out, is first carried out by described step 3, the most under ultraviolet light treatment with irradiation, make substrate surface reach
To atomic cleanliness degree, then spin coating CoFe2O4Precursor liquid；
Described step 5 is before carrying out, first to CoFe2O4Crystalline state film carries out ultraviolet light treatment with irradiation, makes CoFe2O4Crystalline state film surface
Reach atomic cleanliness degree, then spin coating Bi0.96Sr0.04FeO3Base film precursor liquid.
High magnetic Bi the most according to claim 40.96Sr0.04FeO3Base/CoFe2O4The preparation method of laminated film, it is special
Levy and be: in described step 3 and step 5, spin coating rotating speed during spin coating is 3600～4000r/min, and spin coating time is 10～15s.
High magnetic Bi the most according to claim 40.96Sr0.04FeO3Base/CoFe2O4The preparation method of laminated film, it is special
Levy and be: in described step 3 and step 5, the baking time after spin coating is 6～10min.
High magnetic Bi the most according to claim 40.96Sr0.04FeO3Base/CoFe2O4The preparation method of laminated film, it is special
Levy and be: the annealing time in described step 3 is 7～annealing time in 15min, step 5 is 6～12min.
High magnetic Bi the most according to claim 40.96Sr0.04FeO3Base/CoFe2O4The preparation method of laminated film, it is special
Levy and be: described high magnetic Bi0.96Sr0.04FeO3Base/CoFe2O4Laminated film is by 4～8 layer crystal states CoFe2O4Thin film and 8～15
Layer crystal state Bi0.96Sr0.04FeO3Base film is constituted.
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| CN109111127A (en) * | 2018-09-18 | 2019-01-01 | 陕西科技大学 | A kind of BLSFMC/CMFO film and preparation method thereof with resistance switch effect |
| CN109205683A (en) * | 2018-09-18 | 2019-01-15 | 陕西科技大学 | A kind of the BLSFMC/CFLO laminated film and preparation method of symmetrical rectangular ferroelectric hysteresis loop |
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| CN109111127A (en) * | 2018-09-18 | 2019-01-01 | 陕西科技大学 | A kind of BLSFMC/CMFO film and preparation method thereof with resistance switch effect |
| CN109205683A (en) * | 2018-09-18 | 2019-01-15 | 陕西科技大学 | A kind of the BLSFMC/CFLO laminated film and preparation method of symmetrical rectangular ferroelectric hysteresis loop |
| CN109205683B (en) * | 2018-09-18 | 2020-08-25 | 陕西科技大学 | BLSFMC/CFLO composite film with symmetrical rectangular hysteresis loop and preparation method thereof |
| CN109111127B (en) * | 2018-09-18 | 2021-06-29 | 陕西科技大学 | BLSFMC/CMFO film with resistance switching effect and preparation method thereof |
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