CN105837196A - Bi0.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4 ferromagnetic composite film and preparation method thereof - Google Patents

Bi0.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4 ferromagnetic composite film and preparation method thereof Download PDF

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CN105837196A
CN105837196A CN201610188153.2A CN201610188153A CN105837196A CN 105837196 A CN105837196 A CN 105837196A CN 201610188153 A CN201610188153 A CN 201610188153A CN 105837196 A CN105837196 A CN 105837196A
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film
ferromagnetism
spin coating
crystalline state
laminated film
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谈国强
杨玮
耶维
乐忠威
夏傲
任慧君
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Shaanxi University of Science and Technology
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Abstract

The invention provides a Bi0.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4 ferromagnetic composite film and a preparation method thereof. The ferromagnetic composite film comprises a Bi0.92-xHo0.08AExFe0.97Mn0.03O3 crystalline film and a Zn1-yNiyFe2O4 crystalline film, which are compounded together. The preparation method is as below: first respectively preparing a Zn1-yNiyFe2O4 precursor solution and a Bi0.92-xHo0.08AExFe0.97Mn0.03O3 precursor solution, wherein AE is Sr, Ca, Ba or Pb, x equals to 0.01-0.04, and y equals to 0.1-0.9; preparing a plurality of Zn1-yNiyFe2O4 films on a substrate by spin coating; and then preparing plurality of Bi0.92-xHo0.08AExFe0.97Mn0.03O3 films on the Zn1-yNiyFe2O4 films by spin coating, so as to obtain the ferromagnetic composite film. The method regulates the crystal structure of BiFeO3 by doping, and uses ferromagnetic Zn1-yNiyFe2O4 as the magnetic layer, so as to substantially increase the ferroelectric and ferromagnetic properties of the film, and effectively reduce the leakage current density of the film.

Description

A kind of Bi0.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4Ferromagnetism laminated film and preparation method thereof
Technical field
The invention belongs to field of functional materials, relate to a kind of method that substrate surface in functionalization prepares ferromagnetism laminated film, tool Body relates to a kind of Bi0.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4Ferromagnetism laminated film and preparation method thereof.
Background technology
Single-phase magnetoelectricity multi-ferroic material the most also could not be applied in reality, is primarily due to the Curie temperature of major part monophase materials relatively Low, the most just there is magnetoelectric effect, and magnetoelectric effect is the faintest.Although single-phase BiFeO3The Curie temperature of material and Neel temperature all more than room temperature, but due to BiFeO3Spiral magnetic structure so that BiFeO3In G type anti-ferromagnetism, Only showing faint ferromagnetism under low electric field, its less magneto-electric coupled characteristic hinders its actual application at many ferrum aspect.Phase Instead, multiferroic magnetic electric compound material can have the strong magnetoelectric effect under room temperature, thus has actual application value.
But limit BiFeO at present3The maximum problem of thin film application is exactly low-resistivity, it is impossible at room temperature measure its ferroelectricity Matter.Traditional slow annealing technique prepares BiFeO3Time, Lacking oxygen is issued to dynamic equilibrium at high annealing, when annealing process is tied Bundle, part Lacking oxygen is detained wherein, forms the gathering of Lacking oxygen, causes the skew of oxygen dosage, this skew that ferrum valence state is occurred Fluctuation (Fe3+It is converted into Fe2+).The fluctuation of ferrum valence state causes big leakage conductance, so that BiFeO3Leakage current is relatively big, due to big leakage Lead make its ferroelectricity cannot correct measurement and obtain saturated polarization.ZnNiFe2O4Crystal belongs to cubic system, cube face-centered lattice, Fd3m Space group.The normal spinel structure material being made up of Zn-Fe-O ternary system is the magnetisable material of function admirable, has high saturated The intensity of magnetization, high-coercive force, high magnetic permeability, big magnetocrystalline anisotropy, big magnetostriction and high chemical stability, Being 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, is also suitable for Apply under high frequency and hyperfrequency.If the multi-ferroic material of excellent performance just can be obtained in conjunction with the advantage of both the above material, but There is presently no relevant report.
Summary of the invention
It is an object of the invention to provide a kind of Bi0.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4Ferromagnetism laminated film And preparation method thereof, it is possible to effectively reduce BiFeO3Leakage current, improve its ferroelectricity and ferromagnetic property simultaneously.
To achieve these goals, the present invention adopts the following technical scheme that
A kind of Bi0.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4Ferromagnetism laminated film, including the upper strata being combined with each other Film and lower membrane, wherein upper layer film is Bi0.92-xHo0.08AExFe0.97Mn0.03O3Crystalline state film, AE=Sr, Ca, Ba or Pb, X=0.01～0.04；Lower membrane is Zn1-yNiyFe2O4Crystalline state film, y=0.1～0.9.
Described Bi0.92-xHo0.08AExFe0.97Mn0.03O3Crystalline state film is the perovskite structure of distortion, and rhombohedral system, space group is R3m(160)；Zn1-yNiyFe2O4Crystalline state film is Emission in Cubic, spinel structure, and space group is Fd-3m (227).
Described Bi0.89Ho0.08Sr0.03Fe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4The saturation magnetization of ferromagnetism laminated film is Ms=57～59emu/cm3, remanent magnetization is Mr=4～6emu/cm3, the leakage current density under 300kV/cm electric field is 3.3×10-4A/cm2；Remanent polarization under 1kHz frequency, 60V electric field is Pr=115～116 μ C/cm2, coercive field is Ec=500～510kV/cm；
Described Bi0.91Ho0.08Ca0.01Fe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4The saturation magnetization of ferromagnetism laminated film is Ms=71～72emu/cm3, remanent magnetization is Mr=3～5emu/cm3, residual polarization under 1kHz frequency, 60V electric field Intensity is Pr=24～25 μ C/cm2, coercive field is Ec=460～500kV/cm；
Described Bi0.89Ho0.08Ba0.03Fe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4The saturation magnetization of ferromagnetism laminated film is Ms=61～63emu/cm3, remanent magnetization is Mr=4～7emu/cm3, residual polarization under 1kHz frequency, 60V electric field Intensity is Pr=43～45 μ C/cm2, coercive field is Ec=550～570kV/cm.
A kind of Bi0.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4The preparation method of ferromagnetism laminated film, including following step Rapid:
Step 1, is dissolved in ethylene glycol monomethyl ether for 1-y:y:2 in molar ratio by zinc nitrate, nickel acetate and ferric nitrate, after stirring Add acetic anhydride, obtain Zn1-yNiyFe2O4Precursor liquid；Wherein y=0.1～0.9, Zn1-yNiyFe2O4Fe ion in precursor liquid Concentration is 0.1～0.2mol/L；
Step 2, is 0.97-x:0.08:x:0.97:0.03 by bismuth nitrate, holmium nitrate, nitric acid AE, ferric nitrate and manganese nitrate in molar ratio It is dissolved in solvent, obtains Bi0.92-xHo0.08AExFe0.97Mn0.03O3Precursor solution；Wherein AE is Sr, Ca, Ba or Pb, X=0.01～0.04, Bi0.92-xHo0.08AExFe0.97Mn0.03O3In precursor solution, the total concentration of metal ion is 0.003～0.3mol/L, Solvent is the mixed liquor of ethylene glycol monomethyl ether and acetic anhydride；
Step 3, uses spin-coating method spin coating Zn on substrate1-yNiyFe2O4Precursor liquid, obtains Zn1-yNiyFe2O4Wet film, Zn1-yNiyFe2O4Wet film toasts to obtain dry film after spin coating at 190～210 DEG C, anneals in atmosphere at 590～610 DEG C, To crystalline state Zn1-yNiyFe2O4Thin film；
Step 4, treats crystalline state Zn1-yNiyFe2O4After film cooling, in crystalline state Zn1-yNiyFe2O4Step 3 is repeated on thin film, until Reach desired thickness, obtain Zn1-yNiyFe2O4Crystalline state film；
Step 5, at Zn1-yNiyFe2O4Spin coating Bi on crystalline state film0.92-xHo0.08AExFe0.97Mn0.03O3Precursor solution, obtains Bi0.92-xHo0.08AExFe0.97Mn0.03O3Wet film, Bi0.92-xHo0.08AExFe0.97Mn0.03O3Wet film after spin coating at 190～210 DEG C Under toast to obtain dry film, anneal in atmosphere at 540～560 DEG C, obtain crystalline state Bi0.92-xHo0.08AExFe0.97Mn0.03O3Thin film；
Step 6, treats crystalline state Bi0.92-xHo0.08AExFe0.97Mn0.03O3After film cooling, repeat step 5 thereon, until it reaches Desired thickness, i.e. obtains Bi0.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4Ferromagnetism laminated film.
Described Zn1-yNiyFe2O4In 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.
