CN104445996B - Multiferroic Bi0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3-NiFe2O4 composite film and preparation method thereof - Google Patents
Multiferroic Bi0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3-NiFe2O4 composite film and preparation method thereof Download PDFInfo
- Publication number
- CN104445996B CN104445996B CN201410766816.5A CN201410766816A CN104445996B CN 104445996 B CN104445996 B CN 104445996B CN 201410766816 A CN201410766816 A CN 201410766816A CN 104445996 B CN104445996 B CN 104445996B
- Authority
- CN
- China
- Prior art keywords
- film
- nife
- crystalline state
- spin coating
- multiferroic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a multiferroic Bi0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3-NiFe2O4 composite film and a preparation method thereof. The composite film comprises a Bi0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3 crystalline state film and a NiFe2O4 crystalline state film which are compounded together. The preparation method comprises the following steps: respectively preparing a Bi0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3 precursor solution and a NiFe2O4 precursor solution; and spinning on a substrate to prepare a multilayer NiFe2O4 film, and spinning on the NiFe2O4 film to prepare a multilayer Bi0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3 film, thereby obtaining the target product. The equipment requirement is simple, the prepared film is high in uniformity, the doping amount is easy to control, and the ferroelectric properties and ferromagnetic properties of the film are greatly improved. Meanwhile, the leakage current density of the film is effectively reduced.
Description
Technical field
The invention belongs to Material Field, is related to multiferroic Bi0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3-NiFe2O4It is compound
Film and preparation method thereof.
Background technology
In recent years, BiFeO3As a kind of new iron store, with ferroelectricity and anti-ferromagnetism, and with weak
Ferromagnetism causes the great interest of people.BiFeO3Simple perovskite structure with tripartite's distortion, has simultaneously under room temperature
Ferroelectric order (TC=810 DEG C) and G type antiferromagnetic orders (TN=380 DEG C), are one of a few single phase multi-iron materials.
BiFeO3Magnetoelectricity coupling is shown in information Store, spin electric device, information Store, image, pyroelectric effect, infrared Jiao of uncooled IRFPA
The aspects such as planar array are extensively applied.However, pure phase BiFeO3There is a problem that big leakage is led, cause him to obtain saturation
Ferroelectric hysteresis loop and its weak ferromagnetism essence, so as to limit its practical application.
The content of the invention
It is an object of the invention to provide multiferroic Bi0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3-NiFe2O4Composite membrane
And preparation method thereof, the method can effectively reduce the leakage current of composite membrane, while improving the ferroelectricity and ferromagnetism of composite membrane.
To achieve these goals, the present invention is adopted the following technical scheme that：
A kind of multiferroic Bi0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3-NiFe2O4Composite membrane, including what is be combined with each other
Lower membrane and upper layer film, wherein lower membrane are NiFe2O4Crystalline state film, upper layer film is Bi0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3
Crystalline state film, RE be La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu, x=0.01～0.15.
The Bi0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3The crystal formation of crystalline state film is that tripartite's phase and Tetragonal coexist, its
The space structure group of middle tripartite's phase is R3m:R, the space structure group of Tetragonal is P4；NiFe2O4The crystal formation of crystalline state film for cube
Phase, space structure group is Fd-3m:1.
Its saturation magnetization at room temperature is 20～40emu/cm3, remanent polarization be 2～10emu/cm；
Leakage current density under 40V test voltages is 1 × 10-5～9 × 10-5A/cm2；Under 1kHz frequencies and 937kV/cm test electric fields
Saturated polarization be 70～120 μ C/cm2, remanent polarization be 50～90 μ C/cm2, coercive field be 500～800kV/
cm。
A kind of multiferroic Bi0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3-NiFe2O4The preparation method of composite membrane, including with
Lower step：
Step 1, is in molar ratio 1:2 are dissolved in ferric nitrate and nickel nitrate in EGME, add after stirring
Acetic anhydride, obtains NiFe2O4Precursor liquid；Wherein NiFe2O4Fe ion concentrations are 0.1～0.25mol/L in precursor liquid；
Step 2, is in molar ratio 1-x:0.04:x:0.94:0.04:0.02 by bismuth nitrate, strontium nitrate, nitric acid RE, nitric acid
Iron, manganese nitrate and chromic nitrate are dissolved in solvent, obtain Bi0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3Precursor solution, wherein
Bi0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3The total concentration of metal ion is 0.003～0.3mol/L, RE in precursor solution
For La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu, x=0.01～0.15, solvent be EGME and
The mixed liquor of acetic anhydride；
Step 3, using spin-coating method on FTO/glass substrates spin coating NiFe2O4Precursor liquid, obtains NiFe2O4Film,
NiFe2O4Film toasts to obtain dry film Jing after spin coating at 200～240 DEG C, anneals in atmosphere at 550～600 DEG C, obtains
Crystalline state NiFe2O4Film；
Step 4, treats crystalline state NiFe2O4After film cooling, in crystalline state NiFe2O4Repeat step 3 on film, until it reaches institute
Thickness is needed, NiFe is obtained2O4Crystalline state film；
Step 5, in NiFe2O4Spin coating Bi on crystalline state film0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3Precursor solution, obtains
Bi0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3Film, Bi0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3Film is Jing after spin coating
Dry film is toasted to obtain at 200～260 DEG C, is annealed in atmosphere at 500～550 DEG C, obtain crystalline state Bi0.96- xSr0.04RExFe0.94Mn0.04Cr0.02O3Film；
Step 6, treats crystalline state Bi0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3After film cooling, in crystalline state Bi0.96- xSr0.04RExFe0.94Mn0.04Cr0.02O3Repeat step 5 on film, until it reaches desired thickness, obtain multiferroic Bi0.96- xSr0.04RExFe0.94Mn0.04Cr0.02O3-NiFe2O4Composite membrane.
The NiFe2O4The volume ratio of EGME and acetic anhydride is (2.5～3.5) in precursor liquid:1；
The volume ratio of EGME and acetic anhydride is (2.5～3.5) in the solvent:1.
The step 3 is first cleaned to FTO/glass substrates before carrying out, then treatment with irradiation under ultraviolet light, is made
FTO/glass substrate surfaces reach atomic cleanliness degree, then spin coating NiFe2O4Precursor liquid；
The step 5 is before carrying out first to NiFe2O4Crystalline state film carries out ultraviolet light process, makes NiFe2O4Crystalline state film table
Face reaches atomic cleanliness degree, then spin coating Bi0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3Precursor solution.
Spin coating rotating speed in the step 3 and step 5 is 3500～4500r/min, and spin coating time is 10～20s.
Baking time in the step 3 and step 5 after spin coating is 5～15min.
Annealing time is 5～20min in the step 3 and step 5.
Crystalline state NiFe2O4The number of plies of film is 2～6 layers, crystalline state Bi0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3Film
The number of plies is 12～16 layers.
Relative to prior art, the invention has the advantages that：
1. multiferroic Bi that the present invention is provided0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3-NiFe2O4The preparation of composite membrane
Method, select lanthanide series rare earth elements RE (RE=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) and
Sr carries out BiFeO3A positions doping, select Cr and Mn carry out the doping of B positions, because the ionic radius of rare earth elements RE is comparable to Bi3 +, Mn and Cr radiuses are less than Fe3+, after doping, rare earth element, Mn and Cr can be melting into into lattice admittedly, can make be in approximately originally
The bismuth ferrite crystal lattices distortion of perovskite structure, structural aberration aggravation, simultaneously because Sr2+To Bi3+Further replacement, and
Mn and Cr elements appraising at the current rate in annealing process, the volatilization of the Bi that can effectively draw up reduces Fe in film2+With containing for Lacking oxygen
Amount, so as to polarization intensity of the enhanced film under extra electric field, reduces the leakage current density of film, while discharging its macroscopical magnetic
Property, improve the ferroelectricity and ferromagnetic property of film.But due to BiFeO3Itself has the essence of weak magnetic, so the present invention is combined
NiFe2O4Film is combined with it.NiFe2O4With very strong magnetic, while its magnetic coercive field and very little, are preferable composite woods
Material.The present invention passes through alkaline earth element Sr, rare earth elements RE and the element codope BiFeO of transition metal Mn, Cr tetra-3, and tie
Close ferromagnetic NiFe2O4, make obtained Bi0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3-NiFe2O4Composite membrane has simultaneously
Excellent ferroelectric properties and ferromagnetic property.
2. currently used for preparation BiFeO3The method of film has a lot, such as chemical vapour deposition technique (CVD), magnetron sputtering method
(rf magnetron sputtering), deposition of metal organic method (MOD), metal-organic chemical vapor deposition equipment method
(MOCVD), liquid phase deposition (LPD), molecular beam epitaxy (MBE), pulsed laser deposition (PLD), sol-gel process
(Sol-Gel) etc..Additive method is compared, Sol-Gel methods are simple due to equipment, and reaction is easily carried out, and reaction temperature is relatively low, easily
Operation, suitably prepares film on big surface and surface in irregular shape, easily realizes the Uniform Doped on molecular level, with
And be widely used for preparing ferroelectric material the advantages of chemical constituent controllable precise.Prepared using sol-gel process in the present invention
BiFeO3Film, by rare earth element, alkaline earth element Sr and the element codope of transition metal (Mn, Cr) four, while compound
NiFe2O4Film, on FTO substrates Bi is prepared0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3-NiFe2O4Composite membrane, equipment
It is required that simply experiment condition easily reaches, and doping is easily controlled, and can be by doping and NiFe2O4Film it is compound significantly
Degree improves BiFeO3The ferroelectric properties and ferromagnetic property of film, obtained Bi0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3-
NiFe2O4Compound film uniformity preferably, with relatively low leakage current density, higher anti-breakdown electric field, is provided simultaneously with more excellent
Ferroelectric properties and ferromagnetic property.
3. multiferroic Bi that the present invention is provided0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3-NiFe2O4Composite membrane, in original
Adulterate alkaline earth element Sr, rare earth elements RE and transition metal Mn, Cr in this approximate bismuth ferrite crystal lattices in perovskite structure,
Distort bismuth ferrite crystal lattices, structural aberration aggravation, while reducing Fe in film2+With the content of Lacking oxygen, so as to enhanced film exists
Polarization intensity under extra electric field, while discharging its macroscopic magnetization, improves the ferroelectric properties and ferromagnetic property of film, reduces thin
The leakage current density of film, and with reference to ferromagnetism, the NiFe of low coercive field2O4Film, makes the Bi of the present invention0.96- xSr0.04RExFe0.94Mn0.04Cr0.02O3-NiFe2O4Composite membrane has excellent ferroelectric properties and ferromagnetic property simultaneously.
Description of the drawings
Fig. 1 is Bi prepared by the embodiment of the present invention 40.85Sr0.04Sm0.11Fe0.94Mn0.04Cr0.02O3-NiFe2O4Composite membrane
XRD；
Fig. 2 is Bi prepared by the embodiment of the present invention 40.85Sr0.04Sm0.11Fe0.94Mn0.04Cr0.02O3-NiFe2O4Composite membrane
SEM schemes；
Fig. 3 is Bi prepared by the embodiment of the present invention 40.85Sr0.04Sm0.11Fe0.94Mn0.04Cr0.02O3-NiFe2O4Composite membrane
Leakage current density figure；
Fig. 4 is Bi prepared by the embodiment of the present invention 40.85Sr0.04Sm0.11Fe0.94Mn0.04Cr0.02O3-NiFe2O4Composite membrane
Ferroelectric hysteresis loop figure；
Fig. 5 is Bi prepared by the embodiment of the present invention 40.85Sr0.04Sm0.11Fe0.94Mn0.04Cr0.02O3-NiFe2O4Composite membrane
Hysteresis curve figure.
Specific embodiment
Below in conjunction with the accompanying drawings the present invention is described in further detail with currently preferred specific embodiment.
Multiferroic Bi that the present invention is provided0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3-NiFe2O4Composite membrane, including compound
Lower membrane together and upper layer film, wherein lower membrane are NiFe2O4Crystalline state film, upper layer film is Bi0.96- xSr0.04RExFe0.94Mn0.04Cr0.02O3Crystalline state film, RE be La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or
Lu, x=0.01～0.15.Bi0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3The crystal formation of crystalline state film is that tripartite's phase and Tetragonal are common
Deposit, wherein the space structure group of tripartite's phase is R3m:R, the space structure group of Tetragonal is P4；NiFe2O4The crystal formation of crystalline state film is
Emission in Cubic, space structure group is Fd-3m:1.Its saturation magnetization at room temperature is 20～40emu/cm3, residual polarization it is strong
Spend for 2～10emu/cm；Leakage current density under 40V test voltages is 1 × 10-5～9 × 10-5A/cm2；In 1kHz frequencies and
Saturated polarization under 937kV/cm test electric fields is 70～120 μ C/cm2, remanent polarization be 50～90 μ C/cm2, rectify
Stupid field is 500～800kV/cm.
Embodiment 1
Step 1, is in molar ratio 1 by ferric nitrate and nickel nitrate:2 are dissolved in EGME, after stirring 30min, then add
Enter acetic anhydride, obtain the stable NiFe that Fe ion concentrations are 0.15mol/L2O4The body of precursor liquid, EGME and acetic anhydride
Product is than being 3:1；
Step 2, is raw material (bismuth nitrate excess, x by bismuth nitrate, strontium nitrate, cerous nitrate, ferric nitrate, manganese nitrate and chromic nitrate
=0.01, RE=Ce), in molar ratio 0.99:0.04:0.01:0.94:0.04:0.02 EGME and vinegar for being dissolved in mixing
In acid anhydrides, the stable Bi that concentration of metal ions is 0.15mol/L is obtained0.95Ce0.04Sm0.01Fe0.94Mn0.04Cr0.02O3Forerunner
Liquid solution；Wherein the volume ratio of EGME and acetic anhydride is 3:1；
Step 3：From FTO/glass substrates be substrate, by the FTO/glass substrates of well cutting be sequentially placed into detergent,
Ultrasonic wave cleaning in acetone, ethanol, with a large amount of distilled water flushing substrates after each ultrasonic wave cleaning 10min, is finally blown with nitrogen
It is dry.Then FTO/glass substrates are put into into 60 DEG C of baking oven baking 5min, take out and stand to room temperature.Again by clean FTO/glass
Substrate is placed in ultraviolet radiation instrument and irradiates 40min, substrate surface is reached " atomic cleanliness degree ".Using spin-coating method in FTO/
Spin coating NiFe on glass substrates2O4Precursor liquid, prepares NiFe2O4Film, spin coating rotating speed is 4000r/min, and spin coating time is
15s, after spin coating terminates, toasts 10min and obtains dry film at a temperature of 220 DEG C, then anneals layer by layer in air at a temperature of 560 DEG C
17min, obtains crystalline state NiFe2O4Film；
Step 4, treats crystalline state NiFe2O4After film cooling, in crystalline state NiFe2O4Repeat step 3 on film, are repeated 3 times, and obtain
To NiFe2O4Crystalline state film；
Step 5, by NiFe2O4Crystalline state film is placed in ultraviolet radiation instrument and irradiates 40min so as to which surface reaches atomic cleanliness
Degree；Again in NiFe2O4Spin coating Bi on crystalline state film0.95Ce0.04Sm0.01Fe0.94Mn0.04Cr0.02O3Precursor solution, spin coating rotating speed is
4000r/min, spin coating time is 15s, after spin coating spin coating terminates, in 220 DEG C of temperature baking 12min dry film is obtained, then in 540 DEG C of temperature
Anneal layer by layer 8min in the lower air of degree, obtains crystalline state Bi0.95Ce0.04Sm0.01Fe0.94Mn0.04Cr0.02O3Film；
Step 6, treats crystalline state Bi0.95Ce0.04Sm0.01Fe0.94Mn0.04Cr0.02O3After film cooling, in crystalline state
Bi0.95Ce0.04Sm0.01Fe0.94Mn0.04Cr0.02O3Repeat step 5 on film, are repeated 12 times, and obtain multiferroic
Bi0.95Ce0.04Sm0.01Fe0.94Mn0.04Cr0.02O3-NiFe2O4Composite membrane.
Embodiment 2
Step 1, is in molar ratio 1 by ferric nitrate and nickel nitrate:2 are dissolved in EGME, after stirring 30min, then add
Enter acetic anhydride, obtain the stable NiFe that Fe ion concentrations are 0.1mol/L2O4The body of precursor liquid, EGME and acetic anhydride
Product is than being 2.5:1；
Step 2, is raw material (bismuth nitrate excess, x by bismuth nitrate, strontium nitrate, neodymium nitrate, ferric nitrate, manganese nitrate and chromic nitrate
=0.04, RE=Nd), in molar ratio 0.96:0.04:0.04:0.94:0.04:0.02 EGME and vinegar for being dissolved in mixing
In acid anhydrides, the stable Bi that concentration of metal ions is 0.003mol/L is obtained0.92Sr0.04Nd0.04Fe0.94Mn0.04Cr0.02O3Forerunner
Liquid solution；Wherein the volume ratio of EGME and acetic anhydride is 2.5:1；
Step 3：From FTO/glass substrates be substrate, by the FTO/glass substrates of well cutting be sequentially placed into detergent,
Ultrasonic wave cleaning in acetone, ethanol, with a large amount of distilled water flushing substrates after each ultrasonic wave cleaning 10min, is finally blown with nitrogen
It is dry.Then FTO/glass substrates are put into into 60 DEG C of baking oven baking 5min, take out and stand to room temperature.Again by clean FTO/glass
Substrate is placed in ultraviolet radiation instrument and irradiates 40min, substrate surface is reached " atomic cleanliness degree ".Using spin-coating method in FTO/
Spin coating NiFe on glass substrates2O4Precursor liquid, prepares NiFe2O4Film, spin coating rotating speed is 3500r/min, and spin coating time is
10s, after spin coating terminates, toasts 15min and obtains dry film at a temperature of 200 DEG C, then anneals layer by layer in air at a temperature of 550 DEG C
20min, obtains crystalline state NiFe2O4Film；
Step 4, treats crystalline state NiFe2O4After film cooling, in crystalline state NiFe2O4Repeat step 3 on film, are repeated 1 times, and obtain
To NiFe2O4Crystalline state film；
Step 5, by NiFe2O4Crystalline state film is placed in ultraviolet radiation instrument and irradiates 40min so as to which surface reaches atomic cleanliness
Degree；Again in NiFe2O4Spin coating Bi on crystalline state film0.92Sr0.04Nd0.04Fe0.94Mn0.04Cr0.02O3Precursor solution, spin coating rotating speed is
3500r/min, spin coating time is 10s, after spin coating spin coating terminates, in 200 DEG C of temperature baking 15min dry film is obtained, then in 500 DEG C of temperature
Anneal layer by layer 20min in the lower air of degree, obtains crystalline state Bi0.92Sr0.04Nd0.04Fe0.94Mn0.04Cr0.02O3Film；
Step 6, treats crystalline state Bi0.92Sr0.04Nd0.04Fe0.94Mn0.04Cr0.02O3After film cooling, in crystalline state
Bi0.92Sr0.04Nd0.04Fe0.94Mn0.04Cr0.02O3Repeat step 5 on film, are repeated 11 times, and obtain multiferroic
Bi0.92Sr0.04Nd0.04Fe0.94Mn0.04Cr0.02O3-NiFe2O4Composite membrane.
Embodiment 3
Step 1, is in molar ratio 1 by ferric nitrate and nickel nitrate:2 are dissolved in EGME, after stirring 30min, then add
Enter acetic anhydride, obtain the stable NiFe that Fe ion concentrations are 0.25mol/L2O4The body of precursor liquid, EGME and acetic anhydride
Product is than being 3.5:1；
Step 2, is raw material (bismuth nitrate excess, x by bismuth nitrate, strontium nitrate, europium nitrate, ferric nitrate, manganese nitrate and chromic nitrate
=0.07, RE=Eu), in molar ratio 0.93:0.04:0.07:0.94:0.04:0.02 EGME and vinegar for being dissolved in mixing
In acid anhydrides, the stable Bi that concentration of metal ions is 0.3mol/L is obtained0.89Sr0.04Eu0.07Fe0.94Mn0.04Cr0.02O3Presoma
Solution；Wherein the volume ratio of EGME and acetic anhydride is 3.5:1；
Step 3：From FTO/glass substrates be substrate, by the FTO/glass substrates of well cutting be sequentially placed into detergent,
Ultrasonic wave cleaning in acetone, ethanol, with a large amount of distilled water flushing substrates after each ultrasonic wave cleaning 10min, is finally blown with nitrogen
It is dry.Then FTO/glass substrates are put into into 60 DEG C of baking oven baking 5min, take out and stand to room temperature.Again by clean FTO/glass
Substrate is placed in ultraviolet radiation instrument and irradiates 40min, substrate surface is reached " atomic cleanliness degree ".Using spin-coating method in FTO/
Spin coating NiFe on glass substrates2O4Precursor liquid, prepares NiFe2O4Film, spin coating rotating speed is 4500r/min, and spin coating time is
20s, after spin coating terminates, toasts 5min and obtains dry film at a temperature of 240 DEG C, then anneals layer by layer in air at a temperature of 580 DEG C
11min, obtains crystalline state NiFe2O4Film；
Step 4, treats crystalline state NiFe2O4After film cooling, in crystalline state NiFe2O4Repeat step 5 on film, are repeated 3 times, and obtain
To NiFe2O4Crystalline state film；
Step 5, by NiFe2O4Crystalline state film is placed in ultraviolet radiation instrument and irradiates 40min so as to which surface reaches atomic cleanliness
Degree；Again in NiFe2O4Spin coating Bi on crystalline state film0.89Sr0.04Eu0.07Fe0.94Mn0.04Cr0.02O3Precursor solution, spin coating rotating speed is
4500r/min, spin coating time is 20s, after spin coating spin coating terminates, in 260 DEG C of temperature baking 5min dry film is obtained, then in 520 DEG C of temperature
Anneal layer by layer 14min in the lower air of degree, obtains crystalline state Bi0.89Sr0.04Eu0.07Fe0.94Mn0.04Cr0.02O3Film；
Step 6, treats crystalline state Bi0.89Sr0.04Eu0.07Fe0.94Mn0.04Cr0.02O3After film cooling, in crystalline state
Bi0.89Sr0.04Eu0.07Fe0.94Mn0.04Cr0.02O3Repeat step 5 on film, are repeated 15 times, and obtain multiferroic
Bi0.89Sr0.04Eu0.07Fe0.94Mn0.04Cr0.02O3-NiFe2O4Composite membrane.
Embodiment 4
Step 1, is in molar ratio 1 by ferric nitrate and nickel nitrate:2 are dissolved in EGME, after stirring 30min, then add
Enter acetic anhydride, obtain the stable NiFe that Fe ion concentrations are 0.2mol/L2O4The body of precursor liquid, EGME and acetic anhydride
Product is than being 3:1；
Step 2, by bismuth nitrate, strontium nitrate, samaric nitrate, ferric nitrate, manganese nitrate and chromic nitrate be raw material (bismuth nitrate excess,
X=0.11, RE=Sm), in molar ratio 0.89:0.04:0.11:0.94:0.04:0.02 EGME and vinegar for being dissolved in mixing
In acid anhydrides, the stable Bi that concentration of metal ions is 0.2mol/L is obtained0.85Sr0.04Sm0.11Fe0.94Mn0.04Cr0.02O3Presoma
Solution；Wherein the volume ratio of EGME and acetic anhydride is 3:1；
Step 3：From FTO/glass substrates be substrate, by the FTO/glass substrates of well cutting be sequentially placed into detergent,
Ultrasonic wave cleaning in acetone, ethanol, with a large amount of distilled water flushing substrates after each ultrasonic wave cleaning 10min, is finally blown with nitrogen
It is dry.Then FTO/glass substrates are put into into 60 DEG C of baking oven baking 5min, take out and stand to room temperature.Again by clean FTO/glass
Substrate is placed in ultraviolet radiation instrument and irradiates 40min, substrate surface is reached " atomic cleanliness degree ".Using spin-coating method in FTO/
Spin coating NiFe on glass substrates2O4Precursor liquid, prepares NiFe2O4Film, spin coating rotating speed is 4000r/min, and spin coating time is
15s, after spin coating terminates, toasts 10min and obtains dry film at a temperature of 220 DEG C, then anneals layer by layer in air at a temperature of 600 DEG C
5min, obtains crystalline state NiFe2O4Film；
Step 4, treats crystalline state NiFe2O4After film cooling, in crystalline state NiFe2O4Repeat step 3 on film, are repeated 3 times, and obtain
To NiFe2O4Crystalline state film；
Step 5, by NiFe2O4Crystalline state film is placed in ultraviolet radiation instrument and irradiates 40min so as to which surface reaches atomic cleanliness
Degree；Again in NiFe2O4Spin coating Bi on crystalline state film0.85Sr0.04Sm0.11Fe0.94Mn0.04Cr0.02O3Precursor solution, spin coating rotating speed is
4000r/min, spin coating time is 15s, after spin coating spin coating terminates, in 230 DEG C of temperature baking 10min dry film is obtained, then in 550 DEG C of temperature
Anneal layer by layer 5min in the lower air of degree, obtains crystalline state Bi0.85Sr0.04Sm0.11Fe0.94Mn0.04Cr0.02O3Film；
Step 6, treats crystalline state Bi0.85Sr0.04Sm0.11Fe0.94Mn0.04Cr0.02O3After film cooling, in crystalline state
Bi0.85Sr0.04Sm0.11Fe0.94Mn0.04Cr0.02O3Repeat step 5 on film, are repeated 14 times, and obtain multiferroic
Bi0.85Sr0.04Sm0.11Fe0.94Mn0.04Cr0.02O3-NiFe2O4Composite membrane.
In crystalline state Bi0.85Sr0.04Sm0.11Fe0.94Mn0.04Cr0.02O3-NiFe2O4Composite film surface ion sputtering prepares Au
Electrode, then 300 DEG C of insulations carry out electrode anneal process.
With Bi obtained in XRD testing example 40.85Sr0.04Sm0.11Fe0.94Mn0.04Cr0.02O3-NiFe2O4The thing of composite membrane
Phase composition structure, with obtained in TF2000 ferroelectricity test system and tests embodiment 4
Bi0.85Sr0.04Sm0.11Fe0.94Mn0.04Cr0.02O3-NiFe2O4The ferroelectric properties of composite membrane, obtained in FE-SEM testing example 4
Bi0.85Sr0.04Sm0.11Fe0.94Mn0.04Cr0.02O3-NiFe2O4The pattern of composite film surface, uses Agilent2901A test implementations
Bi obtained in example 40.85Sr0.04Sm0.11Fe0.94Mn0.04Cr0.02O3-NiFe2O4The leakage current density of composite membrane, it is dry with Superconducting Quantum
Relate to Bi obtained in magnetic tester system testing embodiment 40.85Sr0.04Sm0.11Fe0.94Mn0.04Cr0.02O3-NiFe2O4The iron of composite membrane
Magnetic.As a result as shown in Figure 1, Figure 2, shown in Fig. 3, Fig. 4 and Fig. 5.
Fig. 1 coincide with PDF20-0169 standard cards, it can be seen that, preparation
Bi0.85Sr0.04Sm0.11Fe0.94Mn0.04Cr0.02O3-NiFe2O4Composite membrane has distorted perovskite structure, the appearance without impurity.
Fig. 2 shows obtained Bi0.85Sr0.04Sm0.11Fe0.94Mn0.04Cr0.02O3-NiFe2O4Composite membrane has crystallite dimension
Be evenly distributed, the surface topography that compact structure and grain development are good.
Fig. 3 shows obtained Bi0.85Sr0.04Sm0.11Fe0.94Mn0.04Cr0.02O3-NiFe2O4Composite membrane is in 40V test electricity
The leakage current density of pressure is 4.2 × 10-5A/cm2。
Fig. 4 shows obtained Bi0.85Sr0.04Sm0.11Fe0.94Mn0.04Cr0.02O3-NiFe2O4Composite membrane 1kHz frequencies,
Saturated polarization under 937kV/cm test electric fields is 92.8 μ C/cm2, remanent polarization be 87.7 μ C/cm2, coercive field be
770.4kV/cm。
Fig. 5 shows obtained Bi0.85Sr0.04Sm0.11Fe0.94Mn0.04Cr0.02O3-NiFe2O4Saturation under composite membrane room temperature
The intensity of magnetization is 35.1emu/cm3, remanent magnetization be 2.25emu/cm3。
Embodiment 5
Step 1, is in molar ratio 1 by ferric nitrate and nickel nitrate:2 are dissolved in EGME, after stirring 30min, then add
Enter acetic anhydride, obtain the stable NiFe that Fe ion concentrations are 0.18mol/L2O4The body of precursor liquid, EGME and acetic anhydride
Product is than being 2.8:1；
Step 2, is raw material (bismuth nitrate excess, x by bismuth nitrate, strontium nitrate, gadolinium nitrate, ferric nitrate, manganese nitrate and chromic nitrate
=0.13, RE=Gd), in molar ratio 0.87:0.04:0.13:0.94:0.04:0.02 EGME and vinegar for being dissolved in mixing
In acid anhydrides, the stable Bi that concentration of metal ions is 0.05mol/L is obtained0.83Sr0.04Gd0.13Fe0.94Mn0.04Cr0.02O3Forerunner
Liquid solution；Wherein the volume ratio of EGME and acetic anhydride is 2.8:1；
Step 3：From FTO/glass substrates be substrate, by the FTO/glass substrates of well cutting be sequentially placed into detergent,
Ultrasonic wave cleaning in acetone, ethanol, with a large amount of distilled water flushing substrates after each ultrasonic wave cleaning 10min, is finally blown with nitrogen
It is dry.Then FTO/glass substrates are put into into 60 DEG C of baking oven baking 5min, take out and stand to room temperature.Again by clean FTO/glass
Substrate is placed in ultraviolet radiation instrument and irradiates 40min, substrate surface is reached " atomic cleanliness degree ".Using spin-coating method in FTO/
Spin coating NiFe on glass substrates2O4Precursor liquid, prepares NiFe2O4Film, spin coating rotating speed is 3800r/min, and spin coating time is
13s, after spin coating terminates, toasts 12min and obtains dry film at a temperature of 210 DEG C, then anneals layer by layer in air at a temperature of 590 DEG C
8min, obtains crystalline state NiFe2O4Film；
Step 4, treats crystalline state NiFe2O4After film cooling, in crystalline state NiFe2O4Repeat step 3 on film, are repeated 2 times, and obtain
To NiFe2O4Crystalline state film；
Step 5, by NiFe2O4Crystalline state film is placed in ultraviolet radiation instrument and irradiates 40min so as to which surface reaches atomic cleanliness
Degree；Again in NiFe2O4Spin coating Bi on crystalline state film0.83Sr0.04Gd0.13Fe0.94Mn0.04Cr0.02O3Precursor solution, spin coating rotating speed is
3800r/min, spin coating time is 13s, after spin coating spin coating terminates, in 240 DEG C of temperature baking 8min dry film is obtained, then in 530 DEG C of temperature
Anneal layer by layer 11min in the lower air of degree, obtains crystalline state Bi0.83Sr0.04Gd0.13Fe0.94Mn0.04Cr0.02O3Film；
Step 6, treats crystalline state Bi0.83Sr0.04Gd0.13Fe0.94Mn0.04Cr0.02O3After film cooling, in crystalline state
Bi0.83Sr0.04Gd0.13Fe0.94Mn0.04Cr0.02O3Repeat step 5 on film, are repeated 13 times, and obtain multiferroic
Bi0.83Sr0.04Gd0.13Fe0.94Mn0.04Cr0.02O3-NiFe2O4Composite membrane.
Embodiment 6
Step 1, is in molar ratio 1 by ferric nitrate and nickel nitrate:2 are dissolved in EGME, after stirring 30min, then add
Enter acetic anhydride, obtain the stable NiFe that Fe ion concentrations are 0.22mol/L2O4The body of precursor liquid, EGME and acetic anhydride
Product is than being 3.2:1；
Step 2, is raw material (bismuth nitrate excess, x by bismuth nitrate, strontium nitrate, holmium nitrate, ferric nitrate, manganese nitrate and chromic nitrate
=0.15, RE=Ho), in molar ratio 0.85:0.04:0.15:0.94:0.04:0.02 EGME and vinegar for being dissolved in mixing
In acid anhydrides, the stable Bi that concentration of metal ions is 0.25mol/L is obtained0.81Sr0.04Ho0.15Fe0.94Mn0.04Cr0.02O3Forerunner
Liquid solution；Wherein the volume ratio of EGME and acetic anhydride is 3.2:1；
Step 3：From FTO/glass substrates be substrate, by the FTO/glass substrates of well cutting be sequentially placed into detergent,
Ultrasonic wave cleaning in acetone, ethanol, with a large amount of distilled water flushing substrates after each ultrasonic wave cleaning 10min, is finally blown with nitrogen
It is dry.Then FTO/glass substrates are put into into 60 DEG C of baking oven baking 5min, take out and stand to room temperature.Again by clean FTO/glass
Substrate is placed in ultraviolet radiation instrument and irradiates 40min, substrate surface is reached " atomic cleanliness degree ".Using spin-coating method in FTO/
Spin coating NiFe on glass substrates2O4Precursor liquid, prepares NiFe2O4Film, spin coating rotating speed is 4200r/min, and spin coating time is
17s, after spin coating terminates, toasts 8min and obtains dry film at a temperature of 230 DEG C, then anneals layer by layer in air at a temperature of 570 DEG C
14min, obtains crystalline state NiFe2O4Film；
Step 4, treats crystalline state NiFe2O4After film cooling, in crystalline state NiFe2O4Repeat step 3 on film, are repeated 4 times, and obtain
To NiFe2O4Crystalline state film；
Step 5, by NiFe2O4Crystalline state film is placed in ultraviolet radiation instrument and irradiates 40min so as to which surface reaches atomic cleanliness
Degree；Again in NiFe2O4Spin coating Bi on crystalline state film0.81Sr0.04Ho0.15Fe0.94Mn0.04Cr0.02O3Precursor solution, spin coating rotating speed is
4200r/min, spin coating time is 17s, after spin coating spin coating terminates, in 250 DEG C of temperature baking 6min dry film is obtained, then in 510 DEG C of temperature
Anneal layer by layer 17min in the lower air of degree, obtains crystalline state Bi0.81Sr0.04Ho0.15Fe0.94Mn0.04Cr0.02O3Film；
Step 6, treats crystalline state Bi0.81Sr0.04Ho0.15Fe0.94Mn0.04Cr0.02O3After film cooling, in crystalline state
Bi0.81Sr0.04Ho0.15Fe0.94Mn0.04Cr0.02O3Repeat step 5 on film, are repeated 12 times, and obtain multiferroic
Bi0.81Sr0.04Ho0.15Fe0.94Mn0.04Cr0.02O3-NiFe2O4Composite membrane.
The RE in nitric acid RE used in above-described embodiment can also be La, Pr, Tb, Dy, Er, Tm, Yb or Lu.
Present device requires that simply experiment condition easily reaches, and the uniformity of film of preparation preferably, easily control by doping
System, by the appropriate selection of doping, and NiFe2O4The addition of laminated magnetic film, can increase substantially the ferroelectricity of film
Can, the leakage current density of film is reduced, while improving the ferromagnetism of film.
Above said content is to combine specific preferred embodiment further description made for the present invention, is not
Whole or unique embodiment, those of ordinary skill in the art are by reading description of the invention to technical solution of the present invention
Any equivalent conversion taken, the claim for being the present invention is covered.
Claims (8)
1. a kind of multiferroic Bi0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3-NiFe2O4Composite membrane, it is characterised in that：Including multiple
The lower membrane being combined and upper layer film, wherein lower membrane are NiFe2O4Crystalline state film, upper layer film is Bi0.96- xSr0.04RExFe0.94Mn0.04Cr0.02O3Crystalline state film, RE be La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or
Lu, x=0.01～0.15；Bi0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3The crystal formation of crystalline state film is that tripartite's phase and Tetragonal are common
Deposit, wherein the space structure group of tripartite's phase is R3m:R, the space structure group of Tetragonal is P4；NiFe2O4The crystal formation of crystalline state film is
Emission in Cubic, space structure group is Fd-3m:1；Multiferroic Bi0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3-NiFe2O4Composite membrane
Saturation magnetization at room temperature is 20～40emu/cm3, remanent polarization be 2～10emu/cm3；In 40V test voltages
Under leakage current density be 1 × 10-5～9 × 10-5A/cm2；Saturated polarization under 1kHz frequencies and 937kV/cm test electric fields
Intensity is 70～120 μ C/cm2, remanent polarization be 50～90 μ C/cm2, coercive field be 500～800kV/cm.
2. multiferroic Bi described in claim 10.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3-NiFe2O4The preparation side of composite membrane
Method, it is characterised in that comprise the following steps：
Step 1, is in molar ratio 1:2 are dissolved in ferric nitrate and nickel nitrate in EGME, and acetic acid is added after stirring
Acid anhydride, obtains NiFe2O4Precursor liquid；Wherein NiFe2O4Fe ion concentrations are 0.1～0.25mol/L in precursor liquid；
Step 2, is in molar ratio 1-x:0.04:x:0.94:0.04:0.02 by bismuth nitrate, strontium nitrate, nitric acid RE, ferric nitrate, nitre
Sour manganese and chromic nitrate are dissolved in solvent, obtain Bi0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3Precursor solution, wherein Bi0.96- xSr0.04RExFe0.94Mn0.04Cr0.02O3In precursor solution the total concentration of metal ion be 0.003～0.3mol/L, RE be La,
Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu, x=0.01～0.15, solvent is EGME and acetic acid
The mixed liquor of acid anhydride；
Step 3, using spin-coating method on FTO/glass substrates spin coating NiFe2O4Precursor liquid, obtains NiFe2O4Film, NiFe2O4It is thin
Film toasts to obtain dry film Jing after spin coating at 200～240 DEG C, anneals in atmosphere at 550～600 DEG C, obtains crystalline state
NiFe2O4Film；
Step 4, treats crystalline state NiFe2O4After film cooling, in crystalline state NiFe2O4Repeat step 3 on film, until it reaches required thickness
Degree, obtains NiFe2O4Crystalline state film；
Step 5, in NiFe2O4Spin coating Bi on crystalline state film0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3Precursor solution, obtains
Bi0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3Film, Bi0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3Film Jing after spin coating
Dry film is toasted to obtain at 200～260 DEG C, is annealed in atmosphere at 500～550 DEG C, obtain crystalline state Bi0.96- xSr0.04RExFe0.94Mn0.04Cr0.02O3Film；
Step 6, treats crystalline state Bi0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3After film cooling, in crystalline state Bi0.96- xSr0.04RExFe0.94Mn0.04Cr0.02O3Repeat step 5 on film, until it reaches desired thickness, obtain multiferroic Bi0.96- xSr0.04RExFe0.94Mn0.04Cr0.02O3-NiFe2O4Composite membrane.
3. multiferroic Bi according to claim 20.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3-NiFe2O4The system of composite membrane
Preparation Method, it is characterised in that：The NiFe2O4The volume ratio of EGME and acetic anhydride is (2.5～3.5) in precursor liquid:1；
The volume ratio of EGME and acetic anhydride is (2.5～3.5) in the solvent:1.
4. multiferroic Bi according to claim 20.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3-NiFe2O4The system of composite membrane
Preparation Method, it is characterised in that：The step 3 is first cleaned to FTO/glass substrates before carrying out, then under ultraviolet light according to
Process is penetrated, makes FTO/glass substrate surfaces reach atomic cleanliness degree, then spin coating NiFe2O4Precursor liquid；
The step 5 is before carrying out first to NiFe2O4Crystalline state film carries out ultraviolet light process, makes NiFe2O4Crystalline state film surface reaches
To atomic cleanliness degree, then spin coating Bi0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3Precursor solution.
5. multiferroic Bi according to claim 20.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3-NiFe2O4The system of composite membrane
Preparation Method, it is characterised in that：Spin coating rotating speed in the step 3 and step 5 is 3500～4500r/min, and spin coating time is 10
～20s.
6. multiferroic Bi according to claim 20.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3-NiFe2O4The system of composite membrane
Preparation Method, it is characterised in that：Baking time in the step 3 and step 5 after spin coating is 5～15min.
7. multiferroic Bi according to claim 20.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3-NiFe2O4The system of composite membrane
Preparation Method, it is characterised in that：Annealing time is 5～20min in the step 3 and step 5.
8. multiferroic Bi according to claim 20.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3-NiFe2O4The system of composite membrane
Preparation Method, it is characterised in that：Crystalline state NiFe2O4The number of plies of film is 2～6 layers, crystalline state Bi0.96- xSr0.04RExFe0.94Mn0.04Cr0.02O3The number of plies of film is 12～16 layers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410766816.5A CN104445996B (en) | 2014-12-11 | 2014-12-11 | Multiferroic Bi0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3-NiFe2O4 composite film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410766816.5A CN104445996B (en) | 2014-12-11 | 2014-12-11 | Multiferroic Bi0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3-NiFe2O4 composite film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104445996A CN104445996A (en) | 2015-03-25 |
| CN104445996B true CN104445996B (en) | 2017-04-26 |
Family
ID=52892846
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410766816.5A Active CN104445996B (en) | 2014-12-11 | 2014-12-11 | Multiferroic Bi0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3-NiFe2O4 composite film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104445996B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105837196A (en) * | 2016-03-29 | 2016-08-10 | 陕西科技大学 | Bi0.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4 ferromagnetic composite film and preparation method thereof |
| CN105837199B (en) * | 2016-03-31 | 2019-01-25 | 陕西科技大学 | A kind of Bi0.96Sr0.04Fe0.98-xMnxCo0.02O3More iron thin films and preparation method thereof |
| CN107117830B (en) * | 2017-04-18 | 2019-12-13 | 陕西科技大学 | LaSrMnCo co-doped bismuth ferrite multiferroic film and preparation method thereof |
| CN107140848B (en) * | 2017-04-18 | 2019-10-11 | 陕西科技大学 | A kind of GdSrMnCo is co-doped with bismuth ferrite superlattice film and preparation method thereof |
| CN107140849B (en) * | 2017-04-18 | 2019-10-11 | 陕西科技大学 | A kind of LaSrMnCo/GdSrMnCo is co-doped with bismuth ferrite superlattice film and preparation method thereof |
| CN107021649B (en) * | 2017-04-18 | 2019-06-07 | 陕西科技大学 | A kind of LaSrMnCo is co-doped with bismuth ferrite superlattice film and preparation method thereof |
| CN107032631B (en) * | 2017-04-18 | 2019-10-29 | 陕西科技大学 | A kind of GdSrMnCo is co-doped with more iron thin films of bismuth ferrite and preparation method thereof |
| CN109273255B (en) * | 2018-09-18 | 2021-04-23 | 陕西科技大学 | High-ferromagnetism LSMO thin film and preparation method thereof |
| CN109205683B (en) * | 2018-09-18 | 2020-08-25 | 陕西科技大学 | BLSFMC/CFLO composite film with symmetrical rectangular hysteresis loop and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601247B (en) * | 2013-11-04 | 2015-06-24 | 陕西科技大学 | Bi1-xSmxFe0.94Mn0.04Cr0.02O3 ferroelectric film with high remanent polarization and low leakage current density and preparation method thereof |
| CN103771527B (en) * | 2013-12-20 | 2015-08-12 | 陕西科技大学 | A kind of Bi of low coercive field 0.92dy 0.08fe 1-xmn xo 3ferroelectric membranc and preparation method thereof |
| CN103833349A (en) * | 2014-01-02 | 2014-06-04 | 陕西科技大学 | La0.1Bi0.9FeO3/NiFe2O4 magnetoelectric composite powder and preparation method thereof |
-
2014
- 2014-12-11 CN CN201410766816.5A patent/CN104445996B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104445996A (en) | 2015-03-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104445996B (en) | Multiferroic Bi0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3-NiFe2O4 composite film and preparation method thereof | |
| CN104538140B (en) | Multiferroic Bi1-xRExFe0.97-yMn0.03TMyO3/CoFe2O4 composite film and preparation method thereof | |
| CN104478234B (en) | A kind of Bi0.90er0.10fe0.96co0.02mn0.02o3/ Mn1-xcoxfe2o4composite membrane and preparation method thereof | |
| CN105271798B (en) | A kind of high-ferromagnetic can be with the Bi of ferroelectric properties0.9Er0.1Fe1‑xCoxO3Film and preparation method thereof | |
| CN105837196A (en) | Bi0.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4 ferromagnetic composite film and preparation method thereof | |
| CN104478235B (en) | A kind of multiferroic Bi0.98‑xSr0.02RExFe0.97Mn0.03O3‑CuFe2O4Composite membrane and preparation method thereof | |
| CN103044018A (en) | Method for preparing Bi0.85Sm0.15Fe1-xCrxO3 ferroelectric film via sol-gel process | |
| CN104476832B (en) | A kind of laminated BiFe0.97-xmn0.03tMxo3/ CoFe2o4multiferroic composite membrane and preparation method thereof | |
| CN103121836A (en) | Method for preparing BiFe1-xCrxO3 ferroelectric film by using sol-gel method | |
| CN105906221B (en) | A kind of multiferroic Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4Composite membrane and preparation method thereof | |
| CN104575907B (en) | Bi1-xRExFe1-yTMyO3/CoFe2O4 multiferroic composite film and preparation method thereof | |
| CN104478236A (en) | Bi0.92Ho0.08Fe0.97Mn0.03O3-Zn1-xNixFe2O4 multiferroic composite film and preparation method thereof | |
| CN104478228B (en) | A kind of Bi0.85‑xPr0.15AExFe0.97Mn0.03O3Ferroelectric thin film and preparation method thereof | |
| CN104478229B (en) | A kind of Bi1-xrExfe0.96co0.02mn0.02o3ferroelectric thin film and preparation method thereof | |
| CN104538139B (en) | Bi1-xRExFeO3/CoFe2O4 multiferroic composite membrane and preparation method thereof | |
| CN105859152B (en) | A kind of high magnetism Bi0.96Sr0.04FeO3Base/CoFe2O4Laminated film and preparation method thereof | |
| CN109111127B (en) | BLSFMC/CMFO film with resistance switching effect and preparation method thereof | |
| CN103771527A (en) | Bi0.92Dy0.08Fe(1-x)MnxO3 ferroelectric film with low coercive field and preparation method of film | |
| CN103601247B (en) | Bi1-xSmxFe0.94Mn0.04Cr0.02O3 ferroelectric film with high remanent polarization and low leakage current density and preparation method thereof | |
| CN107082576B (en) | HoSrMnNi codoped bismuth ferrite multiferroic film and preparation method thereof | |
| CN105859273B (en) | A kind of 2-2 type BiFeO3-CuFe2O4 laminated film and preparation method thereof | |
| CN103601249B (en) | A kind of high remnant polarization and high-k BiFe 0.96-ymn 0.04cr yo 3ferroelectric membranc and preparation method thereof | |
| CN104478230A (en) | Bi[0.92-x]Ho0.08AExFe0.97Mn0.03O3 multiferroic film and preparation method thereof | |
| CN107140849B (en) | A kind of LaSrMnCo/GdSrMnCo is co-doped with bismuth ferrite superlattice film and preparation method thereof | |
| CN107021649A (en) | A kind of LaSrMnCo is co-doped with bismuth ferrite superlattice film and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |