CN105906221A - Multiferroic Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4 composite film and preparation method thereof - Google Patents

Multiferroic Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4 composite film and preparation method thereof Download PDF

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CN105906221A
CN105906221A CN201610188155.1A CN201610188155A CN105906221A CN 105906221 A CN105906221 A CN 105906221A CN 201610188155 A CN201610188155 A CN 201610188155A CN 105906221 A CN105906221 A CN 105906221A
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film
composite membrane
crystalline state
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CN105906221B (en
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谈国强
乐忠威
晏霞
任慧君
夏傲
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Shaanxi University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/90—Other aspects of coatings
    • C03C2217/94—Transparent conductive oxide layers [TCO] being part of a multilayer coating
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/116—Deposition methods from solutions or suspensions by spin-coating, centrifugation

Abstract

The invention discloses a multiferroic Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4 composite film and a preparation method thereof. The composite film comprises a Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3 (x=0.01-0.05) crystalline film in the upper layer and a CuFe2O4 crystalline film in the lower layer. The preparation method comprises respectively preparing a Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3 precursor solution and a CuFe2O4 precursor solution, carrying out spin-coating on a substrate with multiple CuFe2O4 films and carrying out spin-coating on the CuFe2O4 film with multiple Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3 films to obtain the multiferroic Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4 composite film. The preparation method has simple equipment requirements, can prepare the film with good uniformity, easily controls a doping amount, improves ferroelectric and ferromagnetic properties of the film and effectively reduces film leakage current density.

Description

A kind of multiferroic Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4Composite membrane 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 multiferroic composite membrane, specifically Relate to a kind of multiferroic Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4Composite membrane and preparation method thereof.
Background technology
BiFeO3It is a kind of typical single phase multi-iron material, is also a kind of unleaded simultaneously and there is ferroelectricity and ferromagnetic material. BiFeO3The intensity of magnetization (M) and electric polarization (P) electromagnetic coupled can occur, can by electric field induction produce magnetic field, simultaneously magnetic field Again can be with evoked electrode, i.e. magnetoelectric effect.This leads in microelectronics, photoelectronics, integrated optics and microelectromechanical systems etc. Territory has a wide range of applications, and is the hot topic of research at present.
But, BiFeO3Middle existence Bi unstable, volatile3+Ion, Bi during sintering3+Ion has a certain amount of Volatilization, thus form Lacking oxygen, cause Fe3+To Fe2+Ion is changed.This phenomenon makes the BiFeO prepared3Film exists bigger Leakage current, poor ferroelectric properties and more weak ferromagnetic property.Which greatly limits BiFeO3The application of material.
In order to solve this problem, people have done substantial amounts of research, mainly take following several method: in A position, B position and A/B The doping of the enterprising row element in position, and compound with thin magnetic film prepare laminated film, to reduce the leakage current of film, improve BiFeO3 The ferroelectric properties of film and ferromagnetic property.
At present, yet there are no take to adulterate Pr, Sr on A position, adulterate on B position Mn, Cu, and and thin magnetic film CuFe2O4 Compound method prepares Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4Composite membrane, to improve BiFeO3Film every The relevant report of performance.
Summary of the invention
It is an object of the invention to provide a kind of multiferroic Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4Composite membrane and Preparation method, the method can 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 multiferroic Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4Composite membrane, including the upper layer film being combined with each other And lower membrane, wherein upper layer film is Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3Crystalline state film, lower membrane is CuFe2O4Crystalline state film, X=0.01～0.05.
Described Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3The crystal formation of crystalline state film is tripartite's phase, and space structure group is R3m:H, Cell parameter is a=b=5.5647, c=13.7472；CuFe2O4The crystal formation of crystalline state film is Emission in Cubic, and space structure group is Fd-3m:2.
Under the test frequency of 1kHz, the dielectric constant of this composite membrane is 167～360；When test frequency is 1kHz, maximum survey When examination electric field is 910kV/cm, the saturated polarization of this composite membrane is 14～120 μ C/cm2, remanent polarization is 6～104 μC/cm2, coercive field is 360～685kV/cm；Under room temperature, the saturation magnetisation value of this composite membrane is 35.5～40.3emu/cm3, surplus Remaining magnetization value is 18.4～24.9emu/cm3。
A kind of multiferroic Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4The preparation method of composite membrane, comprises the following steps:
Step 1: ferric nitrate and copper nitrate are dissolved in EGME for 1:2 in molar ratio, add acetic anhydride after stirring, Obtain CuFe2O4Precursor liquid；Wherein CuFe2O4In precursor liquid, the concentration of Cu ion is 0.15～0.25mol/L；
Step 2: be that 0.88:0.15:0.02:0.97-x:0.03:x is by bismuth nitrate, praseodymium nitrate, strontium nitrate, ferric nitrate, nitre in molar ratio Acid manganese and copper nitrate are dissolved in solvent, obtain Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3Precursor liquid, wherein x=0.01～0.05, Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3In precursor liquid, the total concentration of metal ion is 0.25～0.35mol/L, and solvent is second two Alcohol methyl ether and the mixed liquor of acetic anhydride；
Step 3: use spin-coating method spin coating CuFe on substrate2O4Precursor liquid, obtains CuFe2O4Wet film, CuFe2O4Wet 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 CuFe2O4Film；
Step 4: treat crystalline state CuFe2O4After film cooling, in crystalline state CuFe2O4Step 3 is repeated, until it reaches required on film Thickness, obtains CuFe2O4Crystalline state film；
Step 5: at CuFe2O4Spin coating Bi on crystalline state film0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3Precursor liquid, obtains Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3Wet film, Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3Wet film after spin coating Toast to obtain dry film at 180～210 DEG C, then anneal in atmosphere, obtain crystalline state Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3Film； Wherein annealing temperature is 540～550 DEG C；
Step 6: treat crystalline state Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3After film cooling, repeat step 5 thereon, until reaching To desired thickness, i.e. obtain multiferroic Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4Composite membrane.
Described CuFe2O4In precursor liquid, the volume ratio of EGME and acetic anhydride is (2.5～3.5): 1；The solvent of described step 2 The volume ratio of middle EGME 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 CuFe2O4Precursor liquid；
Described step 5 is before carrying out, first to CuFe2O4Crystalline state film carries out ultraviolet light treatment with irradiation, makes CuFe2O4Crystalline state film surface Reach atomic cleanliness degree, then spin coating Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3Precursor liquid.
In described step 3 and step 5, spin coating rotating speed during spin coating is 3500～4100r/min, and spin coating time is 15～25s.
In described step 3 and step 5, the baking time after spin coating is 10～15min.
Annealing time in described step 3 is 7～annealing time in 15min, step 5 is 6～12min.
Described multiferroic Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4Composite membrane is by 4～8 layer crystal states CuFe2O4Thin Film and 8～15 layer crystal states Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3Film is constituted.
Relative to prior art, the invention have the benefit that
1. multiferroic Bi that the present invention provides0.83Pr0.15Sr0.02Fe0.95Mn0.03Cu0.02O3-CuFe2O4The preparation method of laminated film, Select lanthanide series rare earth element Pr and alkaline earth element Sr to BiFeO3Carry out the doping of A position, select transient metal Mn and Cu To BiFeO3Carry out the doping of B position.Owing to Pr and Sr is to Bi3+Replacement, and Mn, Cu ripple of valence state in annealing process Dynamic, it is possible to effectively to suppress Bi3+Volatilization and Fe3+To Fe2+Transformation so that Bi0.83Pr0.15Sr0.02Fe0.95Mn0.03Cu0.02O3 Film shows macroscopic magnetization, reduces BiFeO3The leakage current density of film, improves BiFeO3The ferroelectric properties of film and ferromagnetic Performance.The present invention is except to BiFeO3Carry out outside the element doping on A/B position, also with there is ferromagnetism, the CuFe of low coercive field2O4 Film is combined, to improve the Bi of preparation0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4The ferromagnetic property of composite membrane, makes Obtain multiferroic Bi of the present invention0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4Composite membrane has the ferroelectric properties of excellence simultaneously And ferromagnetic property.
2. it is currently used for preparing BiFeO3The method of film has a lot, mainly has 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 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 rare earth element Pr and alkaline earth unit Element Sr is to BiFeO3Carry out the doping of A position, transient metal Mn and Cu to BiFeO3Carry out the doping of B position, and composite Cu Fe2O4, Substrate is prepared multiferroic Bi0.83Pr0.15Sr0.02Fe0.95Mn0.03Cu0.02O3-CuFe2O4Composite membrane, equipment requirement is simple, experiment Condition easily reaches, and doping is easily controlled, multiferroic Bi of preparation0.83Pr0.15Sr0.02Fe0.95Mn0.03Cu0.02O3-CuFe2O4Multiple Conjunction film uniformity is good, and can be by doping and CuFe2O4Compound increase substantially its ferroelectricity and ferromagnetic property.
3. the Bi that the present invention provides0.83Pr0.15Sr0.02Fe0.95Mn0.03Cu0.02O3-CuFe2O4Composite membrane, in approximation originally in perovskite In the bismuth ferrite crystal lattices of structure, doped with rare-earth elements Pr, alkaline earth element Sr and transition metal Mn and Cu, make bismuth ferrite crystal lattices Distortion, structural aberration aggravates, and can effectively suppress Bi simultaneously3+Volatilization and Fe3+To Fe2+Transformation so that Bi0.83Pr0.15Sr0.02Fe0.95Mn0.03Cu0.02O3Film shows macroscopic magnetization, reduces BiFeO3The leakage current density of film, carries High BiFeO3The ferroelectric properties of film and ferromagnetic property.And in conjunction with having ferromagnetism, the CuFe of low coercive field2O4Film, makes this The Bi of invention0.83Pr0.15Sr0.02Fe0.95Mn0.03Cu0.02O3-CuFe2O4Composite membrane has ferroelectric properties and the ferromagnetism of excellence simultaneously Energy.
Accompanying drawing explanation
Fig. 1 is Bi prepared by the present invention0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4The XRD of composite membrane；
Fig. 2 is Bi prepared by the present invention0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4The Raman spectrogram of composite membrane；
Fig. 3 is Bi prepared by the present invention0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4The SEM figure of composite membrane, wherein A (), (b), (c) are respectively the Bi that embodiment 1-3 prepares0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4Composite membrane SEM schemes；
Fig. 4 is Bi prepared by the present invention0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4The dielectric constant of composite membrane and dielectric Loss and the graph of a relation testing frequency；
Fig. 5 is Bi prepared by the present invention0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4The leakage current density of composite membrane；
Fig. 6 is Bi prepared by the present invention0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4The ferroelectric hysteresis loop of composite membrane；
Fig. 7 is Bi prepared by the present invention0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4The hysteresis curve of composite membrane.
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.
Multiferroic Bi that the present invention provides0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4(x=0.01～0.05) composite membrane, including The lower membrane being combined with each other and upper layer film, wherein lower membrane is CuFe2O4Crystalline state film, its crystal formation is Emission in Cubic, space structure group For Fd-3m:2；Upper layer film is Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3Crystalline state film, its crystal formation is tripartite's phase, space structure Group is R3m:H, and cell parameter is a=b=5.5647, c=13.7472.