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 Zn1-yNiyFe2O4Precursor liquid；
Described step 5 is before carrying out, first to Zn1-yNiyFe2O4Crystalline state film carries out ultraviolet light treatment with irradiation, makes Zn1-yNiyFe2O4 Crystalline state film surface reaches atomic cleanliness degree, then spin coating Bi0.92-xHo0.08AExFe0.97Mn0.03O3Precursor solution.
In described step 3 and step 5, spin coating rotating speed during spin coating is 3800～4100r/min, and spin coating time is 10～20s.
In described step 3 and step 5, the baking time after spin coating is 8～10min.
Annealing time in described step 3 is 18～annealing time in 22min, step 5 is 8～12min.
Described Bi0.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4Ferromagnetism laminated film is by 1～6 layer crystal states Zn1-yNiyFe2O4Thin film and 3～15 layer crystal states Bi0.92-xHo0.08AExFe0.97Mn0.03O3Thin film is constituted.
Relative to prior art, the method have the advantages that
1. the Bi that the present invention provides0.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4The preparation method of ferromagnetism laminated film, Rare earth element Ho and AE (AE=Ca, Sr, Ba or Pb) is selected to carry out BiFeO3A position doping, select transient metal Mn Carry out BiFeO3B position doping, due to rare earth elementAnd transition metalRadius divide It is not less thanWithAfter doping, rare earth element Ho3+, transient metal Mn2+Can admittedly melt Entering lattice, can make the bismuth ferrite crystal lattices distortion originally approximated in perovskite structure, structural aberration aggravates, simultaneously because AE pair Bi3+Further replacement, and Mn element appraising at the current rate in annealing process, the volatilization of the Bi that can effectively draw up, reduce thin Fe in film2+With the content of Lacking oxygen, make lattice structure be distorted further, thus strengthen Bi0.92-xHo0.08AExFe0.97Mn0.03O3 Thin film polarization intensity under extra electric field.Additionally, the distortion of this structure can suppress the spiral magnetic of spatial modulation special for BFO Structure, discharges the macroscopic magnetization that part is potential, improves Bi0.92-xHo0.08AExFe0.97Mn0.03O3The ferromagnetism of thin film.But due to BiFeO3Itself there is the essence of weak magnetic, so the present invention combines ZnFe2O4Thin film, by Bi0.92-xHo0.08AExFe0.97Mn0.03O3 Thin film and Zn1-yNiyFe2O4Film laminated is together.ZnFe2O4Having the strongest magnetic, magnetic coercive field is the least simultaneously, is reason The composite thought, is doped into ZnFe by Ni2O4Lattice i.e. obtains has ferromagnetism and the Zn of little magnetic coercive field1-yNiyFe2O4.This Invention uses 2-2 type complex form, with AE, rare earth element Ho and the transition metal Mn tri-element codope of A, B position BiFeO3The Bi obtained0.92-xHo0.08AExFe0.97Mn0.03O3As ferroelectric layer, with Ni doping ZnFe2O4Obtain Zn1-yNiyFe2O4As magnetosphere, BiFeO can be solved simultaneously3Leakage conductance electric current is big and the weak two large problems of magnetic, the while of having obtained There is the Bi of superior ferroelectric and ferromagnetic property0.92Ho0.08Fe0.97Mn0.03O3-Zn1-yNiyFe2O4Laminated film.
2. it is currently used for preparing BiFeO3The method of thin film has a lot, such as chemical vapour deposition technique (CVD), magnetron sputtering method (rf Magnetron sputtering), deposition of metal organic method (MOD), metal-organic chemical vapor deposition equipment method (MOCVD), liquid Phase sedimentation (LPD), molecular beam epitaxy (MBE), pulsed laser deposition (PLD), sol-gel process (Sol-Gel) etc..Phase Ratio additive method, Sol-Gel method is simple due to equipment, and reaction is easily carried out, and reaction temperature is relatively low, easily operates, suitably greatly Surface and surface in irregular shape on prepare thin film, easily realize the Uniform Doped on molecular level, and chemical constituent accurately may be used The advantages such as control and be widely used for preparing ferroelectric material.The present invention uses sol-gal process, by AE (AE=Ca, Sr, Ba And Pb), rare earth element Ho and transition metal Mn tri-element codope BiFeO3, and compound Zn1-yNiyFe2O4, at base Bi is prepared on plate0.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4Ferromagnetism laminated film, equipment requirements is simple, tests bar Part easily reaches, and doping is easily controlled, the Bi of preparation0.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4Ferromagnetism is combined Uniformity of film is good, has relatively low leakage current density and higher anti-breakdown electric field, and can be by doping and Zn1-yNiyFe2O4 Compound increase substantially its ferroelectricity and ferromagnetic property.
3. the Bi that the present invention provides0.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4Ferromagnetism laminated film, in approximation originally In adulterate in the bismuth ferrite crystal lattices of perovskite structure AE (AE=Ca, Sr, Ba and Pb), rare earth element Ho and transition metal Mn, makes bismuth ferrite crystal lattices distort, and structural aberration aggravates, and reduces Fe in thin film simultaneously2+With the content of Lacking oxygen, thus strengthen thin Film polarization intensity under extra electric field, discharges its macroscopic magnetization simultaneously, improves ferroelectric properties and the ferromagnetic property of thin film, reduces The leakage current density of thin film, and combine ferromagnetism, the Zn of low coercive field1-yNiyFe2O4Film, makes the present invention's Bi0.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4Ferromagnetism laminated film has the ferroelectric properties and ferromagnetic of excellence simultaneously Performance.
Accompanying drawing explanation
Fig. 1 is Bi prepared by the present invention0.92-xHo0.08AExFe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4(AE=Sr, Ca or Ba) ferrum The XRD figure of magnetic coupling thin film.
Fig. 2 is Bi prepared by the present invention0.92-xHo0.08AExFe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4The SEM of ferromagnetism laminated film Figure, wherein (a) is Bi0.91Ho0.08Ca0.01Fe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4The surface SEM figure of ferromagnetism laminated film； B () is Bi0.89Ho0.08Ba0.03Fe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4The surface SEM figure of ferromagnetism laminated film；(c) be Bi0.89Ho0.08Sr0.03Fe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4The surface SEM figure of ferromagnetism laminated film；(d) be Bi0.89Ho0.08Sr0.03Fe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4The section SEM figure of ferromagnetism laminated film.
Fig. 3 is Bi prepared by the present invention0.92-xHo0.08AExFe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4The dielectric of ferromagnetism laminated film Frequency spectrum and loss spectrogram.
Fig. 4 is Bi prepared by the present invention0.92-xHo0.08AExFe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4The leakage conductance of ferromagnetism laminated film Electric current and the graph of a relation of electric field.
Fig. 5 is Bi prepared by the present invention0.92-xHo0.08AExFe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4The electric hysteresis of ferromagnetism laminated film Loop line figure.
Fig. 6 is Bi prepared by the present invention0.92-xHo0.08AExFe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4The magnetic hysteresis of ferromagnetism laminated film Loop line figure.
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, is dissolved in zinc nitrate, nickel acetate and ferric nitrate in ethylene glycol monomethyl ether for 0.5:0.5:2 (y=0.5) in molar ratio, stirs After mixing 30min, add acetic anhydride, obtain the stable Zn that Fe ion concentration is 0.1mol/L0.5Ni0.5Fe2O4Precursor liquid, Wherein Zn0.5Ni0.5Fe2O4In precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 3:1；
Step 2, is 0.89:0.08:0.03:0.97:0.03 in molar ratio by bismuth nitrate, holmium nitrate, strontium nitrate, ferric nitrate and manganese nitrate Being dissolved in solvent (AE=Sr, x=0.03, bismuth nitrate excess 5%), obtaining metal ion total concentration is the stable of 0.3mol/L Bi0.89Ho0.08Sr0.03Fe0.97Mn0.03O3Precursor solution；Wherein solvent be volume ratio be the mixed of 3:1 ethylene glycol monomethyl ether and acetic anhydride Close liquid；
Step 3, select FTO/glass substrate be substrate, the FTO/glass substrate of well cutting is sequentially placed into detergent, acetone, Ultrasonic waves for cleaning in ethanol, with a large amount of distilled water flushing substrates after each ultrasonic waves for cleaning 10min, finally dries up with nitrogen.Then FTO/glass substrate is put into baking oven be baked to be dried, take out and stand to room temperature.Again clean FTO/glass substrate is placed in purple Outer smooth radiation instrument irradiates 40min, makes substrate surface reach " atomic cleanliness degree ".Use spin-coating method again on FTO/glass substrate Spin coating Zn0.5Ni0.5Fe2O4Precursor solution, obtains Zn0.5Ni0.5Fe2O4Wet film, to Zn0.5Ni0.5Fe2O4Wet film spin coating, spin coating Rotating speed is 4000r/min, and spin coating time is 15s, after spin coating terminates, toasts 8min and obtain dry film at a temperature of 200 DEG C, then at 600 DEG C At a temperature of air is annealed layer by layer 20min, obtain crystalline state Zn0.5Ni0.5Fe2O4Thin film；
Step 4, treats crystalline state Zn0.5Ni0.5Fe2O4After film cooling, in crystalline state Zn0.5Ni0.5Fe2O4Step 3, weight is repeated on thin film Multiple 5 times, obtain Zn0.5Ni0.5Fe2O4Crystalline state film；
Step 5, by Zn0.5Ni0.5Fe2O4Crystalline state film is placed in ultraviolet radiation instrument irradiation 40min so that it is surface reaches atomic cleanliness Degree；Again at Zn0.5Ni0.5Fe2O4Spin coating Bi on crystalline state film0.89Ho0.08Sr0.03Fe0.97Mn0.03O3Precursor solution, obtains Bi0.89Ho0.08Sr0.03Fe0.97Mn0.03O3Wet film, to Bi0.89Ho0.08Sr0.03Fe0.97Mn0.03O3Wet film spin coating, spin coating rotating speed is 4000r/min, spin coating time is 15s, after spin coating terminates, toasts 8min and obtain dry film at 200 DEG C, then at 550 DEG C in air Anneal 10min layer by layer, obtains crystalline state Bi0.89Ho0.08Sr0.03Fe0.97Mn0.03O3Thin film；
Step 6, treats crystalline state Bi0.89Ho0.08Sr0.03Fe0.97Mn0.03O3After film cooling, in crystalline state Bi0.89Ho0.08Sr0.03Fe0.97Mn0.03O3Repeat step 5 on thin film, be repeated 12 times, i.e. obtain Bi0.89Ho0.08Sr0.03Fe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4Ferromagnetism laminated film.
Use XRD determining Bi0.89Ho0.08Sr0.03Fe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4The thing phase composition knot of ferromagnetism laminated film Structure.Bi is measured with FE-SEM0.89Ho0.08Sr0.03Fe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4The microscopic appearance of ferromagnetism laminated film Interracial contact situation.With P-PMF1114-372 ferroelectricity analyser test b i0.89Ho0.08Sr0.03Fe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4 The ferroelectric properties of ferromagnetism laminated film.Test with Agilent E4980A precision LCR table Bi0.89Ho0.08Sr0.03Fe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4The dielectric properties of ferromagnetism laminated film.Survey with Agilent B2900 Examination Bi0.89Ho0.08Sr0.03Fe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4The leakage conductance current characteristics of ferromagnetism laminated film.Use SQUID MPMS-XL-7 test b i0.89Ho0.08Sr0.03Fe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4Ferromagnetism under ferromagnetism laminated film room temperature Energy.Obtaining following result: under 1kHz frequency, 60V electric field, its coercive field is (Ec=500～510kV/cm), remains pole Changing intensity is (Pr=115～116 μ C/cm2)；Saturation magnetization is (Ms=57～59emu/cm3), remanent magnetization is (Mr=4～6emu/cm3)。
Embodiment 2
Step 1, is dissolved in zinc nitrate, nickel acetate and ferric nitrate in ethylene glycol monomethyl ether for 0.5:0.5:2 (y=0.5) in molar ratio, stirs After mixing 30min, add acetic anhydride, obtain the stable Zn that Fe ion concentration is 0.1mol/L0.5Ni0.5Fe2O4Precursor liquid, Wherein Zn0.5Ni0.5Fe2O4In precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 3:1；
Step 2, is 0.91:0.08:0.01:0.97:0.03 in molar ratio by bismuth nitrate, holmium nitrate, calcium nitrate, ferric nitrate and manganese nitrate Being dissolved in solvent (AE=Ca, x=0.01, bismuth nitrate excess 5%), obtaining metal ion total concentration is the stable of 0.3mol/L Bi0.91Ho0.08Ca0.01Fe0.97Mn0.03O3Precursor solution；Wherein solvent be volume ratio be the mixed of 3:1 ethylene glycol monomethyl ether and acetic anhydride Close liquid；
Step 3, select FTO/glass substrate be substrate, the FTO/glass substrate of well cutting is sequentially placed into detergent, acetone, Ultrasonic waves for cleaning in ethanol, with a large amount of distilled water flushing substrates after each ultrasonic waves for cleaning 10min, finally dries up with nitrogen.Then FTO/glass substrate is put into baking oven be baked to be dried, take out and stand to room temperature.Again clean FTO/glass substrate is placed in purple Outer smooth radiation instrument irradiates 40min, makes substrate surface reach " atomic cleanliness degree ".Use spin-coating method again on FTO/glass substrate Spin coating Zn0.5Ni0.5Fe2O4Precursor solution, obtains Zn0.5Ni0.5Fe2O4Wet film, to Zn0.5Ni0.5Fe2O4Wet film spin coating, spin coating Rotating speed is 4000r/min, and spin coating time is 15s, after spin coating terminates, toasts 8min and obtain dry film at a temperature of 200 DEG C, then at 600 DEG C At a temperature of air is annealed layer by layer 20min, obtain crystalline state Zn0.5Ni0.5Fe2O4Thin film；
Step 4, treats crystalline state Zn0.5Ni0.5Fe2O4After film cooling, in crystalline state Zn0.5Ni0.5Fe2O4Step 3, weight is repeated on thin film Multiple 5 times, obtain Zn0.5Ni0.5Fe2O4Crystalline state film；
Step 5, by Zn0.5Ni0.5Fe2O4Crystalline state film is placed in ultraviolet radiation instrument irradiation 40min so that it is surface reaches atomic cleanliness Degree；Again at Zn0.5Ni0.5Fe2O4Spin coating Bi on crystalline state film0.91Ho0.08Ca0.01Fe0.97Mn0.03O3Precursor solution, obtains Bi0.91Ho0.08Ca0.01Fe0.97Mn0.03O3Wet film, to Bi0.91Ho0.08Ca0.01Fe0.97Mn0.03O3Wet film spin coating, spin coating rotating speed is 4000r/min, spin coating time is 15s, after spin coating terminates, toasts 8min and obtain dry film at 200 DEG C, then at 550 DEG C in air Anneal 10min layer by layer, obtains crystalline state Bi0.91Ho0.08Ca0.01Fe0.97Mn0.03O3Thin film；
Step 6, treats crystalline state Bi0.91Ho0.08Ca0.01Fe0.97Mn0.03O3After film cooling, in crystalline state Bi0.91Ho0.08Ca0.01Fe0.97Mn0.03O3Repeat step 5 on thin film, be repeated 12 times, i.e. obtain Bi0.91Ho0.08Ca0.01Fe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4Ferromagnetism laminated film.
Use XRD determining Bi0.91Ho0.08Ca0.01Fe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4The thing phase composition knot of ferromagnetism laminated film Structure.Bi is measured with FE-SEM0.91Ho0.08Ca0.01Fe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4The microscopic appearance of ferromagnetism laminated film Interracial contact situation.With P-PMF1114-372 ferroelectricity analyser test b i0.91Ho0.08Ca0.01Fe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4 The ferroelectric properties of ferromagnetism laminated film.Test with Agilent E4980A precision LCR table Bi0.91Ho0.08Ca0.01Fe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4The dielectric properties of ferromagnetism laminated film.Survey with Agilent B2900 Examination Bi0.91Ho0.08Ca0.01Fe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4The leakage conductance current characteristics of ferromagnetism laminated film.Use SQUID MPMS-XL-7 test b i0.91Ho0.08Ca0.01Fe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4Ferromagnetic under ferromagnetism laminated film room temperature Performance.Obtaining following result: under 1kHz frequency, 60V electric field, its coercive field is (Ec=460～500kV/cm), residue Polarization intensity is (Pr=24～25 μ C/cm2)；Saturation magnetization is (Ms=71～72emu/cm3), remanent magnetization is (Mr=3～5emu/cm3)。
Embodiment 3
Step 1, is dissolved in zinc nitrate, nickel acetate and ferric nitrate in ethylene glycol monomethyl ether for 0.5:0.5:2 (y=0.5) in molar ratio, stirs After mixing 30min, add acetic anhydride, obtain the stable Zn that Fe ion concentration is 0.1mol/L0.5Ni0.5Fe2O4Precursor liquid, Wherein Zn0.5Ni0.5Fe2O4In precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 3:1；
Step 2, is 0.89:0.08:0.03:0.97:0.03 in molar ratio by bismuth nitrate, holmium nitrate, barium nitrate, ferric nitrate and manganese nitrate Being dissolved in solvent (AE=Ba, x=0.03, bismuth nitrate excess 5%), obtaining metal ion total concentration is the stable of 0.3mol/L Bi0.89Ho0.08Ba0.03Fe0.97Mn0.03O3Precursor solution；Wherein solvent be volume ratio be the mixed of 3:1 ethylene glycol monomethyl ether and acetic anhydride Close liquid；
Step 3, select FTO/glass substrate be substrate, the FTO/glass substrate of well cutting is sequentially placed into detergent, acetone, Ultrasonic waves for cleaning in ethanol, with a large amount of distilled water flushing substrates after each ultrasonic waves for cleaning 10min, finally dries up with nitrogen.Then FTO/glass substrate is put into baking oven be baked to be dried, take out and stand to room temperature.Again clean FTO/glass substrate is placed in purple Outer smooth radiation instrument irradiates 40min, makes substrate surface reach " atomic cleanliness degree ".Use spin-coating method again on FTO/glass substrate Spin coating Zn0.5Ni0.5Fe2O4Precursor solution, obtains Zn0.5Ni0.5Fe2O4Wet film, to Zn0.5Ni0.5Fe2O4Wet film spin coating, spin coating Rotating speed is 4000r/min, and spin coating time is 15s, after spin coating terminates, toasts 8min and obtain dry film at a temperature of 200 DEG C, then at 600 DEG C At a temperature of air is annealed layer by layer 20min, obtain crystalline state Zn0.5Ni0.5Fe2O4Thin film；
Step 4, treats crystalline state Zn0.5Ni0.5Fe2O4After film cooling, in crystalline state Zn0.5Ni0.5Fe2O4Step 3, weight is repeated on thin film Multiple 5 times, obtain Zn0.5Ni0.5Fe2O4Crystalline state film；
Step 5, by Zn0.5Ni0.5Fe2O4Crystalline state film is placed in ultraviolet radiation instrument irradiation 40min so that it is surface reaches atomic cleanliness Degree；Again at Zn0.5Ni0.5Fe2O4Spin coating Bi on crystalline state film0.89Ho0.08Ba0.03Fe0.97Mn0.03O3Precursor solution, obtains Bi0.89Ho0.08Ba0.03Fe0.97Mn0.03O3Wet film, to Bi0.89Ho0.08Ba0.03Fe0.97Mn0.03O3Wet film spin coating, spin coating rotating speed is 4000r/min, spin coating time is 15s, after spin coating terminates, toasts 8min and obtain dry film at 200 DEG C, then at 550 DEG C in air Anneal 10min layer by layer, obtains crystalline state Bi0.89Ho0.08Ba0.03Fe0.97Mn0.03O3Thin film；
Step 6, treats crystalline state Bi0.89Ho0.08Ba0.03Fe0.97Mn0.03O3After film cooling, in crystalline state Bi0.89Ho0.08Ba0.03Fe0.97Mn0.03O3Repeat step 5 on thin film, be repeated 12 times, i.e. obtain Bi0.89Ho0.08Ba0.03Fe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4Ferromagnetism laminated film.
Use XRD determining Bi0.89Ho0.08Ba0.03Fe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4The thing phase composition knot of ferromagnetism laminated film Structure.Bi is measured with FE-SEM0.89Ho0.08Ba0.03Fe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4The microscopic appearance of ferromagnetism laminated film Interracial contact situation.With P-PMF1114-372 ferroelectricity analyser test b i0.89Ho0.08Ba0.03Fe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4 The ferroelectric properties of ferromagnetism laminated film.Test with Agilent E4980A precision LCR table Bi0.89Ho0.08Ba0.03Fe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4The dielectric properties of ferromagnetism laminated film.Survey with Agilent B2900 Examination Bi0.89Ho0.08Ba0.03Fe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4The leakage conductance current characteristics of ferromagnetism laminated film.Use SQUID MPMS-XL-7 test b i0.89Ho0.08Ba0.03Fe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4Ferromagnetic under ferromagnetism laminated film room temperature Performance.Obtaining following result: under 1kHz frequency, 60V electric field, its coercive field is (Ec=550～570kV/cm), residue Polarization intensity is (Pr=43～45 μ C/cm2)；Saturation magnetization is (Ms=61～63emu/cm3), remanent magnetization is (Mr=4～7emu/cm3)。
Embodiment 4
Step 1, is dissolved in zinc nitrate, nickel acetate and ferric nitrate in ethylene glycol monomethyl ether for 0.6:0.4:2 (y=0.4) in molar ratio, stirs After mixing 30min, add acetic anhydride, obtain the stable Zn that Fe ion concentration is 0.11mol/L0.6Ni0.4Fe2O4Precursor liquid, Wherein Zn0.6Ni0.4Fe2O4In precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 3:1；
Step 2, is 0.9:0.08:0.02:0.97:0.03 in molar ratio by bismuth nitrate, holmium nitrate, plumbi nitras, ferric nitrate and manganese nitrate Being dissolved in solvent (AE=Pb, x=0.02, bismuth nitrate excess 5%), obtaining metal ion total concentration is the stable of 0.025mol/L Bi0.9Ho0.08Pb0.02Fe0.97Mn0.03O3Precursor solution；Wherein solvent be volume ratio be the mixed of 3:1 ethylene glycol monomethyl ether and acetic anhydride Close liquid；
Step 3, select FTO/glass substrate be substrate, the FTO/glass substrate of well cutting is sequentially placed into detergent, acetone, Ultrasonic waves for cleaning in ethanol, with a large amount of distilled water flushing substrates after each ultrasonic waves for cleaning 10min, finally dries up with nitrogen.Then FTO/glass substrate is put into baking oven be baked to be dried, take out and stand to room temperature.Again clean FTO/glass substrate is placed in purple Outer smooth radiation instrument irradiates 40min, makes substrate surface reach " atomic cleanliness degree ".Use spin-coating method again on FTO/glass substrate Spin coating Zn0.6Ni0.4Fe2O4Precursor solution, obtains Zn0.6Ni0.4Fe2O4Wet film, to Zn0.6Ni0.4Fe2O4Wet film spin coating, spin coating Rotating speed is 4000r/min, and spin coating time is 15s, after spin coating terminates, toasts 8min and obtain dry film at a temperature of 200 DEG C, then at 600 DEG C At a temperature of air is annealed layer by layer 20min, obtain crystalline state Zn0.6Ni0.4Fe2O4Thin film；
Step 4, treats crystalline state Zn0.6Ni0.4Fe2O4After film cooling, in crystalline state Zn0.6Ni0.4Fe2O4Step 3, weight is repeated on thin film Multiple 3 times, obtain Zn0.6Ni0.4Fe2O4Crystalline state film；
Step 5, by Zn0.6Ni0.4Fe2O4Crystalline state film is placed in ultraviolet radiation instrument irradiation 40min so that it is surface reaches atomic cleanliness Degree；Again at Zn0.6Ni0.4Fe2O4Spin coating Bi on crystalline state film0.9Ho0.08Pb0.02Fe0.97Mn0.03O3Precursor solution, obtains Bi0.9Ho0.08Pb0.02Fe0.97Mn0.03O3Wet film, to Bi0.9Ho0.08Pb0.02Fe0.97Mn0.03O3Wet film spin coating, spin coating rotating speed is 4000r/min, spin coating time is 15s, after spin coating spin coating terminates, toasts 8min and obtain dry film at 200 DEG C, more empty at 550 DEG C Anneal in gas 10min layer by layer, obtains crystalline state Bi0.9Ho0.08Pb0.02Fe0.97Mn0.03O3Thin film；
Step 6, treats crystalline state Bi0.9Ho0.08Pb0.02Fe0.97Mn0.03O3After film cooling, in crystalline state Bi0.9Ho0.08Pb0.02Fe0.97Mn0.03O3Repeat step 5 on thin film, be repeated 4 times, obtain ferromagnetic property Bi0.9Ho0.08Pb0.02Fe0.97Mn0.03O3-Zn0.6Ni0.4Fe2O4Composite membrane.
Embodiment 5
Step 1, is dissolved in zinc nitrate, nickel acetate and ferric nitrate in ethylene glycol monomethyl ether for 0.9:0.1:2 (y=0.1) in molar ratio, stirs After mixing 30min, add acetic anhydride, obtain the stable Zn that Fe ion concentration is 0.15mol/L0.9Ni0.1Fe2O4Precursor liquid, Wherein Zn0.9Ni0.1Fe2O4In precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 2.5:1；
Step 2, is 0.91:0.08:0.01:0.97:0.03 in molar ratio by bismuth nitrate, holmium nitrate, strontium nitrate, ferric nitrate and manganese nitrate Being dissolved in solvent (AE=Sr, x=0.01, bismuth nitrate excess 5%), obtaining metal ion total concentration is the stable of 0.03mol/L Bi0.91Ho0.08Sr0.01Fe0.97Mn0.03O3Precursor solution；Wherein solvent be volume ratio be the mixed of 2.5:1 ethylene glycol monomethyl ether and acetic anhydride Close liquid；
Step 3, select FTO/glass substrate be substrate, the FTO/glass substrate of well cutting is sequentially placed into detergent, acetone, Ultrasonic waves for cleaning in ethanol, with a large amount of distilled water flushing substrates after each ultrasonic waves for cleaning 10min, finally dries up with nitrogen.Then FTO/glass substrate is put into baking oven be baked to be dried, take out and stand to room temperature.Again clean FTO/glass substrate is placed in purple Outer smooth radiation instrument irradiates 40min, makes substrate surface reach " atomic cleanliness degree ".Use spin-coating method again on FTO/glass substrate Spin coating Zn0.9Ni0.1Fe2O4Precursor solution, obtains Zn0.9Ni0.1Fe2O4Wet film, to Zn0.9Ni0.1Fe2O4Wet film spin coating, spin coating Rotating speed is 3800r/min, and spin coating time is 20s, after spin coating terminates, toasts 10min and obtain dry film at a temperature of 190 DEG C, then Anneal in air at a temperature of 590 DEG C 22min layer by layer, obtains crystalline state Zn0.9Ni0.1Fe2O4Thin film；
Step 4, treats crystalline state Zn0.9Ni0.1Fe2O4After film cooling, in crystalline state Zn0.9Ni0.1Fe2O4Step 3, weight is repeated on thin film Multiple 2 times, obtain Zn0.9Ni0.1Fe2O4Crystalline state film；
Step 5, by Zn0.9Ni0.1Fe2O4Crystalline state film is placed in ultraviolet radiation instrument irradiation 40min so that it is surface reaches atomic cleanliness Degree；Again at Zn0.9Ni0.1Fe2O4Spin coating Bi on crystalline state film0.91Ho0.08Sr0.01Fe0.97Mn0.03O3Precursor solution, obtains Bi0.91Ho0.08Sr0.01Fe0.97Mn0.03O3Wet film, to Bi0.91Ho0.08Sr0.01Fe0.97Mn0.03O3Wet film spin coating, spin coating rotating speed is 3800r/min, spin coating time is 20s, after spin coating spin coating terminates, toasts 10min and obtain dry film at 190 DEG C, then at 540 DEG C Anneal in air 12min layer by layer, obtains crystalline state Bi0.91Ho0.08Sr0.01Fe0.97Mn0.03O3Thin film；
Step 6, treats crystalline state Bi0.91Ho0.08Sr0.01Fe0.97Mn0.03O3After film cooling, in crystalline state Bi0.91Ho0.08Sr0.01Fe0.97Mn0.03O3Repeat step 5 on thin film, be repeated 14 times, obtain ferromagnetic property Bi0.91Ho0.08Sr0.01Fe0.97Mn0.03O3-Zn0.9Ni0.1Fe2O4Composite membrane.
Embodiment 6
Step 1, is dissolved in zinc nitrate, nickel acetate and ferric nitrate in ethylene glycol monomethyl ether for 0.1:0.9:2 (y=0.9) in molar ratio, stirs After mixing 30min, add acetic anhydride, obtain the stable Zn that Fe ion concentration is 0.18mol/L0.1Ni0.9Fe2O4Precursor liquid, Wherein Zn0.1Ni0.9Fe2O4In precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 3.5:1；
Step 2, is 0.9:0.08:0.02:0.97:0.03 in molar ratio by bismuth nitrate, holmium nitrate, strontium nitrate, ferric nitrate and manganese nitrate Being dissolved in solvent (AE=Sr, x=0.02, bismuth nitrate excess 5%), obtaining metal ion total concentration is the stable of 0.003mol/L Bi0.9Ho0.08Sr0.02Fe0.97Mn0.03O3Precursor solution；Wherein solvent be volume ratio be the mixed of 3.5:1 ethylene glycol monomethyl ether and acetic anhydride Close liquid；
Step 3, select FTO/glass substrate be substrate, the FTO/glass substrate of well cutting is sequentially placed into detergent, acetone, Ultrasonic waves for cleaning in ethanol, with a large amount of distilled water flushing substrates after each ultrasonic waves for cleaning 10min, finally dries up with nitrogen.Then FTO/glass substrate is put into baking oven be baked to be dried, take out and stand to room temperature.Again clean FTO/glass substrate is placed in purple Outer smooth radiation instrument irradiates 40min, makes substrate surface reach " atomic cleanliness degree ".Use spin-coating method again on FTO/glass substrate Spin coating Zn0.1Ni0.9Fe2O4Precursor solution, obtains Zn0.1Ni0.9Fe2O4Wet film, to Zn0.1Ni0.9Fe2O4Wet film spin coating, spin coating Rotating speed is 3900r/min, and spin coating time is 18s, after spin coating terminates, toasts 9min and obtain dry film at a temperature of 195 DEG C, then at 595 DEG C At a temperature of air is annealed layer by layer 21min, obtain crystalline state Zn0.1Ni0.9Fe2O4Thin film；
Step 4, treats crystalline state Zn0.9Ni0.1Fe2O4After film cooling, in crystalline state Zn0.1Ni0.9Fe2O4Step 3, weight is repeated on thin film Multiple 4 times, obtain Zn0.1Ni0.9Fe2O4Crystalline state film；
Step 5, by Zn0.1Ni0.9Fe2O4Crystalline state film is placed in ultraviolet radiation instrument irradiation 40min so that it is surface reaches atomic cleanliness Degree；Again at Zn0.1Ni0.9Fe2O4Spin coating Bi on crystalline state film0.9Ho0.08Sr0.02Fe0.97Mn0.03O3Precursor solution, obtains Bi0.9Ho0.08Sr0.02Fe0.97Mn0.03O3Wet film, to Bi0.9Ho0.08Sr0.02Fe0.97Mn0.03O3Wet film spin coating, spin coating rotating speed is 3900r/min, spin coating time is 18s, after spin coating spin coating terminates, toasts 9min and obtain dry film at 195 DEG C, more empty at 545 DEG C Anneal in gas 11min layer by layer, obtains crystalline state Bi0.9Ho0.08Sr0.02Fe0.97Mn0.03O3Thin film；
Step 6, treats crystalline state Bi0.9Ho0.08Sr0.02Fe0.97Mn0.03O3After film cooling, in crystalline state Bi0.9Ho0.08Sr0.02Fe0.97Mn0.03O3Repeat step 5 on thin film, be repeated 10 times, obtain ferromagnetic property Bi0.9Ho0.08Sr0.02Fe0.97Mn0.03O3-Zn0.1Ni0.9Fe2O4Composite membrane.
Embodiment 7
Step 1, is dissolved in zinc nitrate, nickel acetate and ferric nitrate in ethylene glycol monomethyl ether for 0.3:0.7:2 (y=0.7) in molar ratio, stirs After mixing 30min, add acetic anhydride, obtain the stable Zn that Fe ion concentration is 0.2mol/L0.3Ni0.7Fe2O4Precursor liquid, Wherein Zn0.3Ni0.7Fe2O4In precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 3.2:1；
Step 2, is 0.88:0.08:0.04:0.97:0.03 in molar ratio by bismuth nitrate, holmium nitrate, strontium nitrate, ferric nitrate and manganese nitrate Being dissolved in solvent (AE=Sr, x=0.04, bismuth nitrate excess 5%), obtaining metal ion total concentration is the stable of 0.01mol/L Bi0.88Ho0.08Sr0.04Fe0.97Mn0.03O3Precursor solution；Wherein solvent be volume ratio be the mixed of 3.2:1 ethylene glycol monomethyl ether and acetic anhydride Close liquid；
Step 3, select FTO/glass substrate be substrate, the FTO/glass substrate of well cutting is sequentially placed into detergent, acetone, Ultrasonic waves for cleaning in ethanol, with a large amount of distilled water flushing substrates after each ultrasonic waves for cleaning 10min, finally dries up with nitrogen.Then FTO/glass substrate is put into baking oven be baked to be dried, take out and stand to room temperature.Again clean FTO/glass substrate is placed in purple Outer smooth radiation instrument irradiates 40min, makes substrate surface reach " atomic cleanliness degree ".Use spin-coating method again on FTO/glass substrate Spin coating Zn0.3Ni0.7Fe2O4Precursor solution, obtains Zn0.3Ni0.7Fe2O4Wet film, to Zn0.3Ni0.7Fe2O4Wet film spin coating, spin coating Rotating speed is 4100r/min, and spin coating time is 10s, after spin coating terminates, toasts 8.5min and obtain dry film at a temperature of 205 DEG C, then Anneal in air at a temperature of 605 DEG C 19min layer by layer, obtains crystalline state Zn0.3Ni0.7Fe2O4Thin film；
Step 4, treats crystalline state Zn0.3Ni0.7Fe2O4After film cooling, in crystalline state Zn0.3Ni0.7Fe2O4Step 3, weight is repeated on thin film Multiple 1 time, obtain Zn0.3Ni0.7Fe2O4Crystalline state film；
Step 5, by Zn0.3Ni0.7Fe2O4Crystalline state film is placed in ultraviolet radiation instrument irradiation 40min so that it is surface reaches atomic cleanliness Degree；Again at Zn0.3Ni0.7Fe2O4Spin coating Bi on crystalline state film0.88Ho0.08Sr0.04Fe0.97Mn0.03O3Precursor solution, obtains Bi0.88Ho0.08Sr0.04Fe0.97Mn0.03O3Wet film, to Bi0.88Ho0.08Sr0.04Fe0.97Mn0.03O3Wet film spin coating, spin coating rotating speed is 4100r/min, spin coating time is 10s, after spin coating spin coating terminates, toasts 8.5min and obtain dry film at 205 DEG C, then at 555 DEG C Anneal in air 9min layer by layer, obtains crystalline state Bi0.88Ho0.08Sr0.04Fe0.97Mn0.03O3Thin film；
Step 6, treats crystalline state Bi0.88Ho0.08Sr0.04Fe0.97Mn0.03O3After film cooling, in crystalline state Bi0.88Ho0.08Sr0.04Fe0.97Mn0.03O3Repeat step 5 on thin film, be repeated 8 times, obtain ferromagnetic property Bi0.88Ho0.08Sr0.04Fe0.97Mn0.03O3-Zn0.3Ni0.7Fe2O4Composite membrane.
Embodiment 8
Step 1, is dissolved in zinc nitrate, nickel acetate and ferric nitrate in ethylene glycol monomethyl ether for 0.7:0.3:2 (y=0.3) in molar ratio, stirs After mixing 30min, add acetic anhydride, obtain the stable Zn that Fe ion concentration is 0.16mol/L0.7Ni0.3Fe2O4Precursor liquid, Wherein Zn0.7Ni0.3Fe2O4In precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 2.8:1；
Step 2, is 0.895:0.08:0.025:0.97:0.03 in molar ratio by bismuth nitrate, holmium nitrate, calcium nitrate, ferric nitrate and manganese nitrate Being dissolved in solvent (AE=Ca, x=0.025, bismuth nitrate excess 5%), obtaining metal ion total concentration is the stable of 0.05mol/L Bi0.895Ho0.08Ca0.025Fe0.97Mn0.03O3Precursor solution；Wherein solvent be volume ratio be 2.8:1 ethylene glycol monomethyl ether and acetic anhydride Mixed liquor；
Step 3, select FTO/glass substrate be substrate, the FTO/glass substrate of well cutting is sequentially placed into detergent, acetone, Ultrasonic waves for cleaning in ethanol, with a large amount of distilled water flushing substrates after each ultrasonic waves for cleaning 10min, finally dries up with nitrogen.Then FTO/glass substrate is put into baking oven be baked to be dried, take out and stand to room temperature.Again clean FTO/glass substrate is placed in purple Outer smooth radiation instrument irradiates 40min, makes substrate surface reach " atomic cleanliness degree ".Use spin-coating method again on FTO/glass substrate Spin coating Zn0.7Ni0.3Fe2O4Precursor solution, obtains Zn0.7Ni0.3Fe2O4Wet film, to Zn0.7Ni0.3Fe2O4Wet film spin coating, spin coating Rotating speed is 3850r/min, and spin coating time is 16s, after spin coating terminates, toasts 8.2min and obtain dry film at a temperature of 210 DEG C, then Anneal in air at a temperature of 610 DEG C 18min layer by layer, obtains crystalline state Zn0.7Ni0.3Fe2O4Thin film；
Step 4, treats crystalline state Zn0.7Ni0.3Fe2O4After film cooling, in crystalline state Zn0.7Ni0.3Fe2O4Step 3, weight is repeated on thin film Multiple 5 times, obtain Zn0.7Ni0.3Fe2O4Crystalline state film；
Step 5, by Zn0.7Ni0.3Fe2O4Crystalline state film is placed in ultraviolet radiation instrument irradiation 40min so that it is surface reaches atomic cleanliness Degree；Again at Zn0.7Ni0.3Fe2O4Spin coating Bi on crystalline state film0.895Ho0.08Ca0.025Fe0.97Mn0.03O3Precursor solution, obtains Bi0.895Ho0.08Ca0.025Fe0.97Mn0.03O3Wet film, to Bi0.895Ho0.08Ca0.025Fe0.97Mn0.03O3Wet film spin coating, spin coating rotating speed is 3850r/min, spin coating time is 16s, after spin coating spin coating terminates, toasts 8.2min and obtain dry film at 210 DEG C, then at 560 DEG C Anneal in air 8min layer by layer, obtains crystalline state Bi0.895Ho0.08Ca0.025Fe0.97Mn0.03O3Thin film；
Step 6, treats crystalline state Bi0.895Ho0.08Ca0.025Fe0.97Mn0.03O3After film cooling, in crystalline state Bi0.895Ho0.08Ca0.025Fe0.97Mn0.03O3Repeat step 5 on thin film, be repeated 5 times, obtain ferromagnetic property Bi0.895Ho0.08Ca0.025Fe0.97Mn0.03O3-Zn0.7Ni0.3Fe2O4Composite membrane.
Embodiment 9
Step 1, is dissolved in zinc nitrate, nickel acetate and ferric nitrate in ethylene glycol monomethyl ether for 0.8:0.2:2 (y=0.2) in molar ratio, stirs After mixing 30min, add acetic anhydride, obtain the stable Zn that Fe ion concentration is 0.14mol/L0.8Ni0.2Fe2O4Precursor liquid, Wherein Zn0.8Ni0.2Fe2O4In precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 2.9:1；
Step 2, is 0.905:0.08:0.015:0.97:0.03 in molar ratio by bismuth nitrate, holmium nitrate, barium nitrate, ferric nitrate and manganese nitrate Being dissolved in solvent (AE=Ba, x=0.015, bismuth nitrate excess 5%), obtaining metal ion total concentration is the stable of 0.1mol/L Bi0.905Ho0.08Ba0.015Fe0.97Mn0.03O3Precursor solution；Wherein solvent be volume ratio be 2.9:1 ethylene glycol monomethyl ether and acetic anhydride Mixed liquor；
Step 3, select FTO/glass substrate be substrate, the FTO/glass substrate of well cutting is sequentially placed into detergent, acetone, Ultrasonic waves for cleaning in ethanol, with a large amount of distilled water flushing substrates after each ultrasonic waves for cleaning 10min, finally dries up with nitrogen.Then FTO/glass substrate is put into baking oven be baked to be dried, take out and stand to room temperature.Again clean FTO/glass substrate is placed in purple Outer smooth radiation instrument irradiates 40min, makes substrate surface reach " atomic cleanliness degree ".Use spin-coating method again on FTO/glass substrate Spin coating Zn0.8Ni0.2Fe2O4Precursor solution, obtains Zn0.8Ni0.2Fe2O4Wet film, to Zn0.8Ni0.2Fe2O4Wet film spin coating, spin coating Rotating speed is 3950r/min, and spin coating time is 14s, after spin coating terminates, toasts 9.5min and obtain dry film at a temperature of 198 DEG C, then Anneal in air at a temperature of 598 DEG C 20.5min layer by layer, obtains crystalline state Zn0.8Ni0.2Fe2O4Thin film；
Step 4, treats crystalline state Zn0.8Ni0.2Fe2O4After film cooling, in crystalline state Zn0.8Ni0.2Fe2O4Step 3, weight is repeated on thin film Multiple 2 times, obtain Zn0.8Ni0.2Fe2O4Crystalline state film；
Step 5, by Zn0.8Ni0.2Fe2O4Crystalline state film is placed in ultraviolet radiation instrument irradiation 40min so that it is surface reaches atomic cleanliness Degree；Again at Zn0.8Ni0.2Fe2O4Spin coating Bi on crystalline state film0.905Ho0.08Ba0.015Fe0.97Mn0.03O3Precursor solution, obtains Bi0.905Ho0.08Ba0.015Fe0.97Mn0.03O3Wet film, to Bi0.905Ho0.08Ba0.015Fe0.97Mn0.03O3Wet film spin coating, spin coating rotating speed is 3950r/min, spin coating time is 14s, after spin coating spin coating terminates, toasts 9.5min and obtain dry film at 198 DEG C, then at 548 DEG C Anneal in air 10.5min layer by layer, obtains crystalline state Bi0.905Ho0.08Ba0.015Fe0.97Mn0.03O3Thin film；
Step 6, treats crystalline state Bi0.905Ho0.08Ba0.015Fe0.97Mn0.03O3After film cooling, in crystalline state Bi0.905Ho0.08Ba0.015Fe0.97Mn0.03O3Repeat step 5 on thin film, be repeated 2 times, obtain ferromagnetic property Bi0.905Ho0.08Ba0.015Fe0.97Mn0.03O3-Zn0.8Ni0.2Fe2O4Composite membrane.
Embodiment 10
Step 1, is dissolved in zinc nitrate, nickel acetate and ferric nitrate in ethylene glycol monomethyl ether for 0.4:0.6:2 (y=0.6) in molar ratio, stirs After mixing 30min, add acetic anhydride, obtain the stable Zn that Fe ion concentration is 0.12mol/L0.4Ni0.6Fe2O4Precursor liquid, Wherein Zn0.4Ni0.6Fe2O4In precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 3.1:1；
Step 2, is 0.885:0.08:0.035:0.97:0.03 in molar ratio by bismuth nitrate, holmium nitrate, plumbi nitras, ferric nitrate and manganese nitrate Being dissolved in solvent (AE=Pb, x=0.035, bismuth nitrate excess 5%), obtaining metal ion total concentration is the stable of 0.2mol/L Bi0.885Ho0.08Pb0.035Fe0.97Mn0.03O3Precursor solution；Wherein solvent be volume ratio be 3.1:1 ethylene glycol monomethyl ether and acetic anhydride Mixed liquor；
Step 3, select FTO/glass substrate be substrate, the FTO/glass substrate of well cutting is sequentially placed into detergent, acetone, Ultrasonic waves for cleaning in ethanol, with a large amount of distilled water flushing substrates after each ultrasonic waves for cleaning 10min, finally dries up with nitrogen.Then FTO/glass substrate is put into baking oven be baked to be dried, take out and stand to room temperature.Again clean FTO/glass substrate is placed in purple Outer smooth radiation instrument irradiates 40min, makes substrate surface reach " atomic cleanliness degree ".Use spin-coating method again on FTO/glass substrate Spin coating Zn0.4Ni0.6Fe2O4Precursor solution, obtains Zn0.4Ni0.6Fe2O4Wet film, to Zn0.4Ni0.6Fe2O4Wet film spin coating, spin coating Rotating speed is 4050r/min, and spin coating time is 12s, after spin coating terminates, toasts 8.8min and obtain dry film at a temperature of 202 DEG C, then Anneal in air at a temperature of 602 DEG C 19.5min layer by layer, obtains Zn0.4Ni0.6Fe2O4Crystalline state film；
Step 4, by Zn0.4Ni0.6Fe2O4Crystalline state film is placed in ultraviolet radiation instrument irradiation 40min so that it is surface reaches atomic cleanliness Degree；Again at Zn0.4Ni0.6Fe2O4Spin coating Bi on crystalline state film0.885Ho0.08Pb0.035Fe0.97Mn0.03O3Precursor solution, obtains Bi0.885Ho0.08Pb0.035Fe0.97Mn0.03O3Wet film, to Bi0.885Ho0.08Pb0.035Fe0.97Mn0.03O3Wet film spin coating, spin coating rotating speed is 4050r/min, spin coating time is 12s, after spin coating spin coating terminates, toasts 8.8min and obtain dry film at 202 DEG C, then at 552 DEG C Anneal in air 9.5min layer by layer, obtains crystalline state Bi0.885Ho0.08Pb0.035Fe0.97Mn0.03O3Thin film；
Step 5, treats crystalline state Bi0.885Ho0.08Pb0.035Fe0.97Mn0.03O3After film cooling, in crystalline state Bi0.885Ho0.08Pb0.035Fe0.97Mn0.03O3Repeat step 5 on thin film, be repeated 6 times, obtain ferromagnetic property Bi0.885Ho0.08Pb0.035Fe0.97Mn0.03O3-Zn0.4Ni0.6Fe2O4Composite membrane.
The Bi below present invention prepared0.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4The performance of ferromagnetism laminated film Test and analyze.
Use XRD determining Bi0.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4The thing phase composition knot of ferromagnetism laminated film Structure；Bi is measured with FE-SEM0.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4Microscopic appearance circle of ferromagnetism laminated film Face contact situation；With P-PMF1114-372 ferroelectricity analyser test b i0.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4 The ferroelectric properties of ferromagnetism laminated film.Test with Agilent E4980A precision LCR table Bi0.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4The dielectric properties of ferromagnetism laminated film.Survey with Agilent B2900 Examination Bi0.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4The leakage conductance current characteristics of ferromagnetism laminated film；Use SQUID MPMS-XL-7 test b i0.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4Ferromagnetism under ferromagnetism laminated film room temperature Energy.Carrying out above test by the laminated film preparing embodiment 1～3, result is as shown in Fig. 1～5.
As can be known from Fig. 1, the Bi that prepared by the present invention0.92-xHo0.08AExFe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4Ferromagnetism THIN COMPOSITE Film, wherein Bi0.92-xHo0.08AExFe0.97Mn0.03O3Having the perovskite structure of distortion, rhombohedral system mutually, space group is R3m (160), does not has impurity to occur.Also observe that more weak ZnFe simultaneously2O4Characteristic peak, this outer film does not has other miscellaneous The appearance of matter.
The Bi that as can be seen from Figure 2 prepared by the present invention0.92-xHo0.08AExFe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4Ferromagnetism THIN COMPOSITE Film surfacing, crystallite dimension is 50～100nm, in conjunction with Bi in Fig. 2 (d)0.89Ho0.08Sr0.03Fe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4 The section SEM figure of ferromagnetism laminated film, it can be seen that Bi0.89Ho0.08Sr0.03Fe0.97Mn0.03O3And Zn0.5Ni0.5Fe2O4Thin film connects Touching good, interface is clear, diffusing phenomenon does not occur.
Fig. 3 is Bi0.92-xHo0.08AExFe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4The dielectric properties figure of multiferroic laminated film, from figure In can be seen that Bi0.89Ho0.08Sr0.03Fe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4Multiferroic laminated film shows obvious dielectric dispersion Phenomenon, there is dielectric loss peak when frequency is 10kHz in dielectric loss, and this is due to Bi0.89Ho0.08Sr0.03Fe0.97Mn0.03O3 And Zn0.5Ni0.5Fe2O4The directric relaxation phenomenon that the electric capacity difference of thin film causes, this meets Maxwell Wagner directric relaxation.
As shown in Figure 4, Bi0.92-xHo0.08AExFe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4Ferromagnetism laminated film has relatively low leakage Electrical conduction current density, and Bi0.89Ho0.08Sr0.03Fe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4The leakage current of ferromagnetism laminated film is minimum.
Fig. 5 is Bi0.92-xHo0.08AExFe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4Ferromagnetism laminated film at room temperature, frequency 1kHz, The ferroelectric hysteresis loop recorded during electric field 60V, it can be seen that Bi0.89Ho0.08Sr0.03Fe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4Ferromagnetism is multiple The coercive field closing thin film is Ec=500～510kV/cm, and remanent polarization is Pr=115～116 μ C/cm2, Bi0.91Ho0.08Ca0.01Fe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4The coercive field of ferromagnetism laminated film is Ec=460～500kV/cm, Remanent polarization is Pr=24～25 μ C/cm2, Bi0.89Ho0.08Ba0.03Fe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4Ferromagnetism THIN COMPOSITE The coercive field of film is Ec=550～570kV/cm, and remanent polarization is Pr=43～45 μ C/cm2。
Fig. 6 is Bi0.92-xHo0.08AExFe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4The hysteresis curve of ferromagnetism laminated film, can see Go out Bi0.92-xHo0.08AExFe0.97Mn0.03O3With ferromagnetism spinel-type Zn0.5Ni0.5Fe2O4After crystalline film is compound, saturated magnetization Intensity is significantly improved, wherein Bi0.89Ho0.08Sr0.03Fe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4Ferromagnetism laminated film saturated Magnetization M s is 57～58emu/cm3, Bi0.89Ho0.08Ba0.03Fe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4Ferromagnetism laminated film Saturation magnetization Ms be 61～63emu/cm3, Bi0.91Ho0.08Ca0.01Fe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4Ferromagnetism is multiple The saturation magnetization closing thin film is the highest, Ms=71～72emu/cm3。
Present device requires simple, and experiment condition easily reaches, and the uniformity of film of preparation is preferable, and doping is easily controlled, logical The suitable selection of overdoping amount, and Zn1-yNiyFe2O4The interpolation of laminated magnetic film, it is possible to increase substantially BiFeO3Thin film Ferroelectric properties, reduces the leakage current density of thin film, the most significantly improves the ferromagnetism of thin film.
Above said content is to combine concrete preferred implementation further description made for the present invention, is not all of or only The embodiment of one, it is any etc. that technical solution of the present invention is taked by those of ordinary skill in the art by reading description of the invention The conversion of effect, the claim being the present invention is contained.

Claims (10)

1. a Bi0.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4Ferromagnetism laminated film, it is characterised in that: include The upper layer film being combined with each other and lower membrane, wherein upper layer film is Bi0.92-xHo0.08AExFe0.97Mn0.03O3Crystalline state film, AE=Sr, Ca, Ba or Pb, x=0.01～0.04；Lower membrane is Zn1-yNiyFe2O4Crystalline state film, y=0.1～0.9.
Bi the most according to claim 10.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4Ferromagnetism laminated film, It is characterized in that: described Bi0.92-xHo0.08AExFe0.97Mn0.03O3Crystalline state film is the perovskite structure of distortion, and rhombohedral system is empty Between point group be R3m (160)；Zn1-yNiyFe2O4Crystalline state film is Emission in Cubic, spinel structure, and space group is Fd-3m (227).
Bi the most according to claim 10.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4Ferromagnetism laminated film, It is characterized in that: described Bi0.89Ho0.08Sr0.03Fe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4The saturated magnetization of ferromagnetism laminated film Intensity is Ms=57～59emu/cm3, remanent magnetization is Mr=4～6emu/cm3, leakage current under 300kV/cm electric field Density is 3.3 × 10-4A/cm2；Remanent polarization under 1kHz frequency, 60V electric field is Pr=115～116 μ C/cm2, rectify Stupid field is Ec=500～510kV/cm；
Described Bi0.91Ho0.08Ca0.01Fe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4The saturation magnetization of ferromagnetism laminated film is Ms=71～72emu/cm3, remanent magnetization is Mr=3～5emu/cm3, residual polarization under 1kHz frequency, 60V electric field Intensity is Pr=24～25 μ C/cm2, coercive field is Ec=460～500kV/cm；
Described Bi0.89Ho0.08Ba0.03Fe0.97Mn0.03O3-Zn0.5Ni0.5Fe2O4The saturation magnetization of ferromagnetism laminated film is Ms=61～63emu/cm3, remanent magnetization is Mr=4～7emu/cm3, residual polarization under 1kHz frequency, 60V electric field Intensity is Pr=43～45 μ C/cm2, coercive field is Ec=550～570kV/cm.
4. a Bi0.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4The preparation method of ferromagnetism laminated film, its feature It is, comprises the following steps:
Step 1, is dissolved in ethylene glycol monomethyl ether for 1-y:y:2 in molar ratio by zinc nitrate, nickel acetate and ferric nitrate, after stirring Add acetic anhydride, obtain Zn1-yNiyFe2O4Precursor liquid；Wherein y=0.1～0.9, Zn1-yNiyFe2O4Fe ion in precursor liquid Concentration is 0.1～0.2mol/L；
Step 2, is 0.97-x:0.08:x:0.97:0.03 by bismuth nitrate, holmium nitrate, nitric acid AE, ferric nitrate and manganese nitrate in molar ratio It is dissolved in solvent, obtains Bi0.92-xHo0.08AExFe0.97Mn0.03O3Precursor solution；Wherein AE is Sr, Ca, Ba or Pb, X=0.01～0.04, Bi0.92-xHo0.08AExFe0.97Mn0.03O3In precursor solution, the total concentration of metal ion is 0.003～0.3mol/L, Solvent is the mixed liquor of ethylene glycol monomethyl ether and acetic anhydride；
Step 3, uses spin-coating method spin coating Zn on substrate1-yNiyFe2O4Precursor liquid, obtains Zn1-yNiyFe2O4Wet film, Zn1-yNiyFe2O4Wet film toasts to obtain dry film after spin coating at 190～210 DEG C, anneals in atmosphere at 590～610 DEG C, To crystalline state Zn1-yNiyFe2O4Thin film；
Step 4, treats crystalline state Zn1-yNiyFe2O4After film cooling, in crystalline state Zn1-yNiyFe2O4Step 3 is repeated on thin film, until Reach desired thickness, obtain Zn1-yNiyFe2O4Crystalline state film；
Step 5, at Zn1-yNiyFe2O4Spin coating Bi on crystalline state film0.92-xHo0.08AExFe0.97Mn0.03O3Precursor solution, obtains Bi0.92-xHo0.08AExFe0.97Mn0.03O3Wet film, Bi0.92-xHo0.08AExFe0.97Mn0.03O3Wet film after spin coating at 190～210 DEG C Under toast to obtain dry film, anneal in atmosphere at 540～560 DEG C, obtain crystalline state Bi0.92-xHo0.08AExFe0.97Mn0.03O3Thin film；
Step 6, treats crystalline state Bi0.92-xHo0.08AExFe0.97Mn0.03O3After film cooling, repeat step 5 thereon, until it reaches Desired thickness, i.e. obtains Bi0.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4Ferromagnetism laminated film.
Bi the most according to claim 40.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4Ferromagnetism laminated film Preparation method, it is characterised in that: described Zn1-yNiyFe2O4In precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is (2.5～3.5): 1；In the solvent of described step 2, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is (2.5～3.5): 1.
Bi the most according to claim 40.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4Ferromagnetism laminated film Preparation method, it is characterised in that: substrate, before carrying out, is first carried out by described step 3, the most under ultraviolet light treatment with irradiation, Substrate surface is made to reach atomic cleanliness degree, then spin coating Zn1-yNiyFe2O4Precursor liquid；
Described step 5 is before carrying out, first to Zn1-yNiyFe2O4Crystalline state film carries out ultraviolet light treatment with irradiation, makes Zn1-yNiyFe2O4 Crystalline state film surface reaches atomic cleanliness degree, then spin coating Bi0.92-xHo0.08AExFe0.97Mn0.03O3Precursor solution.
Bi the most according to claim 40.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4Ferromagnetism laminated film Preparation method, it is characterised in that: in described step 3 and step 5, spin coating rotating speed during spin coating is 3800～4100r/min, during spin coating Between be 10～20s.
Bi the most according to claim 40.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4Ferromagnetism laminated film Preparation method, it is characterised in that: in described step 3 and step 5, the baking time after spin coating is 8～10min.
Bi the most according to claim 40.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4Ferromagnetism laminated film Preparation method, it is characterised in that: the annealing time in described step 3 is 18～annealing time in 22min, step 5 is 8～12min.
Bi the most according to claim 40.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4Ferromagnetism laminated film Preparation method, it is characterised in that: described Bi0.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4Ferromagnetism laminated film by 1～6 layer crystal states Zn1-yNiyFe2O4Thin film and 3～15 layer crystal states Bi0.92-xHo0.08AExFe0.97Mn0.03O3Thin film is constituted.
CN201610188153.2A 2016-03-29 2016-03-29 Bi0.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4 ferromagnetic composite film and preparation method thereof Pending CN105837196A (en)

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CN107082577A (en) * 2017-04-18 2017-08-22 陕西科技大学 A kind of HoSrMnZn is co-doped with bismuth ferrite/Mn and mixes zinc ferrite laminated film and preparation method thereof
CN107082578A (en) * 2017-04-18 2017-08-22 陕西科技大学 A kind of HoSrMnNi is co-doped with tripartite's bismuth ferrite superlattice film and preparation method thereof
CN107082576A (en) * 2017-04-18 2017-08-22 陕西科技大学 A kind of HoSrMnNi is co-doped with many iron thin films of bismuth ferrite and preparation method thereof
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CN107162437A (en) * 2017-04-18 2017-09-15 陕西科技大学 A kind of HoSrMnZn is co-doped with bismuth ferrite superlattice film and preparation method thereof
CN107245704A (en) * 2017-04-18 2017-10-13 陕西科技大学 A kind of HoSrMnNi/HoSrMnZn is co-doped with bismuth ferrite superlattice film and preparation method thereof
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CN107082578A (en) * 2017-04-18 2017-08-22 陕西科技大学 A kind of HoSrMnNi is co-doped with tripartite's bismuth ferrite superlattice film and preparation method thereof
CN107082579B (en) * 2017-04-18 2020-05-05 陕西科技大学 HoSrMnZn co-doped bismuth ferrite multiferroic film and preparation method thereof
CN107032632B (en) * 2017-04-18 2019-05-17 陕西科技大学 A kind of HoSrMnNi is co-doped with bismuth ferrite superlattice film and preparation method thereof
CN107082579A (en) * 2017-04-18 2017-08-22 陕西科技大学 A kind of HoSrMnZn is co-doped with many iron thin films of bismuth ferrite and preparation method thereof
CN107140848A (en) * 2017-04-18 2017-09-08 陕西科技大学 A kind of GdSrMnCo is co-doped with bismuth ferrite superlattice film and preparation method thereof
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CN107245704A (en) * 2017-04-18 2017-10-13 陕西科技大学 A kind of HoSrMnNi/HoSrMnZn is co-doped with bismuth ferrite superlattice film and preparation method thereof
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Application publication date: 20160810