CN104478234B - A kind of Bi0.90er0.10fe0.96co0.02mn0.02o3/ Mn1-xcoxfe2o4composite membrane and preparation method thereof - Google Patents
A kind of Bi0.90er0.10fe0.96co0.02mn0.02o3/ Mn1-xcoxfe2o4composite membrane and preparation method thereof Download PDFInfo
- Publication number
- CN104478234B CN104478234B CN201410764660.7A CN201410764660A CN104478234B CN 104478234 B CN104478234 B CN 104478234B CN 201410764660 A CN201410764660 A CN 201410764660A CN 104478234 B CN104478234 B CN 104478234B
- Authority
- CN
- China
- Prior art keywords
- film
- crystalline state
- thin film
- spin coating
- obtains
- 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
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Compounds Of Iron (AREA)
- Thin Magnetic Films (AREA)
Abstract
The invention provides a kind of Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3/Mn1‑xCoxFe2O4Composite membrane and preparation method thereof, this composite membrane includes the Bi being combined with each other0.90Er0.10Fe0.96Co0.02Mn0.02O3Crystalline state film and Mn1‑ xCoxFe2O4Crystalline state film；Bi is prepared the most respectively during preparation0.90Er0.10Fe0.96Co0.02Mn0.02O3Precursor solution and Mn1‑ xCoxFe2O4Precursor liquid；Then on substrate, multilamellar Mn is prepared in spin coating1‑xCoxFe2O4Film, then at Mn1‑xCoxFe2O4On film, multilamellar Bi is prepared in spin coating0.90Er0.10Fe0.96Co0.02Mn0.02O3Film, obtains target product.Present device requires simple, and the uniformity of film of preparation is preferable, and doping is easily controlled, and ferroelectric properties and the ferromagnetic property of thin film is greatly improved, effectively reduces the leakage current density of thin film simultaneously.
Description
Technical field
The invention belongs to field of functional materials, relate to laminated film and preparation method thereof, be specifically related to a kind of Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3/Mn1-xCoxFe2O4Composite membrane and preparation method thereof.
Background technology
BiFeO3There is one of multi-iron material of ferroelectric order (TC=810 DEG C) and G type antiferromagnetic order (TN=380 DEG C) as minority the most simultaneously, due to its magneto-electric coupled character show at information storage, spin electric device, image, the extensive application of the aspect such as pyroelectric effect, uncooled infrared focal plane array.In recent years around BiFeO3The research of multi-iron material gets more and more.Pure phase BiFeO3There is the perovskite structure (belonging to R3c point group) of distortion, six oxygen atoms at the Fe atom at structure cell center and the center of area define ferrum oxygen octahedra, instability due to perovskite cell configuration, cubic cell forms triangle perovskite structure along the direction stretching of body diagonal (111), Bi ion is subjected to displacement along (111) direction relative to ferrum oxygen octahedra, result in the uneven of crystal structure and produces spontaneous polarization.
But, at BiFeO3In due to Fe3+The fluctuation of valence state and at BiFeO3The volatilization of Bi in membrane-film preparation process, causes the formation of Lacking oxygen in thin film, thus BiFeO3Bigger leakage current often occurs, hardly results in than more saturated polarization curve.Meanwhile, BiFeO3Material weak magnetic at room temperature also limit it and obtains and develop further.
Summary of the invention
It is an object of the invention to provide a kind of Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3/Mn1-xCoxFe2O4Composite membrane and preparation method thereof, it is possible to effectively reduce leakage current, improve ferroelectric properties and ferromagnetic property simultaneously.
To achieve these goals, the present invention adopts the following technical scheme that
A kind of Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3/Mn1-xCoxFe2O4Composite membrane, including the lower membrane being combined with each other and upper layer film, wherein lower membrane is Mn1-xCoxFe2O4Crystalline state film, upper layer film is Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3Crystalline state film, x=0～0.4.
Described Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3Crystalline state film is class tetragonal phase structure；Mn1-xCoxFe2O4Crystalline state film is Emission in Cubic structure, and space structure group is Fd-3m.
Described x=0.01～0.4.
A kind of Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3/Mn1-xCoxFe2O4The preparation method of composite membrane, comprises the following steps:
Step 1, is dissolved in ferric nitrate, cobalt nitrate and manganese acetate in ethylene glycol monomethyl ether for 2:x:1-x in molar ratio, adds acetic anhydride, obtains Mn1-xCoxFe2O4Precursor liquid, wherein Mn1-xCoxFe2O4In precursor liquid, the total concentration of metal ion is 0.1～0.3mol/L, x=0～0.4；
Step 2, is dissolved in bismuth nitrate, ferric nitrate, Erbium trinitrate, cobalt nitrate and manganese acetate in solvent for 0.945:0.96:0.10:0.02:0.02 in molar ratio, obtains Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3Precursor solution, wherein Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3In precursor solution, the total concentration of metal ion is 0.1～0.3mol/L, and solvent is the mixed liquor of ethylene glycol monomethyl ether and acetic anhydride；
Step 3, uses spin-coating method spin coating Mn on FTO/glass substrate1-xCoxFe2O4Precursor liquid, obtains Mn1-xCoxFe2O4Thin film, Mn1-xCoxFe2O4Thin film toasts to obtain dry film after spin coating at 180～200 DEG C, anneals in atmosphere, obtain crystalline state Mn at 600～620 DEG C1-xCoxFe2O4Thin film；
Step 4, treats crystalline state Mn1-xCoxFe2O4After film cooling, in crystalline state Mn1-xCoxFe2O4Repeat step 3 on thin film, until it reaches desired thickness, obtain Mn1-xCoxFe2O4Crystalline state film；
Step 5, at Mn1-xCoxFe2O4Spin coating Bi on crystalline state film0.90Er0.10Fe0.96Co0.02Mn0.02O3Precursor solution, obtains Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3Thin film, Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3Thin film toasts to obtain dry film after spin coating under 180～200 DEG C of temperature, anneals in atmosphere, obtain crystalline state Bi at 520～550 DEG C0.90Er0.10Fe0.96Co0.02Mn0.02O3Thin film；
Step 6, treats crystalline state Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3After film cooling, in crystalline state Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3Repeat step 5 on thin film, until it reaches desired thickness, obtain Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3/Mn1-xCoxFe2O4Composite membrane.