Embodiment 1
Step 1: ferric nitrate and copper nitrate are dissolved in EGME for 1:2 in molar ratio, after stirring 30min, adds vinegar Acid anhydrides stirring 90min, obtains the stable CuFe that Cu ion concentration is 0.15mol/L2O4Precursor liquid, CuFe2O4Precursor liquid The volume ratio of middle EGME and acetic anhydride is 3:1；
Step 2: be that 0.88:0.15:0.02:0.96:0.03:0.01 is by bismuth nitrate, praseodymium nitrate, strontium nitrate, ferric nitrate, nitre in molar ratio Acid manganese and copper nitrate are dissolved in solvent (x=0.01, bismuth nitrate excess 5%), and the total concentration obtaining metal ion is the steady of 0.25mol/L Fixed Bi0.83Pr0.15Sr0.02Fe0.96Mn0.03Cu0.01O3Precursor liquid；Solvent be volume ratio be EGME and the acetic anhydride of 3:1 Mixed liquor；
Step 3: select FTO/glass substrate, the FTO/glass substrate of well cutting is sequentially placed in washing agent, acetone, ethanol Ultrasonic Cleaning, with a large amount of distilled water flushing substrates after each Ultrasonic 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 CuFe2O4Precursor liquid, obtains CuFe2O4Wet film, to CuFe2O4Wet film spin coating, spin coating rotating speed is 3800r/min, even The glue time is 15s, after spin coating terminates, toasts 12min and obtain dry film, then the 9min that anneals layer by layer in air at 580 DEG C at 180 DEG C, Obtain crystalline state CuFe2O4Film；
Step 4: treat crystalline state CuFe2O4After film cooling, in crystalline state CuFe2O4Repeat step 3 on film, be repeated 6 times, To CuFe2O4Crystalline state film；
Step 5: by CuFe2O4Crystalline state film is placed in ultraviolet radiation instrument irradiation 40min so that it is surface reaches atomic cleanliness degree； Then at CuFe2O4Spin coating Bi on crystalline state film0.83Pr0.15Sr0.02Fe0.96Mn0.03Cu0.01O3Precursor liquid, obtains Bi0.83Pr0.15Sr0.02Fe0.96Mn0.03Cu0.01O3Wet film, to Bi0.83Pr0.15Sr0.02Fe0.96Mn0.03Cu0.01O3Wet film spin coating, spin coating Rotating speed is 3800r/min, and spin coating time is 15s, after spin coating terminates, toasts 12min and obtain dry film at 180 DEG C, then at 540 DEG C Anneal in lower air 12min layer by layer, obtains crystalline state Bi0.83Pr0.15Sr0.02Fe0.96Mn0.03Cu0.01O3Film；
Step 6: treat crystalline state Bi0.83Pr0.15Sr0.02Fe0.96Mn0.03Cu0.01O3After film cooling, in crystalline state Bi0.83Pr0.15Sr0.02Fe0.96Mn0.03Cu0.01O3Repeat step 5 on film, be repeated 14 times, obtain multiferroic Bi0.83Pr0.15Sr0.02Fe0.96Mn0.03Cu0.01O3-CuFe2O4Composite membrane.
Use XRD test b i0.83Pr0.15Sr0.02Fe0.96Mn0.03Cu0.01O3-CuFe2O4The thing phase composition structure of composite membrane.With FE-SEM measures Bi0.83Pr0.15Sr0.02Fe0.96Mn0.03Cu0.01O3-CuFe2O4The microscopic appearance interracial contact situation of composite membrane.With Agilent E4980A precision LCR table test b i0.83Pr0.15Sr0.02Fe0.96Mn0.03Cu0.01O3-CuFe2O4The dielectricity of composite membrane Can, when test frequency is 1kHz, Bi0.83Pr0.15Sr0.02Fe0.96Mn0.03Cu0.01O3-CuFe2O4The dielectric constant of composite membrane is 355. With Agilent B2900 test b i0.83Pr0.15Sr0.02Fe0.96Mn0.03Cu0.01O3-CuFe2O4The leakage conductance current characteristics of composite membrane.With TF2000 ferroelectricity analyzer test b i0.83Pr0.15Sr0.02Fe0.96Mn0.03Cu0.01O3-CuFe2O4The ferroelectric properties of composite membrane, test frequency Rate is 1kHz, when full test electric field is 910kV/cm, and Bi0.83Pr0.15Sr0.02Fe0.96Mn0.03Cu0.01O3-CuFe2O4Composite membrane Saturated polarization be 93 μ C/cm2, remanent polarization is 86 μ C/cm2, coercive field is 685kV/cm.Use SQUID MPMS-XL-7 test b i0.83Pr0.15Sr0.02Fe0.96Mn0.03Cu0.01O3-CuFe2O4Ferromagnetic property under composite membrane room temperature, room temperature Under, Bi0.83Pr0.15Sr0.02Fe0.96Mn0.03Cu0.01O3-CuFe2O4The saturation magnetisation value of composite membrane is 35.5emu/cm3, remanence Change value is 18.4emu/cm3。
Embodiment 2
Step 1: ferric nitrate and copper nitrate are dissolved in EGME for 1:2 in molar ratio, after stirring 30min, adds vinegar Acid anhydrides stirring 90min, obtains the stable CuFe that Cu ion concentration is 0.15mol/L2O4Precursor liquid, CuFe2O4Precursor liquid The volume ratio of middle EGME and acetic anhydride is 3:1；
Step 2: be that 0.88:0.15:0.02:0.95:0.03:0.02 is by bismuth nitrate, praseodymium nitrate, strontium nitrate, ferric nitrate, nitre in molar ratio Acid manganese and copper nitrate are dissolved in solvent (x=0.02, bismuth nitrate excess 5%), and the total concentration obtaining metal ion is the steady of 0.25mol/L Fixed Bi0.83Pr0.15Sr0.02Fe0.95Mn0.03Cu0.02O3Precursor liquid；Solvent be volume ratio be EGME and the acetic anhydride of 3:1 Mixed liquor；
Step 3: select FTO/glass substrate, the FTO/glass substrate of well cutting is sequentially placed in washing agent, acetone, ethanol Ultrasonic Cleaning, with a large amount of distilled water flushing substrates after each Ultrasonic 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 CuFe2O4Precursor liquid, obtains CuFe2O4Wet film, to CuFe2O4Wet film spin coating, spin coating rotating speed is 3800r/min, even The glue time is 15s, after spin coating terminates, toasts 12min and obtain dry film, then the 9min that anneals layer by layer in air at 580 DEG C at 180 DEG C, Obtain crystalline state CuFe2O4Film；
Step 4: treat crystalline state CuFe2O4After film cooling, in crystalline state CuFe2O4Repeat step 3 on film, be repeated 6 times, To CuFe2O4Crystalline state film；
Step 5: by CuFe2O4Crystalline state film is placed in ultraviolet radiation instrument irradiation 40min so that it is surface reaches atomic cleanliness degree； Then at CuFe2O4Spin coating Bi on crystalline state film0.83Pr0.15Sr0.02Fe0.95Mn0.03Cu0.02O3Precursor liquid, obtains Bi0.83Pr0.15Sr0.02Fe0.95Mn0.03Cu0.02O3Wet film, to Bi0.83Pr0.15Sr0.02Fe0.95Mn0.03Cu0.02O3Wet film spin coating, spin coating Rotating speed is 3800r/min, and spin coating time is 15s, after spin coating terminates, toasts 12min and obtain dry film at 180 DEG C, then at 540 DEG C Anneal in lower air 12min layer by layer, obtains crystalline state Bi0.83Pr0.15Sr0.02Fe0.95Mn0.03Cu0.02O3Film；
Step 6: treat crystalline state Bi0.83Pr0.15Sr0.02Fe0.95Mn0.03Cu0.02O3After film cooling, in crystalline state Bi0.83Pr0.15Sr0.02Fe0.95Mn0.03Cu0.02O3Repeat step 5 on film, be repeated 14 times, obtain multiferroic Bi0.83Pr0.15Sr0.02Fe0.95Mn0.03Cu0.02O3-CuFe2O4Composite membrane.
Use XRD test b i0.83Pr0.15Sr0.02Fe0.95Mn0.03Cu0.02O3-CuFe2O4The thing phase composition structure of composite membrane.With FE-SEM measures Bi0.83Pr0.15Sr0.02Fe0.95Mn0.03Cu0.02O3-CuFe2O4The microscopic appearance interracial contact situation of composite membrane.With Agilent E4980A precision LCR table test b i0.83Pr0.15Sr0.02Fe0.95Mn0.03Cu0.02O3-CuFe2O4The dielectricity of composite membrane Can, when test frequency is 1kHz, Bi0.83Pr0.15Sr0.02Fe0.95Mn0.03Cu0.02O3-CuFe2O4The dielectric constant of composite membrane is 360. With Agilent B2900 test b i0.83Pr0.15Sr0.02Fe0.95Mn0.03Cu0.02O3-CuFe2O4The leakage conductance current characteristics of composite membrane.With TF2000 ferroelectricity analyzer test b i0.83Pr0.15Sr0.02Fe0.95Mn0.03Cu0.02O3-CuFe2O4The ferroelectric properties of composite membrane, test frequency Rate is 1kHz, when full test electric field is 910kV/cm, and Bi0.83Pr0.15Sr0.02Fe0.95Mn0.03Cu0.02O3-CuFe2O4Composite membrane Saturated polarization be 120 μ C/cm2, remanent polarization is 104 μ C/cm2, coercive field is 495kV/cm.Use SQUID MPMS-XL-7 test b i0.83Pr0.15Sr0.02Fe0.95Mn0.03Cu0.02O3-CuFe2O4Ferromagnetic property under composite membrane room temperature, room temperature Under, Bi0.83Pr0.15Sr0.02Fe0.95Mn0.03Cu0.02O3-CuFe2O4The saturation magnetisation value of composite membrane is 38emu/cm3, remanent magnetization Value is 24.9emu/cm3。
Embodiment 3
Step 1: ferric nitrate and copper nitrate are dissolved in EGME for 1:2 in molar ratio, after stirring 30min, adds vinegar Acid anhydrides stirring 90min, obtains the stable CuFe that Cu ion concentration is 0.15mol/L2O4Precursor liquid, CuFe2O4Precursor liquid The volume ratio of middle EGME and acetic anhydride is 3:1；
Step 2: be that 0.88:0.15:0.02:0.94:0.03:0.03 is by bismuth nitrate, praseodymium nitrate, strontium nitrate, ferric nitrate, nitre in molar ratio Acid manganese and copper nitrate are dissolved in solvent (x=0.03, bismuth nitrate excess 5%), and the total concentration obtaining metal ion is the steady of 0.25mol/L Fixed Bi0.83Pr0.15Sr0.02Fe0.94Mn0.03Cu0.03O3Precursor liquid；Solvent be volume ratio be EGME and the acetic anhydride of 3:1 Mixed liquor；
Step 3: select FTO/glass substrate, the FTO/glass substrate of well cutting is sequentially placed in washing agent, acetone, ethanol Ultrasonic Cleaning, with a large amount of distilled water flushing substrates after each Ultrasonic 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 CuFe2O4Precursor liquid, obtains CuFe2O4Wet film, to CuFe2O4Wet film spin coating, spin coating rotating speed is 3800r/min, even The glue time is 15s, after spin coating terminates, toasts 12min and obtain dry film, then the 9min that anneals layer by layer in air at 580 DEG C at 180 DEG C, Obtain crystalline state CuFe2O4Film；
Step 4: treat crystalline state CuFe2O4After film cooling, in crystalline state CuFe2O4Repeat step 3 on film, be repeated 6 times, To CuFe2O4Crystalline state film；
Step 5: by CuFe2O4Crystalline state film is placed in ultraviolet radiation instrument irradiation 40min so that it is surface reaches atomic cleanliness degree； Then at CuFe2O4Spin coating Bi on crystalline state film0.83Pr0.15Sr0.02Fe0.94Mn0.03Cu0.03O3Precursor liquid, obtains Bi0.83Pr0.15Sr0.02Fe0.94Mn0.03Cu0.03O3Wet film, to Bi0.83Pr0.15Sr0.02Fe0.94Mn0.03Cu0.03O3Wet film spin coating, spin coating Rotating speed is 3800r/min, and spin coating time is 15s, after spin coating terminates, toasts 12min and obtain dry film at 180 DEG C, then at 540 DEG C Anneal in lower air 12min layer by layer, obtains crystalline state Bi0.83Pr0.15Sr0.02Fe0.94Mn0.03Cu0.03O3Film；
Step 6: treat crystalline state Bi0.83Pr0.15Sr0.02Fe0.94Mn0.03Cu0.03O3After film cooling, in crystalline state Bi0.83Pr0.15Sr0.02Fe0.94Mn0.03Cu0.03O3Repeat step 5 on film, be repeated 14 times, obtain multiferroic Bi0.83Pr0.15Sr0.02Fe0.94Mn0.03Cu0.03O3-CuFe2O4Composite membrane.
Use XRD test b i0.83Pr0.15Sr0.02Fe0.94Mn0.03Cu0.03O3-CuFe2O4The thing phase composition structure of composite membrane.With FE-SEM measures Bi0.83Pr0.15Sr0.02Fe0.94Mn0.03Cu0.03O3-CuFe2O4The microscopic appearance interracial contact situation of composite membrane.With Agilent E4980A precision LCR table test b i0.83Pr0.15Sr0.02Fe0.94Mn0.03Cu0.03O3-CuFe2O4The dielectricity of composite membrane Can, when test frequency is 1kHz, Bi0.83Pr0.15Sr0.02Fe0.94Mn0.03Cu0.03O3-CuFe2O4The dielectric constant of composite membrane is 167. With Agilent B2900 test b i0.83Pr0.15Sr0.02Fe0.94Mn0.03Cu0.03O3-CuFe2O4The leakage conductance current characteristics of composite membrane.With TF2000 ferroelectricity analyzer test b i0.83Pr0.15Sr0.02Fe0.94Mn0.03Cu0.03O3-CuFe2O4The ferroelectric properties of composite membrane, test frequency Rate is 1kHz, when full test electric field is 910kV/cm, and Bi0.83Pr0.15Sr0.02Fe0.94Mn0.03Cu0.03O3-CuFe2O4Composite membrane Saturated polarization be 14 μ C/cm2, remanent polarization is 6 μ C/cm2, coercive field is 360kV/cm.Use SQUID MPMS-XL-7 test b i0.83Pr0.15Sr0.02Fe0.94Mn0.03Cu0.03O3-CuFe2O4Ferromagnetic property under composite membrane room temperature, room temperature Under, Bi0.83Pr0.15Sr0.02Fe0.94Mn0.03Cu0.03O3-CuFe2O4The saturation magnetisation value of composite membrane is 40.3emu/cm3, remanence Change value is 23emu/cm3。
Embodiment 4
Step 1: ferric nitrate and copper nitrate are dissolved in EGME for 1:2 in molar ratio, after stirring 30min, adds vinegar Acid anhydrides stirring 90min, obtains the stable CuFe that Cu ion concentration is 0.2mol/L2O4Precursor liquid, CuFe2O4In precursor liquid The volume ratio of EGME and acetic anhydride is 2.5:1；
Step 2: be that 0.88:0.15:0.02:0.93:0.03:0.04 is by bismuth nitrate, praseodymium nitrate, strontium nitrate, ferric nitrate, nitre in molar ratio Acid manganese and copper nitrate are dissolved in solvent (x=0.04, bismuth nitrate excess 5%), and the total concentration obtaining metal ion is the steady of 0.35mol/L Fixed Bi0.83Pr0.15Sr0.02Fe0.93Mn0.03Cu0.04O3Precursor liquid；Solvent be volume ratio be EGME and the acetic anhydride of 2.5:1 Mixed liquor；
Step 3: select FTO/glass substrate, the FTO/glass substrate of well cutting is sequentially placed in washing agent, acetone, ethanol Ultrasonic Cleaning, with a large amount of distilled water flushing substrates after each Ultrasonic 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 CuFe2O4Precursor liquid, obtains CuFe2O4Wet film, to CuFe2O4Wet film spin coating, spin coating rotating speed is 3500r/min, even The glue time is 25s, after spin coating terminates, toasts 13min and obtain dry film at 190 DEG C, then anneals 13 at 590 DEG C in air layer by layer Min, obtains crystalline state CuFe2O4Film；
Step 4: treat crystalline state CuFe2O4After film cooling, in crystalline state CuFe2O4Repeat step 3 on film, be repeated 3 times, To CuFe2O4Crystalline state film；
Step 5: by CuFe2O4Crystalline state film is placed in ultraviolet radiation instrument irradiation 40min so that it is surface reaches atomic cleanliness degree； Then at CuFe2O4Spin coating Bi on crystalline state film0.83Pr0.15Sr0.02Fe0.93Mn0.03Cu0.04O3Precursor liquid, obtains Bi0.83Pr0.15Sr0.02Fe0.93Mn0.03Cu0.04O3Wet film, to Bi0.83Pr0.15Sr0.02Fe0.93Mn0.03Cu0.04O3Wet film spin coating, spin coating Rotating speed is 3500r/min, and spin coating time is 25s, after spin coating terminates, toasts 13min and obtain dry film at 190 DEG C, then at 545 DEG C Anneal in lower air 8min layer by layer, obtains crystalline state Bi0.83Pr0.15Sr0.02Fe0.93Mn0.03Cu0.04O3Film；
Step 6: treat crystalline state Bi0.83Pr0.15Sr0.02Fe0.93Mn0.03Cu0.04O3After film cooling, in crystalline state Bi0.83Pr0.15Sr0.02Fe0.93Mn0.03Cu0.04O3Repeat step 5 on film, be repeated 7 times, obtain multiferroic Bi0.83Pr0.15Sr0.02Fe0.93Mn0.03Cu0.04O3-CuFe2O4Composite membrane.
Embodiment 5
Step 1: ferric nitrate and copper nitrate are dissolved in EGME for 1:2 in molar ratio, after stirring 30min, adds vinegar Acid anhydrides stirring 90min, obtains the stable CuFe that Cu ion concentration is 0.25mol/L2O4Precursor liquid, CuFe2O4Precursor liquid The volume ratio of middle EGME and acetic anhydride is 3.5:1；
Step 2: be that 0.88:0.15:0.02:0.92:0.03:0.05 is by bismuth nitrate, praseodymium nitrate, strontium nitrate, ferric nitrate, nitre in molar ratio Acid manganese and copper nitrate are dissolved in solvent (x=0.05, bismuth nitrate excess 5%), and the total concentration obtaining metal ion is the steady of 0.3mol/L Fixed Bi0.83Pr0.15Sr0.02Fe0.92Mn0.03Cu0.05O3Precursor liquid；Solvent be volume ratio be EGME and the acetic anhydride of 3.5:1 Mixed liquor；
Step 3: select FTO/glass substrate, the FTO/glass substrate of well cutting is sequentially placed in washing agent, acetone, ethanol Ultrasonic Cleaning, with a large amount of distilled water flushing substrates after each Ultrasonic 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 CuFe2O4Precursor liquid, obtains CuFe2O4Wet film, to CuFe2O4Wet film spin coating, spin coating rotating speed is 4100r/min, even The glue time is 17s, after spin coating terminates, toasts 11min and obtain dry film, then the 7min that anneals layer by layer in air at 600 DEG C at 200 DEG C, Obtain crystalline state CuFe2O4Film；
Step 4: treat crystalline state CuFe2O4After film cooling, in crystalline state CuFe2O4Repeat step 3 on film, be repeated 4 times, To CuFe2O4Crystalline state film；
Step 5: by CuFe2O4Crystalline state film is placed in ultraviolet radiation instrument irradiation 40min so that it is surface reaches atomic cleanliness degree； Then at CuFe2O4Spin coating Bi on crystalline state film0.83Pr0.15Sr0.02Fe0.92Mn0.03Cu0.05O3Precursor liquid, obtains Bi0.83Pr0.15Sr0.02Fe0.92Mn0.03Cu0.05O3Wet film, to Bi0.83Pr0.15Sr0.02Fe0.92Mn0.03Cu0.05O3Wet film spin coating, spin coating Rotating speed is 4100r/min, and spin coating time is 17s, after spin coating terminates, toasts 11min and obtain dry film at 200 DEG C, then at 550 DEG C Anneal in lower air 6min layer by layer, obtains crystalline state Bi0.83Pr0.15Sr0.02Fe0.92Mn0.03Cu0.05O3Film；
Step 6: treat crystalline state Bi0.83Pr0.15Sr0.02Fe0.92Mn0.03Cu0.05O3After film cooling, in crystalline state Bi0.83Pr0.15Sr0.02Fe0.92Mn0.03Cu0.05O3Repeat step 5 on film, be repeated 9 times, obtain multiferroic Bi0.83Pr0.15Sr0.02Fe0.92Mn0.03Cu0.05O3-CuFe2O4Composite membrane.
Embodiment 6
Step 1: ferric nitrate and copper nitrate are dissolved in EGME for 1:2 in molar ratio, after stirring 30min, adds vinegar Acid anhydrides stirring 90min, obtains the stable CuFe that Cu ion concentration is 0.18mol/L2O4Precursor liquid, CuFe2O4Precursor liquid The volume ratio of middle EGME and acetic anhydride is 2.8:1；
Step 2: be 0.88:0.15:0.02:0.955:0.03:0.015 in molar ratio by bismuth nitrate, praseodymium nitrate, strontium nitrate, ferric nitrate, Manganese nitrate and copper nitrate are dissolved in solvent (x=0.015, bismuth nitrate excess 5%), and the total concentration obtaining metal ion is 0.28mol/L Stable Bi0.83Pr0.15Sr0.02Fe0.955Mn0.03Cu0.015O3Precursor liquid；Solvent be volume ratio be EGME and the vinegar of 2.8:1 The mixed liquor of acid anhydrides；
Step 3: select FTO/glass substrate, the FTO/glass substrate of well cutting is sequentially placed in washing agent, acetone, ethanol Ultrasonic Cleaning, with a large amount of distilled water flushing substrates after each Ultrasonic 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 CuFe2O4Precursor liquid, obtains CuFe2O4Wet film, to CuFe2O4Wet film spin coating, spin coating rotating speed is 4000r/min, even The glue time is 20s, after spin coating terminates, toasts 10min and obtain dry film at 210 DEG C, then anneals 15 at 585 DEG C in air layer by layer Min, obtains crystalline state CuFe2O4Film；
Step 4: treat crystalline state CuFe2O4After film cooling, in crystalline state CuFe2O4Repeat step 3 on film, be repeated 5 times, To CuFe2O4Crystalline state film；
Step 5: by CuFe2O4Crystalline state film is placed in ultraviolet radiation instrument irradiation 40min so that it is surface reaches atomic cleanliness degree； Then at CuFe2O4Spin coating Bi on crystalline state film0.83Pr0.15Sr0.02Fe0.955Mn0.03Cu0.015O3Precursor liquid, obtains Bi0.83Pr0.15Sr0.02Fe0.955Mn0.03Cu0.015O3Wet film, to Bi0.83Pr0.15Sr0.02Fe0.955Mn0.03Cu0.015O3Wet film spin coating, even Glue rotating speed is 4000r/min, and spin coating time is 20s, after spin coating terminates, toasts 10min and obtain dry film at 210 DEG C, then at 542 DEG C Anneal in lower air 10min layer by layer, obtains crystalline state Bi0.83Pr0.15Sr0.02Fe0.955Mn0.03Cu0.015O3Film；
Step 6: treat crystalline state Bi0.83Pr0.15Sr0.02Fe0.955Mn0.03Cu0.015O3After film cooling, in crystalline state Bi0.83Pr0.15Sr0.02Fe0.955Mn0.03Cu0.015O3Repeat step 5 on film, be repeated 10 times, obtain multiferroic Bi0.83Pr0.15Sr0.02Fe0.955Mn0.03Cu0.015O3-CuFe2O4Composite membrane.
Embodiment 7
Step 1: ferric nitrate and copper nitrate are dissolved in EGME for 1:2 in molar ratio, after stirring 30min, adds vinegar Acid anhydrides stirring 90min, obtains the stable CuFe that Cu ion concentration is 0.22mol/L2O4Precursor liquid, CuFe2O4Precursor liquid The volume ratio of middle EGME and acetic anhydride is 3.2:1；
Step 2: be 0.88:0.15:0.02:0.945:0.03:0.025 in molar ratio by bismuth nitrate, praseodymium nitrate, strontium nitrate, ferric nitrate, Manganese nitrate and copper nitrate are dissolved in solvent (x=0.025, bismuth nitrate excess 5%), and the total concentration obtaining metal ion is 0.32mol/L Stable Bi0.83Pr0.15Sr0.02Fe0.945Mn0.03Cu0.025O3Precursor liquid；Solvent be volume ratio be EGME and the vinegar of 3.2:1 The mixed liquor of acid anhydrides；
Step 3: select FTO/glass substrate, the FTO/glass substrate of well cutting is sequentially placed in washing agent, acetone, ethanol Ultrasonic Cleaning, with a large amount of distilled water flushing substrates after each Ultrasonic 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 CuFe2O4Precursor liquid, obtains CuFe2O4Wet film, to CuFe2O4Wet film spin coating, spin coating rotating speed is 3700r/min, even The glue time is 22s, after spin coating terminates, toasts 15min and obtain dry film, then the 1min that anneals layer by layer in air at 595 DEG C at 185 DEG C, Obtain crystalline state CuFe2O4Film；
Step 4: treat crystalline state CuFe2O4After film cooling, in crystalline state CuFe2O4Repeat step 3 on film, be repeated 7 times, To CuFe2O4Crystalline state film；
Step 5: by CuFe2O4Crystalline state film is placed in ultraviolet radiation instrument irradiation 40min so that it is surface reaches atomic cleanliness degree； Then at CuFe2O4Spin coating Bi on crystalline state film0.83Pr0.15Sr0.02Fe0.945Mn0.03Cu0.025O3Precursor liquid, obtains Bi0.83Pr0.15Sr0.02Fe0.945Mn0.03Cu0.025O3Wet film, to Bi0.83Pr0.15Sr0.02Fe0.945Mn0.03Cu0.025O3Wet film spin coating, even Glue rotating speed is 3700r/min, and spin coating time is 22s, after spin coating terminates, toasts 15min and obtain dry film at 185 DEG C, then at 548 DEG C Anneal in lower air 7min layer by layer, obtains crystalline state Bi0.83Pr0.15Sr0.02Fe0.945Mn0.03Cu0.025O3Film；
Step 6: treat crystalline state Bi0.83Pr0.15Sr0.02Fe0.945Mn0.03Cu0.025O3After film cooling, in crystalline state Bi0.83Pr0.15Sr0.02Fe0.945Mn0.03Cu0.025O3Repeat step 5 on film, be repeated 12 times, obtain multiferroic Bi0.83Pr0.15Sr0.02Fe0.945Mn0.03Cu0.025O3-CuFe2O4Composite membrane.
XRD is used to test multiferroic Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4The thing phase composition structure of composite membrane. Multiferroic Bi is measured with FE-SEM0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4The microscopic appearance interracial contact of composite membrane Situation.Multiferroic Bi is tested with Agilent E4980A precision LCR table0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4 The dielectric properties of composite membrane.Multiferroic Bi is tested with Agilent B29000.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4Multiple Close the leakage conductance current characteristics of film.With TF2000 ferroelectricity analyzer test b i0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4 The ferroelectric properties of composite membrane.With SQUID MPMS-XL-7 test b i0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4Multiple Close the ferromagnetic property under film room temperature.By Bi prepared by embodiment 1～30.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4 Composite membrane carries out above test, and result is as shown in Fig. 1～7.
Fig. 1 is multiferroic Bi prepared by the present invention0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4The XRD of composite membrane； Wherein x=0.00 is Bi0.83Pr0.15Sr0.02Fe0.97Mn0.03O3-CuFe2O4Composite membrane, is the method according to the present invention, in step 2 In undope (Fig. 2,5,6,7 with) that Cu prepares.As can be known from Fig. 1, Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3 Having the perovskite structure of distortion, its crystal formation is tripartite's phase, and space structure group is R3m:H, and cell parameter is a=b=5.5647, C=13.7472, does not has impurity to occur.Also observe that CuFe simultaneously2O4Characteristic peak, its crystal formation is Emission in Cubic, space structure Group is Fd-3m:2；This outer film does not has the appearance of other impurity.
Fig. 2 is multiferroic Bi prepared by the present invention0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4The Raman spectrum of composite membrane Figure；Occur in that Bi the most respectively0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3And CuFe2O4Vibrating membrane, further demonstrate that this Invention has prepared Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4Composite membrane.
Fig. 3 is multiferroic Bi prepared by the present invention0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4The SEM figure of composite membrane, Wherein (a), (b), (c) are respectively the Bi that embodiment 1-3 prepares0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4Compound The SEM figure of film；Can be seen that multiferroic Bi prepared by the present invention0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4Composite membrane Surfacing, even grain size.
Fig. 4 is multiferroic Bi prepared by the present invention0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4The dielectric constant of composite membrane Graph of a relation with dielectric loss with test frequency；Figure 4, it is seen that when testing frequency and being 1kHz, prepared by embodiment 1 Multiferroic Bi0.83Pr0.15Sr0.02Fe0.96Mn0.03Cu0.01O3-CuFe2O4The dielectric constant of composite membrane is 355, prepared by embodiment 2 Multiferroic Bi0.83Pr0.15Sr0.02Fe0.95Mn0.03Cu0.02O3-CuFe2O4The dielectric constant of composite membrane is 360, prepared by embodiment 3 Multiferroic Bi0.83Pr0.15Sr0.02Fe0.94Mn0.03Cu0.03O3-CuFe2O4The dielectric constant of composite membrane is 167.
Fig. 5 is multiferroic Bi prepared by the present invention0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4The leakage current of composite membrane is close Degree；From figure 5 it can be seen that Bi prepared by the present invention0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4Laminated film, Under positive field and negative sense electric field, leakage current is asymmetric.
Fig. 6 is multiferroic Bi prepared by the present invention0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4The ferroelectric hysteresis loop of composite membrane； From fig. 6 it can be seen that when test frequency is 1kHz, when full test electric field is 910kV/cm, multiferroic Bi0.83Pr0.15Sr0.02Fe0.96Mn0.03Cu0.01O3-CuFe2O4The saturated polarization of composite membrane is 93 μ C/cm2, remanent polarization It is 86 μ C/cm2, coercive field is 685kV/cm；Multiferroic Bi0.83Pr0.15Sr0.02Fe0.95Mn0.03Cu0.02O3-CuFe2O4Composite membrane Saturated polarization be 120 μ C/cm2, remanent polarization is 104 μ C/cm2, coercive field is 495kV/cm；Multiferroic Bi0.83Pr0.15Sr0.02Fe0.94Mn0.03Cu0.03O3-CuFe2O4The saturated polarization of composite membrane is 14 μ C/cm2, remanent polarization It is 6 μ C/cm2, coercive field is 360kV/cm；And Bi0.83Pr0.15Sr0.02Fe0.97Mn0.03O3-CuFe2O4The saturated polarization of composite membrane Intensity is 96 μ C/cm2, remanent polarization is 87 μ C/cm2, coercive field is 600kV/cm.
Fig. 7 is multiferroic Bi prepared by the present invention0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4The hysteresis curve of composite membrane, It can be seen from figure 7 that under room temperature, multiferroic Bi of embodiment 1 preparation0.83Pr0.15Sr0.02Fe0.96Mn0.03Cu0.01O3-CuFe2O4 The saturation magnetisation value of composite membrane is 35.5emu/cm3, remanent magnetization value is 18.4emu/cm3；The multiferroic of embodiment 2 preparation Bi0.83Pr0.15Sr0.02Fe0.95Mn0.03Cu0.02O3-CuFe2O4The saturation magnetisation value of composite membrane is 38emu/cm3, remanent magnetization value is 24.9emu/cm3；Multiferroic Bi of embodiment 3 preparation0.83Pr0.15Sr0.02Fe0.94Mn0.03Cu0.03O3-CuFe2O4Satisfying of composite membrane It is 40.3emu/cm with magnetization value3, remanent magnetization value is 23emu/cm3；And Bi0.83Pr0.15Sr0.02Fe0.97Mn0.03O3-CuFe2O4 The saturation magnetisation value of composite membrane is 22emu/cm3, remanent magnetization value is 16emu/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 CuFe2O4The interpolation of laminated magnetic film, it is possible to increase substantially BiFeO3The ferroelectricity of film Performance, reduces the leakage current density of film, improves the ferromagnetism of film simultaneously.
Above said content is to combine concrete preferred embodiment 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. multiferroic Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4Composite membrane, it is characterised in that: include being combined Upper layer film together and lower membrane, wherein upper layer film is Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3Crystalline state film, lower membrane is CuFe2O4Crystalline state film, x=0.01～0.05.
Multiferroic Bi the most according to claim 10.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4Composite membrane, it is special Levy and be: described Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3The crystal formation of crystalline state film is tripartite's phase, and space structure group is R3m:H, cell parameter is a=b=5.5647, c=13.7472；CuFe2O4The crystal formation of crystalline state film is Emission in Cubic, and space structure group is Fd-3m:2。
Multiferroic Bi the most according to claim 10.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4Composite membrane, it is special Levying and be: under the test frequency of 1kHz, the dielectric constant of this composite membrane is 167～360；When test frequency is 1kHz, When big test electric field is 910kV/cm, the saturated polarization of this composite membrane is 14～120 μ C/cm2, remanent polarization is 6～104 μ C/cm2, coercive field is 360～685kV/cm；Under room temperature, the saturation magnetisation value of this composite membrane is 35.5～40.3emu/cm3, Remanent magnetization value is 18.4～24.9emu/cm3。
4. multiferroic Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4The preparation method of composite membrane, it is characterised in that Comprise the following steps:
Step 1: ferric nitrate and copper nitrate are dissolved in EGME for 1:2 in molar ratio, add acetic anhydride after stirring, Obtain CuFe2O4Precursor liquid；Wherein CuFe2O4In precursor liquid, the concentration of Cu ion is 0.15～0.25mol/L；
Step 2: be that 0.88:0.15:0.02:0.97-x:0.03:x is by bismuth nitrate, praseodymium nitrate, strontium nitrate, ferric nitrate, nitre in molar ratio Acid manganese and copper nitrate are dissolved in solvent, obtain Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3Precursor liquid, wherein x=0.01～0.05, Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3In precursor liquid, the total concentration of metal ion is 0.25～0.35mol/L, and solvent is second two Alcohol methyl ether and the mixed liquor of acetic anhydride；
Step 3: use spin-coating method spin coating CuFe on substrate2O4Precursor liquid, obtains CuFe2O4Wet film, CuFe2O4Wet 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 CuFe2O4Film；
Step 4: treat crystalline state CuFe2O4After film cooling, in crystalline state CuFe2O4Step 3 is repeated, until it reaches required on film Thickness, obtains CuFe2O4Crystalline state film；
Step 5: at CuFe2O4Spin coating Bi on crystalline state film0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3Precursor liquid, obtains Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3Wet film, Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3Wet film after spin coating Toast to obtain dry film at 180～210 DEG C, then anneal in atmosphere, obtain crystalline state Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3Film； Wherein annealing temperature is 540～550 DEG C；
Step 6: treat crystalline state Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3After film cooling, repeat step 5 thereon, until reaching To desired thickness, i.e. obtain multiferroic Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4Composite membrane.
Multiferroic Bi the most according to claim 40.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4The preparation of composite membrane Method, it is characterised in that: described CuFe2O4In precursor liquid, the volume ratio of EGME and acetic anhydride is (2.5～3.5): 1；Institute Stating the volume ratio of EGME and acetic anhydride in the solvent of step 2 is (2.5～3.5): 1.
Multiferroic Bi the most according to claim 40.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4The preparation of composite membrane 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, makes Substrate surface reaches atomic cleanliness degree, then spin coating CuFe2O4Precursor liquid；
Described step 5 is before carrying out, first to CuFe2O4Crystalline state film carries out ultraviolet light treatment with irradiation, makes CuFe2O4Crystalline state film surface Reach atomic cleanliness degree, then spin coating Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3Precursor liquid.
Multiferroic Bi the most according to claim 40.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4The preparation of composite membrane Method, it is characterised in that: in described step 3 and step 5, spin coating rotating speed during spin coating is 3500～4100r/min, and spin coating time is 15～25s.
Multiferroic Bi the most according to claim 40.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4The preparation of composite membrane Method, it is characterised in that: in described step 3 and step 5, the baking time after spin coating is 10～15min.
Multiferroic Bi the most according to claim 40.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4The preparation of composite membrane Method, it is characterised in that: the annealing time in described step 3 is 7～annealing time in 15min, step 5 is 6～12min.
Multiferroic Bi the most according to claim 40.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4The system of composite membrane Preparation Method, it is characterised in that: described multiferroic Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4Composite membrane is by 4～8 Layer crystal state CuFe2O4Film and 8～15 layer crystal states Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3Film is constituted.
CN201610188155.1A 2016-03-29 2016-03-29 A kind of multiferroic Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4Composite membrane and preparation method thereof Active CN105906221B (en)

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CN107117830A (en) * 2017-04-18 2017-09-01 陕西科技大学 A kind of LaSrMnCo is co-doped with many iron thin films of bismuth ferrite and preparation method thereof
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
CN109336406A (en) * 2018-09-18 2019-02-15 陕西科技大学 A kind of the BGSFMC/CFGO laminated film and preparation method of symmetrical rectangular ferroelectric hysteresis loop

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CN104476832A (en) * 2014-12-11 2015-04-01 陕西科技大学 Laminated BiFe(0.97-x)Mn0.03TMxO3/CoFe2O4 multiferroic composite film and preparation method thereof

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CN103613144A (en) * 2013-11-04 2014-03-05 陕西科技大学 B-site Mn and Cu codoped high remanent polarization BiFeO3 film and preparation method
CN104478235A (en) * 2014-12-11 2015-04-01 陕西科技大学 Multiferroic Bi(0.98-x)Sr0.02RExFe0.97Mn0.03O3-CuFe2O4 composite film and preparation method thereof
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CN107117830A (en) * 2017-04-18 2017-09-01 陕西科技大学 A kind of LaSrMnCo is co-doped with many iron thin films of bismuth ferrite and preparation method thereof
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
CN109336406A (en) * 2018-09-18 2019-02-15 陕西科技大学 A kind of the BGSFMC/CFGO laminated film and preparation method of symmetrical rectangular ferroelectric hysteresis loop
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