CN104538139A - Bi1-xRExFeO3/CoFe2O4 multiferroic composite membrane and preparation method thereof - Google Patents

Bi1-xRExFeO3/CoFe2O4 multiferroic composite membrane and preparation method thereof Download PDF

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CN104538139A
CN104538139A CN201410766087.3A CN201410766087A CN104538139A CN 104538139 A CN104538139 A CN 104538139A CN 201410766087 A CN201410766087 A CN 201410766087A CN 104538139 A CN104538139 A CN 104538139A
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谈国强
罗洋洋
董国华
任慧君
夏傲
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Shaanxi University of Science and Technology
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Abstract

The invention provides a Bi1-xRExFeO3/CoFe2O4 multiferroic composite membrane and a preparation method thereof. The composite membrane comprises a Bi1-xRExFeO3 crystalline state membrane and a CoFe2O4 crystalline state membrane which are combined together, wherein RE is Ce, Pr, Tb, Eu or Yb, x is equal to 0.05-0.15; in the preparation, Bi1-xRExFeO3 precursor solution and CoFe2O4 precursor solution are firstly prepared respectively; and then, multi-layer CoFe2O4 membrane is prepared by spinning on a substrate, and the multi-layer Bi1-xRExFeO3 membrane is prepared by spinning on the CoFe2O4 membrane, so the target product is obtained. The facility request is simple, the homogeneity of the prepared membrane is good, the chemical composition can be accurately controlled, the doping content is easily controlled, and the ferroelectric property and ferromagnetic property of the membrane are greatly improved, so the Bi1-xRExFeO3/CoFe2O4 multiferroic composite membrane has high residual polarization value and residual magnetization value.

Description

A kind of Bi 1-xrE xfeO 3/ CoFe 2o 4multiferroic composite membrane and preparation method thereof
Technical field
The invention belongs to field of functional materials, relate to a kind of Bi 1-xrE xfeO 3/ CoFe 2o 4multiferroic composite membrane and preparation method thereof.
Background technology
Single-phase magnetoelectricity multi-ferroic material also could not be applied in reality so far, mainly because the Curie temperature of most of monophase materials is lower, just have magnetoelectric effect at very low temperature, and magnetoelectric effect is very faint.Although single-phase BiFeO 3the Curie temperature of material and Neel temperature all more than room temperature, but due to BiFeO 3spiral magnetic structure, make BiFeO 3in G type antiferromagnetism, under low electric field, only show faint ferromagnetism, its less magneto-electric coupled characteristic hinders its practical application in many iron.On the contrary, multiferroic magnetic electric compound material can have the strong magnetoelectric effect under room temperature, thus has actual application value.
But limit BiFeO at present 3the maximum problem of film application is exactly low-resistivity, cannot at room temperature measure its ferroelectric property.Traditional slow annealing technique prepares BiFeO 3time, Lacking oxygen is issued to dynamic equilibrium at high annealing, and when annealing process terminates, part Lacking oxygen is detained wherein, forms the gathering of Lacking oxygen, causes the skew of oxygen dosage, and this skew makes iron valence state to fluctuate (Fe 3+be converted into Fe 2+).The fluctuation of iron valence state causes large leakage conductance, thus makes BiFeO 3leakage current is comparatively large, due to large leakage conductance makes its ferroelectricity cannot correct measurement and obtain saturated polarization.
CoFe 2o 4crystal belongs to cubic system, cube face-centered lattice, Fd3m space group.The normal spinel structure material be made up of Co-Fe-O ternary system, it is the magnetisable material of function admirable, there is high saturation and magnetic intensity, high-coercive force, high magnetic permeability, large magnetocrystalline anisotropy, large magnetostriction and high chemical stability, a kind of well magnetic recording material and magneto-optic recording material, outstanding advantage is that resistivity is high, magnetic spectrum characteristic is good, is also suitable for applying under high frequency and hyperfrequency.
How to solve BiFeO 3large and magnetic this two large problems weak of leakage conductance electric current, obtaining the multi-ferroic material of excellent performance, is the research emphasis of current single-phase magnetoelectricity multi-ferroic material.
Summary of the invention
The object of the present invention is to provide a kind of Bi 1-xrE xfeO 3/ CoFe 2o 4multiferroic composite membrane and preparation method thereof, obtained Bi 1-xrE xfeO 3/ CoFe 2o 4multiferroic composite membrane possesses excellent multi-ferrum property, has high residual polarization value and high remanent magnetization value.
To achieve these goals, the present invention adopts following technical scheme:
A kind of Bi 1-xrE xfeO 3/ CoFe 2o 4multiferroic composite membrane, comprises the lower membrane and upper layer film that are combined with each other, and wherein lower membrane is CoFe 2o 4crystalline state film, upper layer film is Bi 1-xrE xfeO 3crystalline state film, RE is Ce, Pr, Tb, Eu or Yb, x=0.05 ~ 0.15.
Described Bi 1-xrE xfeO 3the crystal formation of crystalline state film is class tetragonal phase structure, and its growth orientation is (110); CoFe 2o 4the crystal formation of crystalline state film is Emission in Cubic spinel structure, and its space group is Fd-3m.
Its crystallite dimension is 80 ~ 120nm, and under room temperature, its remanent polarization is 100 ~ 130 μ C/cm 2, remanent magnetization is 50 ~ 80emu/cm 3.
A kind of Bi 1-xrE xfeO 3/ CoFe 2o 4the preparation method of multiferroic composite membrane, comprises the following steps:
Step 1 is that 1:2 is by Co (NO in molar ratio 3) 26H 2o and Fe (NO 3) 39H 2o is dissolved in the mixed liquor of EGME and acetic anhydride, stirs, and obtains CoFe 2o 4precursor liquid, CoFe 2o 4in precursor liquid, the concentration of Co ion is 0.05 ~ 0.2mol/L;
Step 2, by Bi (NO 3) 35H 2o, nitric acid RE and Fe (NO 3) 39H 2o is dissolved in the mixed liquor of EGME and acetic anhydride for 1.05-x:x:1 in molar ratio, stirs, and obtains Bi 1-xrE xfeO 3precursor liquid, wherein RE is Ce, Pr, Tb, Eu or Yb, x=0.05 ~ 0.15, Bi 1-xrE xfeO 3in precursor liquid, the total concentration of metal ion is 0.1 ~ 0.3mol/L;
Step 3, adopts spin-coating method spin coating CoFe on FTO/glass substrate 2o 4precursor liquid, obtains CoFe 2o 4film, CoFe 2o 4film toasts to obtain dry film after even glue at 200 ~ 350 DEG C, then 600 ~ 620 DEG C of annealing, obtains crystalline state CoFe 2o 4film;
Step 4, treats crystalline state CoFe 2o 4after film cooling, at crystalline state CoFe 2o 4film repeats step 3, until reach desired thickness, obtains CoFe 2o 4crystalline state film;
Step 5, at CoFe 2o 4spin coating Bi on crystalline state film 1-xrE xfeO 3precursor liquid, obtains Bi 1-xrE xfeO 3film, toasts to obtain dry film after even glue at 200 ~ 260 DEG C, then 500 ~ 550 DEG C of annealing, obtains crystalline state Bi 1-xrE xfeO 3film;
Step 6, treats crystalline state Bi 1-xrE xfeO 3after film cooling, at crystalline state Bi 1-xrE xfeO 3film repeats step 5, until reach desired thickness, obtains Bi 1-xrE xfeO 3/ CoFe 2o 4multiferroic composite membrane.
Described CoFe 2o 4in precursor liquid, the volume ratio of EGME and acetic anhydride is (2.5 ~ 3.5): 1;
Described Bi 1-xrE xfeO 3in precursor liquid, the volume ratio of EGME and acetic anhydride is (2.5 ~ 3.5): 1;
Required time that stirs in step 1 and step 2 is 1.5 ~ 2h.
Described step 3 is first cleaned FTO/glass substrate before carrying out, then treatment with irradiation under ultraviolet light, then spin coating CoFe 2o 4precursor liquid;
Described step 5 before carrying out first to CoFe 2o 4crystalline state film carries out UV-irradiation process, then spin coating Bi 1-xrE xfeO 3precursor liquid.
Even glue rotating speed in described step 3 and step 5 is 3500 ~ 4500r/min, and spin coating time is 10 ~ 20s.
Baking time in described step 3 and step 5 after even glue is 5 ~ 15min.
Annealing time in described step 3 is 15 ~ 30min, and the annealing time in step 5 is 5 ~ 15min.
Crystalline state CoFe 2o 4the number of plies of film is 3 ~ 11 layers, crystalline state Bi 1-xrE xfeO 3the number of plies of film is 12 ~ 16 layers.
Relative to prior art, the present invention has following beneficial effect:
1. Bi provided by the invention 1-xrE xfeO 3/ CoFe 2o 4the preparation method of multiferroic composite membrane, selects rare earth elements RE to carry out BiFeO 3a position doping, effectively can improve BiFeO 3multi-ferrum property, particularly to BiFeO 3ferroelectric properties be significantly improved.This is mainly owing to 2 points, is the rare earth ion doped volatilization that effectively can reduce Bi in A position on the one hand, thus reduces the generation of Lacking oxygen; Another aspect is that the doping of rare earth ion can impel BiFeO 3structural aberration aggravates, and in film, the rollover number of electricdomain increases, thus improves BiFeO 3the ferroelectricity of film.The present invention selects CoFe simultaneously 2o 4as magnetosphere, CoFe 2o 4there is high saturation and magnetic intensity, high-coercive force, high magnetic permeability, large magnetocrystalline anisotropy, large magnetostriction and high chemical stability, be a kind of well magnetic recording material and magneto-optic recording material, and its high resistivity can play certain suppression BiFeO when forming structure of composite membrane 3the effect of leakage conductance electric current.
2. at present for the preparation of BiFeO 3and CoFe 2o 4the method of film has a lot, 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 deposition (LPD), molecular beam epitaxy (MBE), pulsed laser deposition (PLD), sol-gel process (Sol-Gel) etc.Compare additive method, Sol-Gel method, owing to not needing expensive vacuum equipment, is suitable for preparing film on large surface and surface in irregular shape, and the advantage such as chemical constituent controllable precise and be widely used for preparing ferroelectric material.And Sol-Gel method is applicable to the composite membrane of this laminated construction of preparation the present invention very much.Present device requires simple, and experiment condition easily reaches, and doping easily controls, by with magnetic CoFe 2o 4film forms the good 2-2 type composite membrane of interface state, thus obtained Bi 1-xrE xfeO 3/ CoFe 2o 4multiferroic composite membrane, obtained composite membrane uniformity is good, and has excellent multi-ferrum property and high residual polarization value and high remanent magnetization value.
3. Bi provided by the invention 1-xrE xfeO 3/ CoFe 2o 4multiferroic composite membrane is 2-2 type complex form, with A position RE ion doping BiFeO 3as ferroelectric layer, with CoFe 2o 4as magnetosphere, doping makes bismuth ferrite crystal lattices distortion, and structural aberration aggravates, and reduces Fe in film simultaneously 2+with the content of Lacking oxygen, thus the polarization intensity of enhanced film under extra electric field, improve the ferroelectric properties of film, reduce the leakage current density of film, the present invention is by the BiFeO of doping 3and CoFe 2o 4advantages get up, BiFeO can be solved simultaneously 3large and the weak two large problems of magnetic of leakage conductance electric current, the Bi obtained 1-xrE xfeO 3/ CoFe 2o 4multiferroic composite membrane has excellent multi-ferrum property and high residual polarization value and high remanent magnetization value.
Accompanying drawing explanation
Fig. 1 is Bi prepared by the present invention 0.89tb 0.11feO 3/ CoFe 2o 4the XRD figure of multiferroic composite membrane;
Fig. 2 is Bi prepared by the present invention 0.89tb 0.11feO 3/ CoFe 2o 4the SEM figure of multiferroic composite membrane; Wherein (a) schemes for surperficial SEM, and (b) schemes for section SEM;
Fig. 3 is Bi prepared by the present invention 0.89tb 0.11feO 3/ CoFe 2o 4the leakage conductance electric current of multiferroic composite membrane and the graph of a relation of electric field;
Fig. 4 is Bi prepared by the present invention 0.89tb 0.11feO 3/ CoFe 2o 4the electric hysteresis loop figure of multiferroic composite membrane.
Fig. 5 is Bi prepared by the present invention 0.89tb 0.11feO 3/ CoFe 2o 4multiferroic composite membrane magnetic hysteresis loop figure at room temperature.
Embodiment
Below in conjunction with accompanying drawing and the preferred embodiment of the invention, the present invention is described in further detail.
Bi provided by the invention 1-xrE xfeO 3/ CoFe 2o 4multiferroic composite membrane, comprises the lower membrane and upper layer film that are combined with each other, and wherein lower membrane is CoFe 2o 4crystalline state film, its crystal formation is Emission in Cubic spinel structure, and its space group is Fd-3m, and upper layer film is Bi 1-xrE xfeO 3crystalline state film, its crystal formation is class tetragonal phase structure, and its growth orientation is (110), and RE is Ce, Pr, Tb, Eu or Yb, x=0.05 ~ 0.15.The Bi that the present invention obtains 1-xrE xfeO 3/ CoFe 2o 4the crystallite dimension of multiferroic composite membrane is 80 ~ 120nm, and under room temperature, its remanent polarization is 100 ~ 130 μ C/cm 2, remanent magnetization is 50 ~ 80emu/cm 3.
Embodiment 1
Step 1 is that 1:2 is by Co (NO in molar ratio 3) 26H 2o and Fe (NO 3) 39H 2o is dissolved in the mixed liquor of EGME and acetic anhydride, stirs 2h, obtains the CoFe mixed 2o 4precursor liquid, CoFe 2o 4in precursor liquid, the concentration of Co ion is 0.1mol/L, and the volume ratio of EGME and acetic anhydride is 3:1;
Step 2, by Bi (NO 3) 35H 2o, Ce (NO 3) 36H 2o and Fe (NO 3) 39H 2o is that 0.90:0.15:1 (RE=Ce, x=0.15, bismuth nitrate is excessive) is dissolved in the mixed liquor of EGME and acetic anhydride in molar ratio, stirs 2h, obtains the Bi mixed 0.85ce 0.15feO 3precursor liquid, Bi 0.85ce 0.15feO 3in precursor liquid, the total concentration of metal ion is 0.3mol/L, and the volume ratio of EGME and acetic anhydride is 3:1;
Step 3, by the CoFe prepared 2o 4precursor liquid leaves standstill 24h, is cleaned up by FTO/glass substrate surface, and irradiates with ultraviolet radiation instrument, makes FTO/glass substrate surface reach atomic cleanliness degree, impels precursor liquid can good sprawling on substrate; Then spin coating CoFe on FTO/glass substrate 2o 4precursor liquid, obtains CoFe 2o 4film, even glue rotating speed is 4000r/min, and spin coating time is 15s, toasts 15min and obtain dry film after even cementing bundle at 200 DEG C, then at 620 DEG C of short annealing 15min, obtains crystalline state CoFe 2o 4film.
Step 4, treats crystalline state CoFe 2o 4after film cooling, at crystalline state CoFe 2o 4film repeats step 3, repeats 8 times, obtain CoFe 2o 4crystalline state film;
Step 5, by the Bi prepared 0.85ce 0.15feO 3precursor liquid leaves standstill 24h, adopts ultraviolet irradiation CoFe 2o 4crystalline state film 30min, makes CoFe 2o 4the wettability on crystalline state film surface is improved.Then at CoFe 2o 4crystalline state film surface spin coating Bi 0.85ce 0.15feO 3precursor liquid, obtains Bi 0.85ce 0.15feO 3film, even glue rotating speed is 4000r/min, and spin coating time is 15s, toasts 15min and obtain dry film after even cementing bundle at 200 DEG C, then at 550 DEG C of short annealing 5min, obtains crystalline state Bi 0.85ce 0.15feO 3film;
Step 6, treats crystalline state Bi 0.85ce 0.15feO 3after film cooling, at crystalline state Bi 0.85ce 0.15feO 3film repeats step 5, repeats 13 times, obtain the 2-2 type Bi that density high uniformity is good 0.85ce 0.15feO 3/ CoFe 2o 4multiferroic composite membrane.
Embodiment 2
Step 1 is that 1:2 is by Co (NO in molar ratio 3) 26H 2o and Fe (NO 3) 39H 2o is dissolved in the mixed liquor of EGME and acetic anhydride, stirs 2h, obtains the CoFe mixed 2o 4precursor liquid, CoFe 2o 4in precursor liquid, the concentration of Co ion is 0.15mol/L, and the volume ratio of EGME and acetic anhydride is 3:1;
Step 2, by Bi (NO 3) 35H 2o, Tb (NO 3) 36H 2o and Fe (NO 3) 39H 2o is that 0.94:0.11:1 (RE=Tb, x=0.11, bismuth nitrate excessive 5%) is dissolved in the mixed liquor of EGME and acetic anhydride in molar ratio, stirs 2h, obtains the Bi mixed 0.89tb 0.11feO 3precursor liquid, Bi 0.89tb 0.11feO 3in precursor liquid, the total concentration of metal ion is 0.3mol/L, and the volume ratio of EGME and acetic anhydride is 3:1;
Step 3, by the CoFe prepared 2o 4precursor liquid leaves standstill 24h, is cleaned up by FTO/glass substrate surface, and irradiates with ultraviolet radiation instrument, makes FTO/glass substrate surface reach atomic cleanliness degree, impels precursor liquid can good sprawling on substrate; Then spin coating CoFe on FTO/glass substrate 2o 4precursor liquid, obtains CoFe 2o 4film, even glue rotating speed is 4000r/min, and spin coating time is 15s, toasts 12min and obtain dry film after even cementing bundle at 250 DEG C, then at 620 DEG C of short annealing 15min, obtains crystalline state CoFe 2o 4film.
Step 4, treats crystalline state CoFe 2o 4after film cooling, at crystalline state CoFe 2o 4film repeats step 3, repeats 8 times, obtain CoFe 2o 4crystalline state film;
Step 5, by the Bi prepared 0.89tb 0.11feO 3precursor liquid leaves standstill 24h, adopts ultraviolet irradiation CoFe 2o 4crystalline state film 30min, makes CoFe 2o 4the wettability on crystalline state film surface is improved.Then at CoFe 2o 4crystalline state film surface spin coating Bi 0.89tb 0.11feO 3precursor liquid, obtains Bi 0.89tb 0.11feO 3film, even glue rotating speed is 4000r/min, and spin coating time is 15s, toasts 15min and obtain dry film after even cementing bundle at 200 DEG C, then at 550 DEG C of short annealing 5min, obtains crystalline state Bi 0.89tb 0.11feO 3film;
Step 6, treats crystalline state Bi 0.89tb 0.11feO 3after film cooling, at crystalline state Bi 0.89tb 0.11feO 3film repeats step 5, repeats 13 times, obtain the 2-2 type Bi that density high uniformity is good 0.89tb 0.11feO 3/ CoFe 2o 4multiferroic composite membrane.
Adopt XRD determining Bi 0.89tb 0.11feO 3/ CoFe 2o 4the thing phase composition structure of multiferroic composite membrane.Bi is measured with FE-SEM 0.89tb 0.11feO 3/ CoFe 2o 4the microscopic appearance interracial contact situation of multiferroic composite membrane.At Bi 0.89tb 0.11feO 3/ CoFe 2o 4multiferroic composite membrane surface ion Slag coating 0.502mm 2au electrode, then electrode is carried out to the annealing in process of 20 ~ 25min at 270 ~ 280 DEG C.Use TF2000 ferroelectric analyzer test b i again 0.89tb 0.11feO 3/ CoFe 2o 4the ferroelectric properties of multiferroic composite membrane.With Agilent B2900 test b i 0.89tb 0.11feO 3/ CoFe 2o 4the leakage conductance current characteristics of multiferroic composite membrane.With SQUIDMPMS-XL-7 test b i 0.89tb 0.11feO 3/ CoFe 2o 4ferromagnetic property under multiferroic composite membrane room temperature.Result is as shown in Fig. 1 ~ 5.
As can be known from Fig. 1, the Bi for preparing of the present invention 0.89tb 0.11feO 3/ CoFe 2o 4multiferroic composite membrane, wherein Bi 0.89tb 0.11feO 3mutually there is distorted perovskite structure, along with the merging of main peak in XRD can find out the situation that may there is multiphase coexistence, and show the oriented growth along (110) direction.Also can be observed more weak CoFe simultaneously 2o 4characteristic peak, there is no the appearance of other impurity in addition.Bi is described 1-xrE xfeO 3/ CoFe 2o 4the interface of multiferroic composite membrane does not generate second-phase.
The Bi of preparation can be found out from Fig. 2 (a) 0.89tb 0.11feO 3/ CoFe 2o 4multiferroic composite membrane surfacing, crystallite dimension is at 80 ~ 120nm, and the section SEM figure of composition graphs 2 (b) can find out Bi 0.89tb 0.11feO 3and CoFe 2o 4film contacts is good, and interface is clear, does not occur diffusion phenomena, and Bi is described 0.89tb 0.11feO 3/ CoFe 2o 4multiferroic composite membrane defines perfect 2-2 type laminated construction.
As shown in Figure 3, Bi 0.89tb 0.11feO 3/ CoFe 2o 4multiferroic composite membrane has lower leakage conductance current density, and under the test electric field of 100kV/cm, its leakage current density is only 4.25 × 10 -7a/cm 2.
By Bi in Fig. 4 0.89tb 0.11feO 3/ CoFe 2o 4the electric hysteresis loop that multiferroic composite membrane at room temperature records is known, and its saturated polarization is 149.2 μ C/cm 2, remanent polarization is 128.5 μ C/cm 2, coercive field is by force 504.5kV/cm.
By Bi in Fig. 5 0.89tb 0.11feO 3/ CoFe 2o 4the magnetic hysteresis loop that multiferroic composite membrane at room temperature records is known, and its saturation magnetization is 87.8emu/cm 3, remanent magnetization is 51.6emu/cm 3, coercive field is by force 1300Oe.
Embodiment 3
Step 1 is that 1:2 is by Co (NO in molar ratio 3) 26H 2o and Fe (NO 3) 39H 2o is dissolved in the mixed liquor of EGME and acetic anhydride, stirs 2h, obtains the CoFe mixed 2o 4precursor liquid, CoFe 2o 4in precursor liquid, the concentration of Co ion is 0.2mol/L, and the volume ratio of EGME and acetic anhydride is 3:1;
Step 2, by Bi (NO 3) 35H 2o, Eu (NO 3) 36H 2o and Fe (NO 3) 39H 2o is that 0.95:0.1:1 (RE=Eu, x=0.1, bismuth nitrate is excessive) is dissolved in the mixed liquor of EGME and acetic anhydride in molar ratio, stirs 2h, obtains the Bi mixed 0.9eu 0.1feO 3precursor liquid, Bi 0.9eu 0.1feO 3in precursor liquid, the total concentration of metal ion is 0.3mol/L, and the volume ratio of EGME and acetic anhydride is 3:1;
Step 3, by the CoFe prepared 2o 4precursor liquid leaves standstill 24h, is cleaned up by FTO/glass substrate surface, and irradiates with ultraviolet radiation instrument, makes FTO/glass substrate surface reach atomic cleanliness degree, impels precursor liquid can good sprawling on substrate; Then spin coating CoFe on FTO/glass substrate 2o 4precursor liquid, obtains CoFe 2o 4film, even glue rotating speed is 4000r/min, and spin coating time is 15s, toasts 8min and obtain dry film after even cementing bundle at 300 DEG C, then at 620 DEG C of short annealing 15min, obtains crystalline state CoFe 2o 4film.
Step 4, treats crystalline state CoFe 2o 4after film cooling, at crystalline state CoFe 2o 4film repeats step 3, repeats 8 times, obtain CoFe 2o 4crystalline state film;
Step 5, by the Bi prepared 0.9eu 0.1feO 3precursor liquid leaves standstill 30h, adopts ultraviolet irradiation CoFe 2o 4crystalline state film 30min, makes CoFe 2o 4the wettability on crystalline state film surface is improved.Then at CoFe 2o 4crystalline state film surface spin coating Bi 0.9eu 0.1feO 3precursor liquid, obtains Bi 0.9eu 0.1feO 3film, even glue rotating speed is 4000r/min, and spin coating time is 15s, toasts 15min and obtain dry film after even cementing bundle at 200 DEG C, then at 550 DEG C of short annealing 5min, obtains crystalline state Bi 0.9eu 0.1feO 3film;
Step 6, treats crystalline state Bi 0.9eu 0.1feO 3after film cooling, at crystalline state Bi 0.9eu 0.1feO 3film repeats step 5, repeats 13 times, obtain the 2-2 type Bi that density high uniformity is good 0.9eu 0.1feO 3/ CoFe 2o 4multiferroic composite membrane.
Embodiment 4
Step 1 is that 1:2 is by Co (NO in molar ratio 3) 26H 2o and Fe (NO 3) 39H 2o is dissolved in the mixed liquor of EGME and acetic anhydride, stirs 1.5h, obtains the CoFe mixed 2o 4precursor liquid, CoFe 2o 4in precursor liquid, the concentration of Co ion is 0.2mol/L, and the volume ratio of EGME and acetic anhydride is 2.5:1;
Step 2, by Bi (NO 3) 35H 2o, Yb (NO 3) 36H 2o and Fe (NO 3) 39H 2o is that 0.95:0.1:1 (RE=Yb, x=0.1, bismuth nitrate excessive 5%) is dissolved in the mixed liquor of EGME and acetic anhydride in molar ratio, stirs 1.5h, obtains the Bi mixed 0.9yb 0.1feO 3precursor liquid, Bi 0.9yb 0.1feO 3in precursor liquid, the total concentration of metal ion is 0.1mol/L, and the volume ratio of EGME and acetic anhydride is 2.5:1;
Step 3, by the CoFe prepared 2o 4precursor liquid leaves standstill 24h, is cleaned up by FTO/glass substrate surface, and irradiates with ultraviolet radiation instrument, makes FTO/glass substrate surface reach atomic cleanliness degree, impels precursor liquid can good sprawling on substrate; Then spin coating CoFe on FTO/glass substrate 2o 4precursor liquid, obtains CoFe 2o 4film, even glue rotating speed is 3500r/min, and spin coating time is 20s, toasts 5min and obtain dry film after even cementing bundle at 350 DEG C, then at 600 DEG C of short annealing 30min, obtains crystalline state CoFe 2o 4film.
Step 4, treats crystalline state CoFe 2o 4after film cooling, at crystalline state CoFe 2o 4film repeats step 3, repeats 2 times, obtain CoFe 2o 4crystalline state film;
Step 5, by the Bi prepared 0.9yb 0.1feO 3precursor liquid leaves standstill 32h, adopts ultraviolet irradiation CoFe 2o 4crystalline state film 30min, makes CoFe 2o 4the wettability on crystalline state film surface is improved.Then at CoFe 2o 4crystalline state film surface spin coating Bi 0.9yb 0.1feO 3precursor liquid, obtains Bi 0.9yb 0.1feO 3film, even glue rotating speed is 3500r/min, and spin coating time is 20s, toasts 5min and obtain dry film after even cementing bundle at 260 DEG C, then at 500 DEG C of short annealing 15min, obtains crystalline state Bi 0.9yb 0.1feO 3film;
Step 6, treats crystalline state Bi 0.9yb 0.1feO 3after film cooling, at crystalline state Bi 0.9yb 0.1feO 3film repeats step 5, repeats 11 times, obtain the 2-2 type Bi that density high uniformity is good 0.9yb 0.1feO 3/ CoFe 2o 4multiferroic composite membrane.
Embodiment 5
Step 1 is that 1:2 is by Co (NO in molar ratio 3) 26H 2o and Fe (NO 3) 39H 2o is dissolved in the mixed liquor of EGME and acetic anhydride, stirs 1.8h, obtains the CoFe mixed 2o 4precursor liquid, CoFe 2o 4in precursor liquid, the concentration of Co ion is 0.05mol/L, and the volume ratio of EGME and acetic anhydride is 3.5:1;
Step 2, by Bi (NO 3) 35H 2o, Pr (NO 3) 36H 2o and Fe (NO 3) 39H 2o is that 1:0.05:1 (RE=Pr, x=0.05, bismuth nitrate is excessive) is dissolved in the mixed liquor of EGME and acetic anhydride in molar ratio, stirs 1.8h, obtains the Bi mixed 0.95pr 0.05feO 3precursor liquid, Bi 0.95pr 0.05feO 3in precursor liquid, the total concentration of metal ion is 0.2mol/L, and the volume ratio of EGME and acetic anhydride is 3.5:1;
Step 3, by the CoFe prepared 2o 4precursor liquid leaves standstill 24h, is cleaned up by FTO/glass substrate surface, and irradiates with ultraviolet radiation instrument, makes FTO/glass substrate surface reach atomic cleanliness degree, impels precursor liquid can good sprawling on substrate; Then spin coating CoFe on FTO/glass substrate 2o 4precursor liquid, obtains CoFe 2o 4film, even glue rotating speed is 4500r/min, and spin coating time is 10s, toasts 13min and obtain dry film after even cementing bundle at 220 DEG C, then at 610 DEG C of short annealing 20min, obtains crystalline state CoFe 2o 4film.
Step 4, treats crystalline state CoFe 2o 4after film cooling, at crystalline state CoFe 2o 4film repeats step 3, repeats 10 times, obtain CoFe 2o 4crystalline state film;
Step 5, by the Bi prepared 0.95pr 0.05feO 3precursor liquid leaves standstill 28h, adopts ultraviolet irradiation CoFe 2o 4crystalline state film 30min, makes CoFe 2o 4the wettability on crystalline state film surface is improved.Then at CoFe 2o 4crystalline state film surface spin coating Bi 0.95pr 0.05feO 3precursor liquid, obtains Bi 0.95pr 0.05feO 3film, even glue rotating speed is 4500r/min, and spin coating time is 10s, toasts 8min and obtain dry film after even cementing bundle at 240 DEG C, then at 520 DEG C of short annealing 10min, obtains crystalline state Bi 0.95pr 0.05feO 3film;
Step 6, treats crystalline state Bi 0.95pr 0.05feO 3after film cooling, at crystalline state Bi 0.95pr 0.05feO 3film repeats step 5, repeats 14 times, obtain the 2-2 type Bi that density high uniformity is good 0.95pr 0.05feO 3/ CoFe 2o 4multiferroic composite membrane.
Embodiment 6
Step 1 is that 1:2 is by Co (NO in molar ratio 3) 26H 2o and Fe (NO 3) 39H 2o is dissolved in the mixed liquor of EGME and acetic anhydride, stirs 2h, obtains the CoFe mixed 2o 4precursor liquid, CoFe 2o 4in precursor liquid, the concentration of Co ion is 0.12mol/L, and the volume ratio of EGME and acetic anhydride is 2.8:1;
Step 2, by Bi (NO 3) 35H 2o, Tb (NO 3) 36H 2o and Fe (NO 3) 39H 2o is that 0.97:0.08:1 (RE=Tb, x=0.08, bismuth nitrate excessive 5%) is dissolved in the mixed liquor of EGME and acetic anhydride in molar ratio, stirs 2h, obtains the Bi mixed 0.92tb 0.08feO 3precursor liquid, Bi 0.92tb 0.08feO 3in precursor liquid, the total concentration of metal ion is 0.15mol/L, and the volume ratio of EGME and acetic anhydride is 2.5:1;
Step 3, by the CoFe prepared 2o 4precursor liquid leaves standstill 24h, is cleaned up by FTO/glass substrate surface, and irradiates with ultraviolet radiation instrument, makes FTO/glass substrate surface reach atomic cleanliness degree, impels precursor liquid can good sprawling on substrate; Then spin coating CoFe on FTO/glass substrate 2o 4precursor liquid, obtains CoFe 2o 4film, even glue rotating speed is 3800r/min, and spin coating time is 18s, toasts 10min and obtain dry film after even cementing bundle at 280 DEG C, then at 615 DEG C of short annealing 18min, obtains crystalline state CoFe 2o 4film.
Step 4, treats crystalline state CoFe 2o 4after film cooling, at crystalline state CoFe 2o 4film repeats step 3, repeats 5 times, obtain CoFe 2o 4crystalline state film;
Step 5, by the Bi prepared 0.92tb 0.08feO 3precursor liquid leaves standstill 26h, adopts ultraviolet irradiation CoFe 2o 4crystalline state film 30min, makes CoFe 2o 4the wettability on crystalline state film surface is improved.Then at CoFe 2o 4crystalline state film surface spin coating Bi 0.92tb 0.08feO 3precursor liquid, obtains Bi 0.92tb 0.08feO 3film, even glue rotating speed is 3800r/min, and spin coating time is 18s, toasts 10min and obtain dry film after even cementing bundle at 220 DEG C, then at 510 DEG C of short annealing 8min, obtains crystalline state Bi 0.92tb 0.08feO 3film;
Step 6, treats crystalline state Bi 0.92tb 0.08feO 3after film cooling, at crystalline state Bi 0.92tb 0.08feO 3film repeats step 5, repeats 15 times, obtain the 2-2 type Bi that density high uniformity is good 0.92tb 0.08feO 3/ CoFe 2o 4multiferroic composite membrane.
Embodiment 7
Step 1 is that 1:2 is by Co (NO in molar ratio 3) 26H 2o and Fe (NO 3) 39H 2o is dissolved in the mixed liquor of EGME and acetic anhydride, stirs 2h, obtains the CoFe mixed 2o 4precursor liquid, CoFe 2o 4in precursor liquid, the concentration of Co ion is 0.18mol/L, and the volume ratio of EGME and acetic anhydride is 3.2:1;
Step 2, by Bi (NO 3) 35H 2o, Ce (NO 3) 36H 2o and Fe (NO 3) 39H 2o is that 0.92:0.13:1 (RE=Ce, x=0.13, bismuth nitrate is excessive) is dissolved in the mixed liquor of EGME and acetic anhydride in molar ratio, stirs 2h, obtains the Bi mixed 0.87ce 0.13feO 3precursor liquid, Bi 0.87ce 0.13feO 3in precursor liquid, the total concentration of metal ion is 0.25mol/L, and the volume ratio of EGME and acetic anhydride is 3.2:1;
Step 3, by the CoFe prepared 2o 4precursor liquid leaves standstill 24h, is cleaned up by FTO/glass substrate surface, and irradiates with ultraviolet radiation instrument, makes FTO/glass substrate surface reach atomic cleanliness degree, impels precursor liquid can good sprawling on substrate; Then spin coating CoFe on FTO/glass substrate 2o 4precursor liquid, obtains CoFe 2o 4film, even glue rotating speed is 4200r/min, and spin coating time is 12s, toasts 6min and obtain dry film after even cementing bundle at 320 DEG C, then at 605 DEG C of short annealing 25min, obtains crystalline state CoFe 2o 4film.
Step 4, treats crystalline state CoFe 2o 4after film cooling, at crystalline state CoFe 2o 4film repeats step 3, repeats 6 times, obtain CoFe 2o 4crystalline state film;
Step 5, by the Bi prepared 0.87ce 0.13feO 3precursor liquid leaves standstill 24h, adopts ultraviolet irradiation CoFe 2o 4crystalline state film 30min, makes CoFe 2o 4the wettability on crystalline state film surface is improved.Then at CoFe 2o 4crystalline state film surface spin coating Bi 0.87ce 0.13feO 3precursor liquid, obtains Bi 0.87ce 0.13feO 3film, even glue rotating speed is 4200r/min, and spin coating time is 12s, toasts 12min and obtain dry film after even cementing bundle at 210 DEG C, then at 530 DEG C of short annealing 12min, obtains crystalline state Bi 0.87ce 0.13feO 3film;
Step 6, treats crystalline state Bi 0.87ce 0.13feO 3after film cooling, at crystalline state Bi 0.87ce 0.13feO 3film repeats step 5, repeats 12 times, obtain the 2-2 type Bi that density high uniformity is good 0.87ce 0.13feO 3/ CoFe 2o 4multiferroic composite membrane.
The present invention adopts spin-coating method and the technique of successively annealing on FTO substrate, prepare the CoFe of density high even grain size 2o 4film.And then at CoFe 2o 4/ FTO prepares Bi 1-xrE xfeO 3film, final formation 2-2 type Bi 1-xrE xfeO 3/ CoFe 2o 4(rare earth element such as RE=Ce, Pr, Tb, Eu, Yb) multiferroic composite membrane.The present invention adopts sol gel process, equipment requirement is simple, be suitable for preparing film on large surface and surface in irregular shape, and chemical constituent controllable precise, and by rare earth doped, crystal structure is regulated and controled, thus increase substantially the ferroelectric properties of film, adopt the CoFe of ferromagnetism spinel structure simultaneously 2o 4as magnetosphere, make Bi 1-xrE xfeO 3/ CoFe 2o 4many ferroelectric propertiess of laminated film significantly improve.
The foregoing is only one embodiment of the present invention, it not whole or unique execution mode, the conversion of those of ordinary skill in the art by reading specification 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 (10)

1. a Bi 1-xrE xfeO 3/ CoFe 2o 4multiferroic composite membrane, is characterized in that: comprise the lower membrane and upper layer film that are combined with each other, and wherein lower membrane is CoFe 2o 4crystalline state film, upper layer film is Bi 1-xrE xfeO 3crystalline state film, RE is Ce, Pr, Tb, Eu or Yb, x=0.05 ~ 0.15.
2. Bi according to claim 1 1-xrE xfeO 3/ CoFe 2o 4multiferroic composite membrane, is characterized in that: described Bi 1-xrE xfeO 3the crystal formation of crystalline state film is class tetragonal phase structure, and its growth orientation is (110); CoFe 2o 4the crystal formation of crystalline state film is Emission in Cubic spinel structure, and its space group is Fd-3m.
3. Bi according to claim 1 and 2 1-xrE xfeO 3/ CoFe 2o 4multiferroic composite membrane, is characterized in that: its crystallite dimension is 80 ~ 120nm, and under room temperature, its remanent polarization is 100 ~ 130 μ C/cm 2, remanent magnetization is 50 ~ 80emu/cm 3.
4. a Bi 1-xrE xfeO 3/ CoFe 2o 4the preparation method of multiferroic composite membrane, is characterized in that, comprises the following steps:
Step 1 is that 1:2 is by Co (NO in molar ratio 3) 26H 2o and Fe (NO 3) 39H 2o is dissolved in the mixed liquor of EGME and acetic anhydride, stirs, and obtains CoFe 2o 4precursor liquid, CoFe 2o 4in precursor liquid, the concentration of Co ion is 0.05 ~ 0.2mol/L;
Step 2, by Bi (NO 3) 35H 2o, nitric acid RE and Fe (NO 3) 39H 2o is dissolved in the mixed liquor of EGME and acetic anhydride for 1.05-x:x:1 in molar ratio, stirs, and obtains Bi 1-xrE xfeO 3precursor liquid, wherein RE is Ce, Pr, Tb, Eu or Yb, x=0.05 ~ 0.15, Bi 1-xrE xfeO 3in precursor liquid, the total concentration of metal ion is 0.1 ~ 0.3mol/L;
Step 3, adopts spin-coating method spin coating CoFe on FTO/glass substrate 2o 4precursor liquid, obtains CoFe 2o 4film, CoFe 2o 4film toasts to obtain dry film after even glue at 200 ~ 350 DEG C, then 600 ~ 620 DEG C of annealing, obtains crystalline state CoFe 2o 4film;
Step 4, treats crystalline state CoFe 2o 4after film cooling, at crystalline state CoFe 2o 4film repeats step 3, until reach desired thickness, obtains CoFe 2o 4crystalline state film;
Step 5, at CoFe 2o 4spin coating Bi on crystalline state film 1-xrE xfeO 3precursor liquid, obtains Bi 1-xrE xfeO 3film, toasts to obtain dry film after even glue at 200 ~ 260 DEG C, then 500 ~ 550 DEG C of annealing, obtains crystalline state Bi 1-xrE xfeO 3film;
Step 6, treats crystalline state Bi 1-xrE xfeO 3after film cooling, at crystalline state Bi 1-xrE xfeO 3film repeats step 5, until reach desired thickness, obtains Bi 1-xrE xfeO 3/ CoFe 2o 4multiferroic composite membrane.
5. Bi according to claim 4 1-xrE xfeO 3/ CoFe 2o 4the preparation method of multiferroic composite membrane, is characterized in that: described CoFe 2o 4in precursor liquid, the volume ratio of EGME and acetic anhydride is (2.5 ~ 3.5): 1;
Described Bi 1-xrE xfeO 3in precursor liquid, the volume ratio of EGME and acetic anhydride is (2.5 ~ 3.5): 1;
Required time that stirs in step 1 and step 2 is 1.5 ~ 2h.
6. Bi according to claim 4 1-xrE xfeO 3/ CoFe 2o 4the preparation method of multiferroic composite membrane, is characterized in that: described step 3 is first cleaned FTO/glass substrate before carrying out, then treatment with irradiation under ultraviolet light, then spin coating CoFe 2o 4precursor liquid;
Described step 5 before carrying out first to CoFe 2o 4crystalline state film carries out UV-irradiation process, then spin coating Bi 1-xrE xfeO 3precursor liquid.
7. Bi according to claim 4 1-xrE xfeO 3/ CoFe 2o 4the preparation method of multiferroic composite membrane, is characterized in that: the even glue rotating speed in described step 3 and step 5 is 3500 ~ 4500r/min, and spin coating time is 10 ~ 20s.
8. Bi according to claim 4 1-xrE xfeO 3/ CoFe 2o 4the preparation method of multiferroic composite membrane, is characterized in that: the baking time in described step 3 and step 5 after even glue is 5 ~ 15min.
9. Bi according to claim 4 1-xrE xfeO 3/ CoFe 2o 4the preparation method of multiferroic composite membrane, is characterized in that: the annealing time in described step 3 is 15 ~ 30min, and the annealing time in step 5 is 5 ~ 15min.
10. Bi according to claim 4 1-xrE xfeO 3/ CoFe 2o 4the preparation method of multiferroic composite membrane, is characterized in that: crystalline state CoFe 2o 4the number of plies of film is 3 ~ 11 layers, crystalline state Bi 1-xrE xfeO 3the number of plies of film is 12 ~ 16 layers.
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