Described Mn1-xCoxFe2O4In precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is (2.5～3.5): 1；
In described solvent, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is (2.5～3.5): 1.
FTO/glass substrate is first carried out before carrying out by described step 3, the most under ultraviolet light treatment with irradiation, makes FTO/glass substrate surface reach atomic cleanliness degree, then spin coating Mn1-xCoxFe2O4Precursor liquid；
Described step 5 before carrying out first to Mn1-xCoxFe2O4Crystalline state film carries out ultraviolet light treatment with irradiation, makes Mn1-xCoxFe2O4Crystalline state film surface reaches atomic cleanliness degree, then spin coating Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3Precursor solution.
Spin coating rotating speed in described step 3 and step 5 is 3500～4500r/min, and spin coating time is 10～20s.
In described step 3 and step 5, the baking time after spin coating is 5～8min.
Annealing time in described step 3 is 15～annealing time in 22min, step 5 is 5～15min.
Crystalline state Mn1-xCoxFe2O4The number of plies of thin film is 4～8 layers, crystalline state Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3The number of plies of thin film is 12～16 layers.
Relative to prior art, the method have the advantages that
1. the Bi that the present invention provides0.90Er0.10Fe0.96Co0.02Mn0.02O3/Mn1-xCoxFe2O4The preparation method of composite membrane, selects rare earth element er as BiFeO3A position doped chemical, the incorporation of Er can increase the distortion of lattice effectively, and can suppress the volatilization of Bi element, reduces Lacking oxygen content, thus improves the magnetic electricity performance of thin film.Select transition metal Co, Mn to carry out BiFeO simultaneously3The codope of B position, Fe can be suppressed3+To Fe2+Change, thus reduce the defect in thin film, reduce the leakage conductance electric current of thin film, enable thin film to obtain saturated ferroelectric hysteresis loop.But due to BiFeO3Itself there is the essence of weak magnetic, so the present invention uses the Mn with mixed phase spinel structure1-xCoxFe2O4Thin film and Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3Thin film is combined, Mn1-xCoxFe2O4There is ferromagnetism, be preferable composite.The present invention is by rare earth element er and transition metal Mn, Co tri-element codope BiFeO3, and combine ferromagnetic Mn1-xCoxFe2O4, make the Bi prepared0.90Er0.10Fe0.96Co0.02Mn0.02O3/Mn1-xCoxFe2O4Composite membrane has ferroelectric properties and the ferromagnetic property of excellence simultaneously.
2. it is currently used for preparing BiFeO3The method of thin film has a lot, such as chemical vapour deposition technique (CVD), magnetron sputtering method (rf magnetron sputtering), deposition of metal organic method (MOD), metal-organic chemical vapor deposition equipment method (MOCVD), liquid phase deposition (LPD), molecular beam epitaxy (MBE), pulsed laser deposition (PLD), sol-gel process (Sol-Gel) etc..Compare additive method, Sol-Gel method is simple due to equipment, reaction is easily carried out, reaction temperature is relatively low, easily operation, suitably on big surface and surface in irregular shape, prepare thin film, easily realize the Uniform Doped on molecular level, and the advantage such as chemical constituent controllable precise and be widely used for preparing ferroelectric material.The present invention use sol-gal process prepare Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3/Mn1-xCoxFe2O4Composite membrane, equipment requirements is simple, and experiment condition easily reaches, and doping is easily controlled, by MnFe2O4The doping vario-property of thin film and Mn1-xCoxFe2O4Thin film and Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3Being combined of thin film, it is possible to prepare uniformity ferroelectric properties good, high and the Bi of ferromagnetic property0.90Er0.10Fe0.96Co0.02Mn0.02O3/Mn1-xCoxFe2O4Composite membrane.
3. the Bi that the present invention provides0.90Er0.10Fe0.96Co0.02Mn0.02O3/Mn1-xCoxFe2O4Composite membrane, doped with rare-earth elements Er and transition metal Mn, Co in approximation is in the bismuth ferrite crystal lattices of perovskite structure originally, make bismuth ferrite crystal lattices distort, structural aberration aggravates, and reduces Fe in thin film simultaneously2+With the content of Lacking oxygen, thus improve ferroelectric properties and the ferromagnetic property of thin film, reduce the leakage current density of thin film, and combine ferromagnetic Mn1-xCoxFe2O4Film, makes the Bi of the present invention0.90Er0.10Fe0.96Co0.02Mn0.02O3/Mn1-xCoxFe2O4Composite membrane has ferroelectric properties and the ferromagnetic property of excellence simultaneously.
Accompanying drawing explanation
Fig. 1 is Bi prepared by the present invention0.90Er0.10Fe0.96Co0.02Mn0.02O3The XRD figure of crystalline state film；
Fig. 2 is Mn prepared by the present invention1-xCoxFe2O4The XRD figure of crystalline state film.
Detailed description of the invention
With currently preferred specific embodiment, the present invention is described in further detail below in conjunction with the accompanying drawings.
The Bi that the present invention provides0.90Er0.10Fe0.96Co0.02Mn0.02O3/Mn1-xCoxFe2O4Composite membrane, including the lower membrane being combined with each other and upper layer film, wherein lower membrane is Mn1-xCoxFe2O4Crystalline state film, upper layer film is Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3Crystalline state film, x=0～0.4, Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3Crystalline state film is class tetragonal phase structure；Mn1-xCoxFe2O4Crystalline state film is Emission in Cubic structure, and space structure group is Fd-3m.Preferably x=0.01～0.4.
Embodiment 1
Step 1, is dissolved in ethylene glycol monomethyl ether (x=0) for 2:1 in molar ratio by ferric nitrate and manganese acetate, adds acetic anhydride, obtains the stable MnFe that total concentration of metal ions is 0.2mol/L2O4Precursor liquid, wherein the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 3:1；
Step 2, is dissolved in solvent (bismuth nitrate excess) in molar ratio, obtains the stable Bi that metal ion total concentration is 0.3mol/L for 0.945:0.96:0.10:0.02:0.02 by bismuth nitrate, ferric nitrate, Erbium trinitrate, cobalt nitrate and manganese acetate0.90Er0.10Fe0.96Co0.02Mn0.02O3The volume ratio of precursor solution, ethylene glycol monomethyl ether and acetic anhydride is 3:1；
Step 3, selecting FTO/glass substrate is substrate, is sequentially placed in detergent, acetone, ethanol by the FTO/glass substrate of well cutting by ultrasonic waves for cleaning, with a large amount of distilled water flushing substrates after each ultrasonic waves for cleaning 10min, finally dries up with nitrogen；It is subsequently placed in 60 DEG C of baking oven baking 5min, takes out and stand to room temperature；Clean FTO/glass substrate is placed in ultraviolet radiation instrument irradiation 40min again, makes substrate surface reach " atomic cleanliness degree ".Use spin-coating method spin coating MnFe on clean FTO/glass substrate2O4Precursor liquid, obtains MnFe2O4Thin film, spin coating rotating speed is 4000r/min, and spin coating time is 15s, after spin coating terminates, toasts 5min and obtains dry film, then the 15min that anneals the most layer by layer at 620 DEG C, obtain crystalline state MnFe at 200 DEG C2O4Thin film；
Step 4, treats crystalline state MnFe2O4After film cooling, in crystalline state MnFe2O4Repeat step 3 on thin film, be repeated 5 times, obtain MnFe2O4Crystalline state film；
Step 5, by MnFe2O4Crystalline state film is placed in ultraviolet radiation instrument irradiation 40min so that it is surface reaches atomic cleanliness degree；Then at MnFe2O4Spin coating Bi on crystalline state film0.90Er0.10Fe0.96Co0.02Mn0.02O3Precursor solution, obtains Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3Thin film, spin coating rotating speed is 4000r/min, and spin coating time is 15s, after spin coating terminates, toasts 5min and obtains dry film, then the 5min that anneals the most layer by layer at 550 DEG C, obtain crystalline state Bi at 200 DEG C0.90Er0.10Fe0.96Co0.02Mn0.02O3Thin film；
Step 6, treats crystalline state Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3After film cooling, in crystalline state Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3Repeat step 5 on thin film, be repeated 13 times, obtain Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3/MnFe2O4Composite membrane.
Embodiment 2
Step 1, is dissolved in ethylene glycol monomethyl ether (x=0.2) for 2:0.2:0.8 in molar ratio by ferric nitrate, cobalt nitrate and manganese acetate, adds acetic anhydride, obtains the stable Mn that total concentration of metal ions is 0.2mol/L0.8Co0.2Fe2O4Precursor liquid, wherein the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 3:1；
Step 2, is dissolved in solvent (bismuth nitrate excess) in molar ratio, obtains the stable Bi that metal ion total concentration is 0.3mol/L for 0.945:0.96:0.10:0.02:0.02 by bismuth nitrate, ferric nitrate, Erbium trinitrate, cobalt nitrate and manganese acetate0.90Er0.10Fe0.96Co0.02Mn0.02O3The volume ratio of precursor solution, ethylene glycol monomethyl ether and acetic anhydride is 3:1；
Step 3, selecting FTO/glass substrate is substrate, is sequentially placed in detergent, acetone, ethanol by the FTO/glass substrate of well cutting by ultrasonic waves for cleaning, with a large amount of distilled water flushing substrates after each ultrasonic waves for cleaning 10min, finally dries up with nitrogen；It is subsequently placed in 60 DEG C of baking oven baking 5min, takes out and stand to room temperature；Clean FTO/glass substrate is placed in ultraviolet radiation instrument irradiation 40min again, makes substrate surface reach " atomic cleanliness degree ".Use spin-coating method spin coating Mn on clean FTO/glass substrate0.8Co0.2Fe2O4Precursor liquid, obtains Mn0.8Co0.2Fe2O4Thin film, spin coating rotating speed is 4000r/min, and spin coating time is 15s, after spin coating terminates, toasts 5min and obtains dry film, then the 15min that anneals the most layer by layer at 620 DEG C, obtain crystalline state Mn at 200 DEG C0.8Co0.2Fe2O4Thin film；
Step 4, treats crystalline state Mn0.8Co0.2Fe2O4After film cooling, in crystalline state Mn0.8Co0.2Fe2O4Repeat step 3 on thin film, be repeated 5 times, obtain Mn0.8Co0.2Fe2O4Crystalline state film；
Step 5, by Mn0.8Co0.2Fe2O4Crystalline state film is placed in ultraviolet radiation instrument irradiation so that it is surface reaches atomic cleanliness degree；Then at Mn0.8Co0.2Fe2O4Spin coating Bi on crystalline state film0.90Er0.10Fe0.96Co0.02Mn0.02O3Precursor solution, obtains Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3Thin film, spin coating rotating speed is 4000r/min, and spin coating time is 15s, after spin coating terminates, toasts 5min and obtains dry film, then the 5min that anneals the most layer by layer at 550 DEG C, obtain crystalline state Bi at 200 DEG C0.90Er0.10Fe0.96Co0.02Mn0.02O3Thin film；
Step 6, treats crystalline state Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3After film cooling, in crystalline state Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3Repeat step 5 on thin film, be repeated 13 times, obtain Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3/Mn0.8Co0.2Fe2O4Composite membrane.
Embodiment 3
Step 1, is dissolved in ethylene glycol monomethyl ether (x=0.4) for 2:0.4:0.6 in molar ratio by ferric nitrate, cobalt nitrate and manganese acetate, adds acetic anhydride, obtains the stable Mn that total concentration of metal ions is 0.2mol/L0.6Co0.4Fe2O4Precursor liquid, wherein the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 3:1；
Step 2, is dissolved in solvent (bismuth nitrate excess) in molar ratio, obtains the stable Bi that metal ion total concentration is 0.3mol/L for 0.945:0.96:0.10:0.02:0.02 by bismuth nitrate, ferric nitrate, Erbium trinitrate, cobalt nitrate and manganese acetate0.90Er0.10Fe0.96Co0.02Mn0.02O3The volume ratio of precursor solution, ethylene glycol monomethyl ether and acetic anhydride is 3:1；
Step 3, selecting FTO/glass substrate is substrate, is sequentially placed into by the FTO/glass substrate of well cutting
By ultrasonic waves for cleaning in detergent, acetone, ethanol, with a large amount of distilled water flushing substrates after each ultrasonic waves for cleaning 10min, finally dry up with nitrogen；It is subsequently placed in 60 DEG C of baking oven baking 5min, takes out and stand to room temperature；Clean FTO/glass substrate is placed in ultraviolet radiation instrument irradiation 40min again, makes substrate surface reach " atomic cleanliness degree ".Use spin-coating method spin coating Mn on clean FTO/glass substrate0.6Co0.4Fe2O4Precursor liquid, obtains Mn0.6Co0.4Fe2O4Thin film, spin coating rotating speed is 4000r/min, and spin coating time is 15s, after spin coating terminates, toasts 5min and obtains dry film, then the 15min that anneals the most layer by layer at 620 DEG C, obtain crystalline state Mn at 200 DEG C0.6Co0.4Fe2O4Thin film；
Step 4, treats crystalline state Mn0.6Co0.4Fe2O4After film cooling, in crystalline state Mn0.6Co0.4Fe2O4Repeat step 3 on thin film, be repeated 5 times, obtain Mn0.6Co0.4Fe2O4Crystalline state film；
Step 5, by Mn0.6Co0.4Fe2O4Crystalline state film is placed in ultraviolet radiation instrument irradiation so that it is surface reaches atomic cleanliness degree；Then at Mn0.6Co0.4Fe2O4Spin coating Bi on crystalline state film0.90Er0.10Fe0.96Co0.02Mn0.02O3Precursor solution, obtains Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3Thin film, spin coating rotating speed is 4000r/min, and spin coating time is 15s, after spin coating terminates, toasts 5min and obtains dry film, then the 5min that anneals the most layer by layer at 550 DEG C, obtain crystalline state Bi at 200 DEG C0.90Er0.10Fe0.96Co0.02Mn0.02O3Thin film；
Step 6, treats crystalline state Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3After film cooling, in crystalline state Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3Repeat step 5 on thin film, be repeated 13 times, obtain Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3/Mn0.6Co0.4Fe2O4Composite membrane.
Embodiment 4
Step 1, is dissolved in ethylene glycol monomethyl ether (x=0.1) for 2:0.1:0.9 in molar ratio by ferric nitrate, cobalt nitrate and manganese acetate, adds acetic anhydride, obtains the stable Mn that total concentration of metal ions is 0.1mol/L0.9Co0.1Fe2O4Precursor liquid, wherein the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 2.5:1；
Step 2, is dissolved in solvent (bismuth nitrate excess) in molar ratio, obtains the stable Bi that metal ion total concentration is 0.1mol/L for 0.945:0.96:0.10:0.02:0.02 by bismuth nitrate, ferric nitrate, Erbium trinitrate, cobalt nitrate and manganese acetate0.90Er0.10Fe0.96Co0.02Mn0.02O3The volume ratio of precursor solution, ethylene glycol monomethyl ether and acetic anhydride is 2.5:1；
Step 3, selecting FTO/glass substrate is substrate, is sequentially placed in detergent, acetone, ethanol by the FTO/glass substrate of well cutting by ultrasonic waves for cleaning, with a large amount of distilled water flushing substrates after each ultrasonic waves for cleaning 10min, finally dries up with nitrogen；It is subsequently placed in 60 DEG C of baking oven baking 5min, takes out and stand to room temperature；Clean FTO/glass substrate is placed in ultraviolet radiation instrument irradiation 40min again, makes substrate surface reach " atomic cleanliness degree ".Use spin-coating method spin coating Mn on clean FTO/glass substrate0.9Co0.1Fe2O4Precursor liquid, obtains Mn0.9Co0.1Fe2O4Thin film, spin coating rotating speed is 3500r/min, and spin coating time is 20s, after spin coating terminates, toasts 8min and obtains dry film, then the 22min that anneals the most layer by layer at 600 DEG C, obtain crystalline state Mn at 180 DEG C0.9Co0.1Fe2O4Thin film；
Step 4, treats crystalline state Mn0.9Co0.1Fe2O4After film cooling, in crystalline state Mn0.9Co0.1Fe2O4Repeat step 3 on thin film, be repeated 3 times, obtain Mn0.9Co0.1Fe2O4Crystalline state film；
Step 5, by Mn0.9Co0.1Fe2O4Crystalline state film is placed in ultraviolet radiation instrument irradiation so that it is surface reaches atomic cleanliness degree；Then at Mn0.9Co0.1Fe2O4Spin coating Bi on crystalline state film0.90Er0.10Fe0.96Co0.02Mn0.02O3Precursor solution, obtains Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3Thin film, spin coating rotating speed is 3500r/min, and spin coating time is 20s, after spin coating terminates, toasts 8min and obtains dry film, then the 15min that anneals the most layer by layer at 520 DEG C, obtain crystalline state Bi at 180 DEG C0.90Er0.10Fe0.96Co0.02Mn0.02O3Thin film；
Step 6, treats crystalline state Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3After film cooling, in crystalline state Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3Repeat step 5 on thin film, be repeated 11 times, obtain Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3/Mn0.9Co0.1Fe2O4Composite membrane.
Embodiment 5
Step 1, is dissolved in ethylene glycol monomethyl ether (x=0.3) for 2:0.3:0.7 in molar ratio by ferric nitrate, cobalt nitrate and manganese acetate, adds acetic anhydride, obtains the stable Mn that total concentration of metal ions is 0.3mol/L0.7Co0.3Fe2O4Precursor liquid, wherein the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 3.5:1；
Step 2, is dissolved in solvent (bismuth nitrate excess) in molar ratio, obtains the stable Bi that metal ion total concentration is 0.2mol/L for 0.945:0.96:0.10:0.02:0.02 by bismuth nitrate, ferric nitrate, Erbium trinitrate, cobalt nitrate and manganese acetate0.90Er0.10Fe0.96Co0.02Mn0.02O3The volume ratio of precursor solution, ethylene glycol monomethyl ether and acetic anhydride is 3.5:1；
Step 3, selecting FTO/glass substrate is substrate, is sequentially placed in detergent, acetone, ethanol by the FTO/glass substrate of well cutting by ultrasonic waves for cleaning, with a large amount of distilled water flushing substrates after each ultrasonic waves for cleaning 10min, finally dries up with nitrogen；It is subsequently placed in 60 DEG C of baking oven baking 5min, takes out and stand to room temperature；Clean FTO/glass substrate is placed in ultraviolet radiation instrument irradiation 40min again, makes substrate surface reach " atomic cleanliness degree ".Use spin-coating method spin coating Mn on clean FTO/glass substrate0.7Co0.3Fe2O4Precursor liquid, obtains Mn0.7Co0.3Fe2O4Thin film, spin coating rotating speed is 4500r/min, and spin coating time is 10s, after spin coating terminates, toasts 7min and obtains dry film, then the 17min that anneals the most layer by layer at 610 DEG C, obtain crystalline state Mn at 190 DEG C0.7Co0.3Fe2O4Thin film；
Step 4, treats crystalline state Mn0.7Co0.3Fe2O4After film cooling, in crystalline state Mn0.7Co0.3Fe2O4Repeat step 3 on thin film, be repeated 7 times, obtain Mn0.7Co0.3Fe2O4Crystalline state film；
Step 5, by Mn0.7Co0.3Fe2O4Crystalline state film is placed in ultraviolet radiation instrument irradiation so that it is surface reaches atomic cleanliness degree；Then at Mn0.7Co0.3Fe2O4Spin coating Bi on crystalline state film0.90Er0.10Fe0.96Co0.02Mn0.02O3Precursor solution, obtains Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3Thin film, spin coating rotating speed is 4500r/min, and spin coating time is 10s, after spin coating terminates, toasts 7min and obtains dry film, then the 12min that anneals the most layer by layer at 530 DEG C, obtain crystalline state Bi at 190 DEG C0.90Er0.10Fe0.96Co0.02Mn0.02O3Thin film；
Step 6, treats crystalline state Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3After film cooling, in crystalline state Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3Repeat step 5 on thin film, be repeated 15 times, obtain Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3/Mn0.7Co0.3Fe2O4Composite membrane.
Embodiment 6
Step 1, is dissolved in ethylene glycol monomethyl ether (x=0.01) for 2:0.01:0.99 in molar ratio by ferric nitrate, cobalt nitrate and manganese acetate, adds acetic anhydride, obtains the stable Mn that total concentration of metal ions is 0.15mol/L0.99Co0.01Fe2O4Precursor liquid, wherein the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 2.8:1；
Step 2, is dissolved in solvent (bismuth nitrate excess) in molar ratio, obtains the stable Bi that metal ion total concentration is 0.15mol/L for 0.945:0.96:0.10:0.02:0.02 by bismuth nitrate, ferric nitrate, Erbium trinitrate, cobalt nitrate and manganese acetate0.90Er0.10Fe0.96Co0.02Mn0.02O3The volume ratio of precursor solution, ethylene glycol monomethyl ether and acetic anhydride is 2.8:1；
Step 3, selecting FTO/glass substrate is substrate, is sequentially placed in detergent, acetone, ethanol by the FTO/glass substrate of well cutting by ultrasonic waves for cleaning, with a large amount of distilled water flushing substrates after each ultrasonic waves for cleaning 10min, finally dries up with nitrogen；It is subsequently placed in 60 DEG C of baking oven baking 5min, takes out and stand to room temperature；Clean FTO/glass substrate is placed in ultraviolet radiation instrument irradiation 40min again, makes substrate surface reach " atomic cleanliness degree ".Use spin-coating method spin coating Mn on clean FTO/glass substrate0.99Co0.01Fe2O4Precursor liquid, obtains Mn0.99Co0.01Fe2O4Thin film, spin coating rotating speed is 3800r/min, and spin coating time is 18s, after spin coating terminates, toasts 7min and obtains dry film, then the 20min that anneals the most layer by layer at 605 DEG C, obtain crystalline state Mn at 185 DEG C0.99Co0.01Fe2O4Thin film；
Step 4, treats crystalline state Mn0.99Co0.01Fe2O4After film cooling, in crystalline state Mn0.99Co0.01Fe2O4Repeat step 3 on thin film, be repeated 4 times, obtain Mn0.99Co0.01Fe2O4Crystalline state film；
Step 5, by Mn0.99Co0.01Fe2O4Crystalline state film is placed in ultraviolet radiation instrument irradiation 40min so that it is surface reaches atomic cleanliness degree；Then at Mn0.99Co0.01Fe2O4Spin coating Bi on crystalline state film0.90Er0.10Fe0.96Co0.02Mn0.02O3Precursor solution, obtains Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3Thin film, spin coating rotating speed is 3800r/min, and spin coating time is 18s, after spin coating terminates, toasts 7min and obtains dry film, then the 10min that anneals the most layer by layer at 540 DEG C, obtain crystalline state Bi at 185 DEG C0.90Er0.10Fe0.96Co0.02Mn0.02O3Thin film；
Step 6, treats crystalline state Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3After film cooling, in crystalline state Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3Repeat step 5 on thin film, be repeated 12 times, obtain Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3/Mn0.99Co0.01Fe2O4Composite membrane.
Embodiment 7
Step 1, is dissolved in ethylene glycol monomethyl ether (x=0.05) for 2:0.05:0.95 in molar ratio by ferric nitrate, cobalt nitrate and manganese acetate, adds acetic anhydride, obtains the stable Mn that total concentration of metal ions is 0.25mol/L0.95Co0.05Fe2O4Precursor liquid, wherein the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 3.2:1；
Step 2, is dissolved in solvent (bismuth nitrate excess) in molar ratio, obtains the stable Bi that metal ion total concentration is 0.25mol/L for 0.945:0.96:0.10:0.02:0.02 by bismuth nitrate, ferric nitrate, Erbium trinitrate, cobalt nitrate and manganese acetate0.90Er0.10Fe0.96Co0.02Mn0.02O3The volume ratio of precursor solution, ethylene glycol monomethyl ether and acetic anhydride is 3.2:1；
Step 3, selecting FTO/glass substrate is substrate, is sequentially placed in detergent, acetone, ethanol by the FTO/glass substrate of well cutting by ultrasonic waves for cleaning, with a large amount of distilled water flushing substrates after each ultrasonic waves for cleaning 10min, finally dries up with nitrogen；It is subsequently placed in 60 DEG C of baking oven baking 5min, takes out and stand to room temperature；Clean FTO/glass substrate is placed in ultraviolet radiation instrument irradiation 40min again, makes substrate surface reach " atomic cleanliness degree ".Use spin-coating method spin coating Mn on clean FTO/glass substrate0.95Co0.05Fe2O4Precursor liquid, obtains Mn0.95Co0.05Fe2O4Thin film, spin coating rotating speed is 4200r/min, and spin coating time is 12s, after spin coating terminates, toasts 6min and obtains dry film, then the 16min that anneals the most layer by layer at 615 DEG C, obtain crystalline state Mn at 195 DEG C0.95Co0.05Fe2O4Thin film；
Step 4, treats crystalline state Mn0.95Co0.05Fe2O4After film cooling, in crystalline state Mn0.95Co0.05Fe2O4Repeat step 3 on thin film, be repeated 6 times, obtain Mn0.95Co0.05Fe2O4Crystalline state film；
Step 5, by Mn0.95Co0.05Fe2O4Crystalline state film is placed in ultraviolet radiation instrument irradiation 40min so that it is surface reaches atomic cleanliness degree；Then at Mn0.95Co0.05Fe2O4Spin coating Bi on crystalline state film0.90Er0.10Fe0.96Co0.02Mn0.02O3Precursor solution, obtains Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3Thin film, spin coating rotating speed is 4200r/min, and spin coating time is 12s, after spin coating terminates, toasts 8min and obtains dry film, then the 8min that anneals the most layer by layer at 545 DEG C, obtain crystalline state Bi at 195 DEG C0.90Er0.10Fe0.96Co0.02Mn0.02O3Thin film；
Step 6, treats crystalline state Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3After film cooling, in crystalline state Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3Repeat step 5 on thin film, be repeated 14 times, obtain Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3/Mn0.95Co0.05Fe2O4Composite membrane.
Fig. 1 is crystalline state Bi that the present invention prepares0.90Er0.10Fe0.96Co0.02Mn0.02O3The XRD figure of thin film, as it is shown in figure 1, the Bi that the present invention prepares0.90Er0.10Fe0.96Co0.02Mn0.02O3Fine identical with standard card [JCPDS NO.86-1518] of the diffraction maximum of thin film, this shows Er, Co, Mn codope BiFeO of preparation3Thin film is class tetragonal phase structure, and has good degree of crystallinity.
Fig. 2 is crystalline state Mn that the present invention prepares1-xCoxFe2O4The XRD figure spectrum of thin film, x=0～0.4, from figure 2 it can be seen that the doping of Co element does not change MnFe2O4Cubic spinel and Fd-3m space group structure, this structure is beneficial to Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3The performance of thin film improves.
Above said content is to combine concrete preferred implementation further description made for the present invention, it is not all of or unique embodiment, the conversion of any equivalence that technical solution of the present invention is taked by those of ordinary skill in the art by reading description of the invention, the claim being the present invention is contained.
Claims (6)
1. a Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3/Mn1-xCoxFe2O4Composite membrane, it is characterised in that:
Including the lower membrane being combined with each other and upper layer film, wherein lower membrane is Mn1-xCoxFe2O4Crystalline state film, is vertical
Side's phase structure, space structure group is Fd-3m；Upper layer film is Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3Crystalline state film,
For class tetragonal phase structure, x=0.01～0.4.
2. the Bi described in claim 10.90Er0.10Fe0.96Co0.02Mn0.02O3/Mn1-xCoxFe2O4Composite membrane
Preparation method, it is characterised in that comprise the following steps:
Step 1, is dissolved in ferric nitrate, cobalt nitrate and manganese acetate in ethylene glycol monomethyl ether for 2:x:1-x in molar ratio,
Add acetic anhydride, obtain Mn1-xCoxFe2O4Precursor liquid, wherein Mn1-xCoxFe2O4Metal in precursor liquid
The total concentration of ion is 0.1～0.3mol/L, x=0～0.4；
Step 2 is 0.945:0.96:0.10:0.02:0.02 in molar ratio by bismuth nitrate, ferric nitrate, Erbium trinitrate,
Cobalt nitrate and manganese acetate are dissolved in solvent, obtain Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3Precursor solution, wherein
Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3In precursor solution, the total concentration of metal ion is 0.1～0.3mol/L,
Solvent is the mixed liquor of ethylene glycol monomethyl ether and acetic anhydride；
Step 3, uses spin-coating method spin coating Mn on FTO/glass substrate1-xCoxFe2O4Precursor liquid,
Mn1-xCoxFe2O4Thin film, Mn1-xCoxFe2O4Thin film toasts 5～8min after spin coating at 180～200 DEG C,
Dry film, at 600～620 DEG C, anneal 15～22min in atmosphere, obtain crystalline state Mn1-xCoxFe2O4Thin
Film；
Step 4, treats crystalline state Mn1-xCoxFe2O4After film cooling, in crystalline state Mn1-xCoxFe2O4Weight on thin film
Multiple step 3, until it reaches desired thickness, obtains Mn1-xCoxFe2O4Crystalline state film；
Step 5, at Mn1-xCoxFe2O4Spin coating Bi on crystalline state film0.90Er0.10Fe0.96Co0.02Mn0.02O3Presoma
Solution, obtains Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3Thin film, Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3Thin film warp
Under 180～200 DEG C of temperature, toast 5～8min after spin coating, obtain dry film, move back in atmosphere at 520～550 DEG C
Fire 5～15min, obtains crystalline state Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3Thin film；
Step 6, treats crystalline state Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3After film cooling, in crystalline state
Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3Repeat step 5 on thin film, until it reaches desired thickness, obtain
Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3/Mn1-xCoxFe2O4Composite membrane.
Bi the most according to claim 20.90Er0.10Fe0.96Co0.02Mn0.02O3/Mn1-xCoxFe2O4Compound
The preparation method of film, it is characterised in that: described Mn1-xCoxFe2O4Ethylene glycol monomethyl ether and acetic anhydride in precursor liquid
Volume ratio be (2.5～3.5): 1；
In described solvent, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is (2.5～3.5): 1.
Bi the most according to claim 20.90Er0.10Fe0.96Co0.02Mn0.02O3/Mn1-xCoxFe2O4Compound
The preparation method of film, it is characterised in that: FTO/glass substrate is first carried out before carrying out by described step 3,
Treatment with irradiation the most under ultraviolet light, makes FTO/glass substrate surface reach atomic cleanliness degree, then spin coating
Mn1-xCoxFe2O4Precursor liquid；
Described step 5 before carrying out first to Mn1-xCoxFe2O4Crystalline state film carries out ultraviolet light treatment with irradiation, makes
Mn1-xCoxFe2O4Crystalline state film surface reaches atomic cleanliness degree, then spin coating Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3
Precursor solution.
Bi the most according to claim 20.90Er0.10Fe0.96Co0.02Mn0.02O3/Mn1-xCoxFe2O4Compound
The preparation method of film, it is characterised in that: the spin coating rotating speed in described step 3 and step 5 is
3500～4500r/min, spin coating time is 10～20s.
Bi the most according to claim 20.90Er0.10Fe0.96Co0.02Mn0.02O3/Mn1-xCoxFe2O4Compound
The preparation method of film, it is characterised in that: crystalline state Mn1-xCoxFe2O4The number of plies of thin film is 4～8 layers, crystalline state
Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3The number of plies of thin film is 12～16 layers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410764660.7A CN104478234B (en) | 2014-12-11 | 2014-12-11 | A kind of Bi0.90er0.10fe0.96co0.02mn0.02o3/ Mn1-xcoxfe2o4composite membrane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410764660.7A CN104478234B (en) | 2014-12-11 | 2014-12-11 | A kind of Bi0.90er0.10fe0.96co0.02mn0.02o3/ Mn1-xcoxfe2o4composite membrane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104478234A CN104478234A (en) | 2015-04-01 |
| CN104478234B true CN104478234B (en) | 2016-08-17 |
Family
ID=52752874
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410764660.7A Active CN104478234B (en) | 2014-12-11 | 2014-12-11 | A kind of Bi0.90er0.10fe0.96co0.02mn0.02o3/ Mn1-xcoxfe2o4composite membrane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104478234B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105819848B (en) * | 2016-03-29 | 2019-01-04 | 陕西科技大学 | A kind of spinel-type Co1-xMnxFe2O4Ferromagnetic thin film and preparation method thereof |
| 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 |
| CN108793767B (en) * | 2018-06-26 | 2021-09-17 | 陕西科技大学 | CoFe2-xLaxO4Ferromagnetic thin film and preparation method thereof |
| CN108726888B (en) * | 2018-06-26 | 2021-08-17 | 陕西科技大学 | CoFe2-xGdxO4Ferromagnetic thin film and preparation method thereof |
| CN109336406B (en) * | 2018-09-18 | 2021-08-10 | 陕西科技大学 | BGSFMC/CFGO composite film with symmetrical rectangular hysteresis loop 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 |
| CN113248248A (en) * | 2020-08-13 | 2021-08-13 | 深圳先进技术研究院 | Solid solution multiferroic film, preparation method and electronic device applied to 5G storage technology |
Family Cites Families (2)
| 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 |
-
2014
- 2014-12-11 CN CN201410764660.7A patent/CN104478234B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104478234A (en) | 2015-04-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104478234B (en) | A kind of Bi0.90er0.10fe0.96co0.02mn0.02o3/ Mn1-xcoxfe2o4composite membrane and preparation method thereof | |
| CN104445996B (en) | Multiferroic Bi0.96-xSr0.04RExFe0.94Mn0.04Cr0.02O3-NiFe2O4 composite film 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 | |
| CN104538140A (en) | Multiferroic Bi1-xRExFe0.97-yMn0.03TMyO3/CoFe2O4 composite film and preparation method thereof | |
| CN103708562B (en) | Bi0.90Ho0.10Fe1-XMnXO3 ferroelectric film with high remanent polarization and preparation method thereof | |
| CN103723770B (en) | High-dielectric-constant Bi0.92Ho0.08Fe[1-x]MnxO3 ferroelectric film and preparation method thereof | |
| CN104476832B (en) | A kind of laminated BiFe0.97-xmn0.03tMxo3/ CoFe2o4multiferroic composite membrane and preparation method thereof | |
| CN105906221B (en) | A kind of multiferroic Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4Composite membrane and preparation method thereof | |
| CN104478236A (en) | Bi0.92Ho0.08Fe0.97Mn0.03O3-Zn1-xNixFe2O4 multiferroic composite film and preparation method thereof | |
| CN103771527B (en) | A kind of Bi of low coercive field 0.92dy 0.08fe 1-xmn xo 3ferroelectric membranc and preparation method thereof | |
| CN103601248B (en) | Tb, Mn and Ni ternary co-doped low leakage current BiFeO3 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 | |
| CN104575907B (en) | Bi1-xRExFe1-yTMyO3/CoFe2O4 multiferroic composite film and preparation method thereof | |
| CN103601247B (en) | Bi1-xSmxFe0.94Mn0.04Cr0.02O3 ferroelectric film with high remanent polarization and low leakage current density and preparation method thereof | |
| CN105859152B (en) | A kind of high magnetism Bi0.96Sr0.04FeO3Base/CoFe2O4Laminated film and preparation method thereof | |
| CN105859273B (en) | A kind of 2-2 type BiFeO3-CuFe2O4 laminated film and preparation method thereof | |
| CN104538139B (en) | Bi1-xRExFeO3/CoFe2O4 multiferroic composite membrane 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 | |
| CN103626236B (en) | The BiFeO of a kind of B position Mn and Ni codoped high remnant polarization 3film and preparation method thereof | |
| CN104478230A (en) | Bi[0.92-x]Ho0.08AExFe0.97Mn0.03O3 multiferroic film and preparation method thereof | |
| CN107082576A (en) | A kind of HoSrMnNi is co-doped with many iron thin films of bismuth ferrite and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |