CN104478230A - Bi[0.92-x]Ho0.08AExFe0.97Mn0.03O3 multiferroic film and preparation method thereof - Google Patents

Bi[0.92-x]Ho0.08AExFe0.97Mn0.03O3 multiferroic film and preparation method thereof Download PDF

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CN104478230A
CN104478230A CN201410766349.6A CN201410766349A CN104478230A CN 104478230 A CN104478230 A CN 104478230A CN 201410766349 A CN201410766349 A CN 201410766349A CN 104478230 A CN104478230 A CN 104478230A
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谈国强
耶维
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
    • C03C2218/113—Deposition methods from solutions or suspensions by sol-gel processes

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Abstract

The invention provides a Bi[0.92-x]Ho0.08AExFe0.97Mn0.03O3 multiferroic film and a preparation method thereof. The method comprises the following steps: preparing a Bi[0.92-x]Ho0.08AExFe0.97Mn0.03O3 precursor solution from bismuth nitrate, holmium nitrate, nitric acid AE, ferric nitrate and manganese acetate, wherein AE is Ca, Ba or Sr, and x=0.01-0.08; spinning the precursor solution on a substrate; and then spinning, drying and annealing, so as to obtain the Bi[0.92-x]Ho0.08AExFe0.97Mn0.03O3 multiferroic film. The Bi[0.92-x]Ho0.08AExFe0.97Mn0.03O3 multiferroic film is simple in demands on equipment; the experiment condition is easy to achieve; the doping amount is easy to control; the ferroelectric property of the film can be greatly improved; and the prepared Bi[0.92-x]Ho0.08AExFe0.97Mn0.03O3 multiferroic film is good in uniformity, low in leakage current and low in coercive field, and has relatively high remanent polarization.

Description

A kind of multiferroic Bi 0.92-xho 0.08aE xfe 0.97mn 0.03o 3film and preparation method thereof
Technical field
The invention belongs to field of functional materials, relate to a kind of multiferroic Bi 0.92-xho 0.08aE xfe 0.97mn 0.03o 3film and preparation method thereof.
Background technology
BiFeO 3(BFO) at room temperature there is ferroelectricity and antiferromagnetism simultaneously, be considered to one of multi-iron material with applications well potentiality.BFO belongs to R3c point group, and be tripartite's perovskite structure of distortion, be minority can be at room temperature one of multi-iron material of G type antiferromagnetic order (Neel temperature 380 DEG C) and ferroelectric order (Curie temperature 810 DEG C) simultaneously.Under BFO room temperature, there is magneto-electric coupled character, in message memory, spin electric device and pyroelectric effect etc., have potential application prospect.But in the preparation process of BFO, due to the volatilization of Bi, material internal forms Lacking oxygen, and simultaneously owing to there is appraising at the current rate of Fe, its leakage conductance is larger.Therefore, the ferroelectric properties of BFO is generally poor, the more difficult mensuration of its ferroelectric hysteresis loop.On the other hand, special antiferromagnetic spiral magnetic structure makes the magnetic of BFO very weak, and these all significantly limit the application of BFO.
Summary of the invention
The object of the present invention is to provide a kind of multiferroic Bi 0.92-xho 0.08aE xfe 0.97mn 0.03o 3film and preparation method thereof, effectively can reduce BiFeO 3the leakage current of film, improves its ferroelectric and ferromagnetic property simultaneously.
To achieve these goals, the present invention adopts following technical scheme:
A kind of multiferroic Bi 0.92-xho 0.08aE xfe 0.97mn 0.03o 3film, its chemical formula is: Bi 0.92-xho 0.08aE xfe 0.97mn 0.03o 3, AE is Ca, Ba or Sr, x=0.01 ~ 0.08.
Its crystal formation belongs to the perovskite structure of distortion, is rhombohedral system, and space group is R3m (160).
Its leakage current density tested under electric field at 200kV/cm is 3.68 × 10 -4a/cm 2; Remnant polarization under 1kHz frequency and 1000kV/cm test electric field is 71.53 μ C/cm 2, coercive field is 420kV/cm; Saturation magnetization is at room temperature 3.7emu/cm 3, residual magnetization is 0.64emu/cm 3.
A kind of multiferroic Bi 0.92-xho 0.08aE xfe 0.97mn 0.03o 3the preparation method of film, comprises the following steps:
Step 1, by Bismuth trinitrate, holmium nitrate, nitric acid AE, iron nitrate and manganous acetate in molar ratio for 0.97-x:0.08:x:0.97:0.03 is dissolved in solvent, obtains Bi 0.92-xho 0.08aE xfe 0.97mn 0.03o 3precursor liquid, wherein AE is Ca, Ba or Sr, x=0.01 ~ 0.08, Bi 0.92-xho 0.08aE xfe 0.97mn 0.03o 3in precursor liquid, the total concn of metal ion is 0.003 ~ 0.3mol/L, and solvent is the mixed solution of ethylene glycol monomethyl ether and acetic anhydride;
Step 2, adopts spin-coating method spin coating Bi on FTO/glass substrate 0.92-xho 0.08aE xfe 0.97mn 0.03o 3precursor liquid, obtains wet film, and wet film 200 ~ 230 DEG C of bakings, obtains dry film after even glue, and dry film, 520 ~ 550 DEG C of annealing, obtains Bi 0.92-xho 0.08aE xfe 0.97mn 0.03o 3film;
Step 3, after cooling, at Bi 0.92-xho 0.08aE xfe 0.97mn 0.03o 3repeating step 2 on film, until reach desired thickness, obtains multiferroic Bi 0.92-xho 0.08aE xfe 0.97mn 0.03o 3film.
In described solvent, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is (2.5 ~ 3.5): 1.
Described step 2 is first cleaned FTO/glass substrate before carrying out, then radiation treatment under ultraviolet light, makes FTO/glass substrate surface reach atomic cleanliness degree, then spin coating Bi 0.92-xho 0.08aE xfe 0.97mn 0.03o 3precursor liquid.
Even glue rotating speed in described step 2 is 3500 ~ 4000r/min, and spin coating time is 10 ~ 20s.
Baking time in described step 2 is 8 ~ 10min.
Annealing time in described step 2 is 15 ~ 25min.
Relative to prior art, beneficial effect of the present invention is:
1. multiferroic Bi provided by the invention 0.92-xho 0.08aE xfe 0.97mn 0.03o 3the preparation method of film, selects alkaline earth element AE (AE=Ca, Sr, Ba) and lanthanon Ho to carry out BiFeO 3a position doping, select transient metal Mn carry out BiFeO 3the doping of B position, form multiferroic Bi by alkaline earth element AE, rare earth element Ho and transition metal Mn element codoped 0.92-xho 0.08aE xfe 0.97mn 0.03o 3film.Due to rare earth element Ho 3+ and transient metal Mn 2+ radius be less than Bi respectively 3+ and Fe 3+ after doping, rare earth element Ho 3+, transient metal Mn 2+can admittedly be melting into into lattice, can make the approximate bismuth ferrite crystal lattices distortion in perovskite structure originally, structural aberration aggravates, simultaneously because AE is to Bi 3+further substitute, and Mn element appraising at the current rate in annealing process, the volatilization of the Bi that can effectively draw up, reduces Fe in film 2+with the content of Lacking oxygen, crystalline network is distorted further, thus the polarizability of enhanced film under extra electric field.In addition, the distortion of this structure can suppress the spiral magnetic structure of the spatial modulation that BFO is special, discharges the macroscopic magnetization that part is potential, improves the ferromegnetism of film.
2. at present for the preparation of BiFeO 3the method of film has a lot, as chemical Vapor deposition process (CVD), magnetron sputtering method (rf magnetron sputtering), deposition of metal organic method (MOD), metal-organic chemical vapor deposition equipment method (MOCVD), liquid phase deposition (LPD), molecular beam epitaxy (MBE), pulsed laser deposition (PLD), sol-gel method (Sol-Gel) etc.Compare additive method, Sol-Gel method due to equipment simple, reaction is easily carried out, technological process temperature is low, preparation process is easy to control, and is suitable for preparing film on large surface and surface in irregular shape, and mixes some trace elements with being easy to equal and quantitative, and the advantages such as the homogeneity of molecular level can be obtained at short notice, and be widely used for preparing ferroelectric material.Adopt sol-gel method in the present invention, by alkaline earth element AE, rare earth element Ho and transition metal Mn element codoped, Bi prepared by FTO substrate 0.92-xho 0.08aE xfe 0.97mn 0.03o 3film.Present device requires simple, and experiment condition easily reaches, and doping easily controls, obtained multiferroic Bi 0.92-xho 0.08aE xfe 0.97mn 0.03o 3uniformity of film is good, and has lower leakage current density, higher anti-breakdown electric field, possesses comparatively excellent ferroelectric and ferromagnetic property simultaneously.
3. multiferroic Bi provided by the invention 0.92-xho 0.08aE xfe 0.97mn 0.03o 3film, being originally similar to alkali-doped earth elements AE, rare earth element Ho and transition metal Mn in the bismuth ferrite crystal lattices in perovskite structure, make bismuth ferrite crystal lattices distortion, structural aberration aggravates, and can reduce the content of Lacking oxygen, suppresses Fe 3+to Fe 2+change, thus reduce the defect in film, reduce the leakage conductance electric current of film, effectively improve the magnetic electricity performance of film, make the multiferroic Bi that the present invention obtains 0.92-xho 0.08aE xfe 0.97mn 0.03o 3film has ferroelectric properties and the ferromagnetic property of higher anti-breakdown electric field and excellence.
Accompanying drawing explanation
Fig. 1 is Bi prepared by the present invention 0.91ho 0.08ca 0.01fe 0.97mn 0.03o 3the XRD figure of film;
Fig. 2 is Bi prepared by the present invention 0.91ho 0.08ca 0.01fe 0.97mn 0.03o 3the SEM figure of film;
Fig. 3 is Bi prepared by the present invention 0.91ho 0.08ca 0.01fe 0.97mn 0.03o 3the leakage current density figure of film;
Fig. 4 is Bi prepared by the present invention 0.91ho 0.08ca 0.01fe 0.97mn 0.03o 3the ferroelectric hysteresis loop figure of film.
Fig. 5 is Bi prepared by the present invention 0.91ho 0.08ca 0.01fe 0.97mn 0.03o 3the magnetic hysteresis loop figure of film.
Embodiment
Below in conjunction with accompanying drawing and the present invention's preferred specific embodiment, the present invention is described in further detail.
Multiferroic Bi provided by the invention 0.92-xho 0.08aE xfe 0.97mn 0.03o 3film, wherein AE is Ca, Ba or Sr, x=0.01 ~ 0.08, and its crystal formation belongs to the perovskite structure of distortion, is rhombohedral system, and space group is R3m (160).
Embodiment 1
Step 1, for 0.96:0.08:0.01:0.97:0.03, Bismuth trinitrate, holmium nitrate, nitrocalcite, iron nitrate, manganous nitrate are dissolved in (AE=Ca in solvent in molar ratio, x=0.01, Bismuth trinitrate excessive 5%), the total concn obtaining metal ion is the stable Bi of 0.3mol/L 0.91ho 0.08ca 0.01fe 0.97mn 0.03o 3precursor liquid; Solvent is volume ratio is the ethylene glycol monomethyl ether of 3:1 and the mixed solution of acetic anhydride;
Step 2, selects FTO/glass substrate to be substrate, substrate is placed in washing composition, acetone, ethanol successively, uses ultrasonic cleaning 10min respectively, then cleans substrate with distilled water and dries up with nitrogen; The baking oven being placed in 60 DEG C again toasts 5min, takes out afterwards and leaves standstill to room temperature; Finally substrate is placed in ultraviolet radiation instrument and irradiates 40min, substrate surface is reached " atomic cleanliness degree ".Adopt spin-coating method spin coating Bi on the FTO/glass substrate of cleaning 0.91ho 0.08ca 0.01fe 0.97mn 0.03o 3precursor liquid, obtains wet film, and even glue speed is 3800r/min, and spin coating time is 15s, after even cementing bundle, toasts 9min, obtain dry film at 220 DEG C, and dry film is annealed layer by layer in atmosphere 15min at the temperature of 550 DEG C again, obtains Bi 0.91ho 0.08ca 0.01fe 0.97mn 0.03o 3film;
Step 3, after cooling, at Bi 0.91ho 0.08ca 0.01fe 0.97mn 0.03o 3repeating step 2 on film, until reach desired thickness, obtains multiferroic Bi 0.91ho 0.08ca 0.01fe 0.97mn 0.03o 3film.
Multiferroic Bi is tested with XRD 0.91ho 0.08ca 0.01fe 0.97mn 0.03o 3the thing phase composite structure of film, FE-SEM tests multiferroic Bi 0.91ho 0.08ca 0.01fe 0.97mn 0.03o 3the pattern of film surface.At multiferroic Bi 0.92-xho 0.08aE xfe 0.97mn 0.03o 30.502mm is prepared in film surface ion sputtering 2au electrode, then electrode is carried out to the anneal of 20 ~ 25min at 270 ~ 280 DEG C.Multiferroic Bi is tested again with Agilent2901A 0.91ho 0.08ca 0.01fe 0.97mn 0.03o 3the leakage current density of film, with the ferroelectric test system and test multiferroic Bi of TF2000 0.91ho 0.08ca 0.01fe 0.97mn 0.03o 3the ferroelectric properties of film, with superconductive quantum interference magnetic tester system testing multiferroic Bi 0.91ho 0.08ca 0.01fe 0.97mn 0.03o 3the ferromagnetic property of film.Result as shown in Figure 1, Figure 2, shown in Fig. 3, Fig. 4 and Fig. 5.
Fig. 1 and PDF86-1518 standard card coincide, as can be known from Fig. 1, and the multiferroic Bi of preparation 0.91ho 0.08ca 0.01fe 0.97mn 0.03o 3film has distorted perovskite structure, rhombohedral system, and space group is R3m (160), does not have impurity to occur.
Fig. 2 shows the multiferroic Bi obtained 0.91ho 0.08ca 0.01fe 0.97mn 0.03o 3film crystal grain is evenly distributed, compact structure, and grain development is good.
Fig. 3 shows Bi 0.91ho 0.08ca 0.01fe 0.97mn 0.03o 3the leakage current density of film under 200kV/cm tests electric field is 3.68 × 10 -4a/cm 2.
Fig. 4 shows Bi 0.91ho 0.08ca 0.01fe 0.97mn 0.03o 3the remnant polarization of film under 1kHz frequency and 1000kV/cm test electric field is 71.53 μ C/cm 2, coercive field is 420kV/cm.
Fig. 5 shows Bi 0.91ho 0.08ca 0.01fe 0.97mn 0.03o 3film saturation magnetization is at room temperature 3.7emu/cm 3, remnant polarization is 0.64emu/cm 3.
Embodiment 2
Step 1, for 0.94:0.08:0.03:0.97:0.03, Bismuth trinitrate, holmium nitrate, nitrocalcite, iron nitrate, manganous nitrate are dissolved in (AE=Ca in solvent in molar ratio, x=0.03, Bismuth trinitrate excessive 5%), the total concn obtaining metal ion is the stable Bi of 0.003mol/L 0.89ho 0.08ca 0.03fe 0.97mn 0.03o 3precursor liquid; Solvent is volume ratio is the ethylene glycol monomethyl ether of 2.5:1 and the mixed solution of acetic anhydride;
Step 2, selects FTO/glass substrate to be substrate, substrate is placed in washing composition, acetone, ethanol successively, uses ultrasonic cleaning 10min respectively, then cleans substrate with distilled water and dries up with nitrogen; The baking oven being placed in 60 DEG C again toasts 5min, takes out afterwards and leaves standstill to room temperature; Finally substrate is placed in ultraviolet radiation instrument and irradiates 40min, substrate surface is reached " atomic cleanliness degree ".Adopt spin-coating method spin coating Bi on the FTO/glass substrate of cleaning 0.89ho 0.08ca 0.03fe 0.97mn 0.03o 3precursor liquid, obtains wet film, and even glue speed is 3500r/min, and spin coating time is 20s, after even cementing bundle, toasts 8min, obtain dry film at 230 DEG C, and dry film is annealed layer by layer in atmosphere 25min at the temperature of 520 DEG C again, obtains Bi 0.89ho 0.08ca 0.03fe 0.97mn 0.03o 3film;
Step 3, after cooling, at Bi 0.89ho 0.08ca 0.03fe 0.97mn 0.03o 3repeating step 2 on film, until reach desired thickness, obtains multiferroic Bi 0.89ho 0.08ca 0.03fe 0.97mn 0.03o 3film.
Embodiment 3
Step 1, for 0.92:0.08:0.05:0.97:0.03, Bismuth trinitrate, holmium nitrate, nitrocalcite, iron nitrate, manganous nitrate are dissolved in (AE=Ca in solvent in molar ratio, x=0.05, Bismuth trinitrate excessive 5%), the total concn obtaining metal ion is the stable Bi of 0.01mol/L 0.87ho 0.08ca 0.05fe 0.97mn 0.03o 3precursor liquid; Solvent is volume ratio is the ethylene glycol monomethyl ether of 3.5:1 and the mixed solution of acetic anhydride;
Step 2, selects FTO/glass substrate to be substrate, substrate is placed in washing composition, acetone, ethanol successively, uses ultrasonic cleaning 10min respectively, then cleans substrate with distilled water and dries up with nitrogen; The baking oven being placed in 60 DEG C again toasts 5min, takes out afterwards and leaves standstill to room temperature; Finally substrate is placed in ultraviolet radiation instrument and irradiates 40min, substrate surface is reached " atomic cleanliness degree ".Adopt spin-coating method spin coating Bi on the FTO/glass substrate of cleaning 0.87ho 0.08ca 0.05fe 0.97mn 0.03o 3precursor liquid, obtains wet film, and even glue speed is 3600r/min, and spin coating time is 18s, after even cementing bundle, toasts 9.5min, obtain dry film at 210 DEG C, and dry film is annealed layer by layer in atmosphere 22min at the temperature of 530 DEG C again, obtains Bi 0.87ho 0.08ca 0.05fe 0.97mn 0.03o 3film;
Step 3, after cooling, at Bi 0.87ho 0.08ca 0.05fe 0.97mn 0.03o 3repeating step 2 on film, until reach desired thickness, obtains multiferroic Bi 0.87ho 0.08ca 0.05fe 0.97mn 0.03o 3film.
Embodiment 4
Step 1, for 0.9:0.08:0.07:0.97:0.03, Bismuth trinitrate, holmium nitrate, nitrate of baryta, iron nitrate, manganous nitrate are dissolved in (AE=Ba in solvent in molar ratio, x=0.07, Bismuth trinitrate excessive 5%), the total concn obtaining metal ion is the stable Bi of 0.05mol/L 0.85ho 0.08ba 0.07fe 0.97mn 0.03o 3precursor liquid; Solvent is volume ratio is the ethylene glycol monomethyl ether of 2.8:1 and the mixed solution of acetic anhydride;
Step 2, selects FTO/glass substrate to be substrate, substrate is placed in washing composition, acetone, ethanol successively, uses ultrasonic cleaning 10min respectively, then cleans substrate with distilled water and dries up with nitrogen; The baking oven being placed in 60 DEG C again toasts 5min, takes out afterwards and leaves standstill to room temperature; Finally substrate is placed in ultraviolet radiation instrument and irradiates 40min, substrate surface is reached " atomic cleanliness degree ".Adopt spin-coating method spin coating Bi on the FTO/glass substrate of cleaning 0.85ho 0.08ba 0.07fe 0.97mn 0.03o 3precursor liquid, obtains wet film, and even glue speed is 3700r/min, and spin coating time is 16s, after even cementing bundle, toasts 10min, obtain dry film at 200 DEG C, and dry film is annealed layer by layer in atmosphere 18min at the temperature of 540 DEG C again, obtains Bi 0.85ho 0.08ba 0.07fe 0.97mn 0.03o 3film;
Step 3, after cooling, at Bi 0.85ho 0.08ba 0.07fe 0.97mn 0.03o 3repeating step 2 on film, until reach desired thickness, obtains multiferroic Bi 0.85ho 0.08ba 0.07fe 0.97mn 0.03o 3film.
Embodiment 5
Step 1, for 0.95:0.08:0.02:0.97:0.03, Bismuth trinitrate, holmium nitrate, nitrate of baryta, iron nitrate, manganous nitrate are dissolved in (AE=Ba in solvent in molar ratio, x=0.02, Bismuth trinitrate excessive 5%), the total concn obtaining metal ion is the stable Bi of 0.1mol/L 0.9ho 0.08ba 0.02fe 0.97mn 0.03o 3precursor liquid; Solvent is volume ratio is the ethylene glycol monomethyl ether of 3.2:1 and the mixed solution of acetic anhydride;
Step 2, selects FTO/glass substrate to be substrate, substrate is placed in washing composition, acetone, ethanol successively, uses ultrasonic cleaning 10min respectively, then cleans substrate with distilled water and dries up with nitrogen; The baking oven being placed in 60 DEG C again toasts 5min, takes out afterwards and leaves standstill to room temperature; Finally substrate is placed in ultraviolet radiation instrument and irradiates 40min, substrate surface is reached " atomic cleanliness degree ".Adopt spin-coating method spin coating Bi on the FTO/glass substrate of cleaning 0.9ho 0.08ba 0.02fe 0.97mn 0.03o 3precursor liquid, obtains wet film, and even glue speed is 3900r/min, and spin coating time is 12s, after even cementing bundle, toasts 9min, obtain dry film at 215 DEG C, and dry film is annealed layer by layer in atmosphere 17min at the temperature of 545 DEG C again, obtains Bi 0.9ho 0.08ba 0.02fe 0.97mn 0.03o 3film;
Step 3, after cooling, at Bi 0.9ho 0.08ba 0.02fe 0.97mn 0.03o 3repeating step 2 on film, until reach desired thickness, obtains multiferroic Bi 0.9ho 0.08ba 0.02fe 0.97mn 0.03o 3film.
Embodiment 6
Step 1, for 0.91:0.08:0.06:0.97:0.03, Bismuth trinitrate, holmium nitrate, strontium nitrate, iron nitrate, manganous nitrate are dissolved in (AE=Sr in solvent in molar ratio, x=0.06, Bismuth trinitrate excessive 5%), the total concn obtaining metal ion is the stable Bi of 0.2mol/L 0.86ho 0.08sr 0.06fe 0.97mn 0.03o 3precursor liquid; Solvent is volume ratio is the ethylene glycol monomethyl ether of 3:1 and the mixed solution of acetic anhydride;
Step 2, selects FTO/glass substrate to be substrate, substrate is placed in washing composition, acetone, ethanol successively, uses ultrasonic cleaning 10min respectively, then cleans substrate with distilled water and dries up with nitrogen; The baking oven being placed in 60 DEG C again toasts 5min, takes out afterwards and leaves standstill to room temperature; Finally substrate is placed in ultraviolet radiation instrument and irradiates 40min, substrate surface is reached " atomic cleanliness degree ".Adopt spin-coating method spin coating Bi on the FTO/glass substrate of cleaning 0.86ho 0.08sr 0.06fe 0.97mn 0.03o 3precursor liquid, obtains wet film, and even glue speed is 4000r/min, and spin coating time is 10s, after even cementing bundle, toasts 10min, obtain dry film at 205 DEG C, and dry film is annealed layer by layer in atmosphere 20min at the temperature of 535 DEG C again, obtains Bi 0.86ho 0.08sr 0.06fe 0.97mn 0.03o 3film;
Step 3, after cooling, at Bi 0.86ho 0.08sr 0.06fe 0.97mn 0.03o 3repeating step 2 on film, until reach desired thickness, obtains multiferroic Bi 0.86ho 0.08sr 0.06fe 0.97mn 0.03o 3film.
Embodiment 7
Step 1, for 0.89:0.08:0.08:0.97:0.03, Bismuth trinitrate, holmium nitrate, strontium nitrate, iron nitrate, manganous nitrate are dissolved in (AE=Sr in solvent in molar ratio, x=0.08, Bismuth trinitrate excessive 5%), the total concn obtaining metal ion is the stable Bi of 0.15mol/L 0.84ho 0.08sr 0.08fe 0.97mn 0.03o 3precursor liquid; Solvent is volume ratio is the ethylene glycol monomethyl ether of 3:1 and the mixed solution of acetic anhydride;
Step 2, selects FTO/glass substrate to be substrate, substrate is placed in washing composition, acetone, ethanol successively, uses ultrasonic cleaning 10min respectively, then cleans substrate with distilled water and dries up with nitrogen; The baking oven being placed in 60 DEG C again toasts 5min, takes out afterwards and leaves standstill to room temperature; Finally substrate is placed in ultraviolet radiation instrument and irradiates 40min, substrate surface is reached " atomic cleanliness degree ".Adopt spin-coating method spin coating Bi on the FTO/glass substrate of cleaning 0.84ho 0.08sr 0.08fe 0.97mn 0.03o 3precursor liquid, obtains wet film, and even glue speed is 3800r/min, and spin coating time is 14s, after even cementing bundle, toasts 8.5min, obtain dry film at 225 DEG C, and dry film is annealed layer by layer in atmosphere 23min at the temperature of 525 DEG C again, obtains Bi 0.84ho 0.08sr 0.08fe 0.97mn 0.03o 3film;
Step 3, after cooling, at Bi 0.84ho 0.08sr 0.08fe 0.97mn 0.03o 3repeating step 2 on film, until reach desired thickness, obtains multiferroic Bi 0.84ho 0.08sr 0.08fe 0.97mn 0.03o 3film.
Present device requires simple, and experiment condition easily reaches, and the uniformity of film of preparation is better, doping easily controls, and by the suitable selection of doping, can increase substantially the ferroelectric properties of film, reduce the leakage current density of film, improve the ferromegnetism of film simultaneously.
Above said content is in conjunction with concrete preferred implementation further description made for the present invention, it not whole or unique embodiment, the conversion of those of ordinary skill in the art by reading specification sheets of the present invention to any equivalence that technical solution of the present invention is taked, is claim of the present invention and contains.

Claims (9)

1. a multiferroic Bi 0.92-xho 0.08aE xfe 0.97mn 0.03o 3film, is characterized in that: its chemical formula is: Bi 0.92-xho 0.08aE xfe 0.97mn 0.03o 3, AE is Ca, Ba or Sr, x=0.01 ~ 0.08.
2. multiferroic Bi according to claim 1 0.92-xho 0.08aE xfe 0.97mn 0.03o 3film, is characterized in that: its crystal formation belongs to the perovskite structure of distortion, is rhombohedral system, and space group is R3m (160).
3. multiferroic Bi according to claim 1 and 2 0.92-xho 0.08aE xfe 0.97mn 0.03o 3film, is characterized in that: its leakage current density tested under electric field at 200kV/cm is 3.68 × 10 -4a/cm 2; Remnant polarization under 1kHz frequency and 1000kV/cm test electric field is 71.53 μ C/cm 2, coercive field is 420kV/cm; Saturation magnetization is at room temperature 3.7emu/cm 3, residual magnetization is 0.64emu/cm 3.
4. a multiferroic Bi 0.92-xho 0.08aE xfe 0.97mn 0.03o 3the preparation method of film, is characterized in that, comprises the following steps:
Step 1, by Bismuth trinitrate, holmium nitrate, nitric acid AE, iron nitrate and manganous acetate in molar ratio for 0.97-x:0.08:x:0.97:0.03 is dissolved in solvent, obtains Bi 0.92-xho 0.08aE xfe 0.97mn 0.03o 3precursor liquid, wherein AE is Ca, Ba or Sr, x=0.01 ~ 0.08, Bi 0.92-xho 0.08aE xfe 0.97mn 0.03o 3in precursor liquid, the total concn of metal ion is 0.003 ~ 0.3mol/L, and solvent is the mixed solution of ethylene glycol monomethyl ether and acetic anhydride;
Step 2, adopts spin-coating method spin coating Bi on FTO/glass substrate 0.92-xho 0.08aE xfe 0.97mn 0.03o 3precursor liquid, obtains wet film, and wet film 200 ~ 230 DEG C of bakings, obtains dry film after even glue, and dry film, 520 ~ 550 DEG C of annealing, obtains Bi 0.92-xho 0.08aE xfe 0.97mn 0.03o 3film;
Step 3, after cooling, at Bi 0.92-xho 0.08aE xfe 0.97mn 0.03o 3repeating step 2 on film, until reach desired thickness, obtains multiferroic Bi 0.92-xho 0.08aE xfe 0.97mn 0.03o 3film.
5. multiferroic Bi according to claim 4 0.92-xho 0.08aE xfe 0.97mn 0.03o 3the preparation method of film, is characterized in that: in described solvent, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is (2.5 ~ 3.5): 1.
6. multiferroic Bi according to claim 4 0.92-xho 0.08aE xfe 0.97mn 0.03o 3the preparation method of film, is characterized in that: described step 2 is first cleaned FTO/glass substrate before carrying out, then radiation treatment under ultraviolet light, makes FTO/glass substrate surface reach atomic cleanliness degree, then spin coating Bi 0.92-xho 0.08aE xfe 0.97mn 0.03o 3precursor liquid.
7. multiferroic Bi according to claim 4 0.92-xho 0.08aE xfe 0.97mn 0.03o 3the preparation method of film, is characterized in that: the even glue rotating speed in described step 2 is 3500 ~ 4000r/min, and spin coating time is 10 ~ 20s.
8. multiferroic Bi according to claim 4 0.92-xho 0.08aE xfe 0.97mn 0.03o 3the preparation method of film, is characterized in that: the baking time in described step 2 is 8 ~ 10min.
9. multiferroic Bi according to claim 4 0.92-xho 0.08aE xfe 0.97mn 0.03o 3the preparation method of film, is characterized in that: the annealing time of described step 2 is 15 ~ 25min.
CN201410766349.6A 2014-12-11 2014-12-11 Bi[0.92-x]Ho0.08AExFe0.97Mn0.03O3 multiferroic film and preparation method thereof Pending CN104478230A (en)

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