CN105271798B - A kind of high-ferromagnetic can be with the Bi of ferroelectric properties0.9Er0.1Fe1‑xCoxO3Film and preparation method thereof - Google Patents
A kind of high-ferromagnetic can be with the Bi of ferroelectric properties0.9Er0.1Fe1‑xCoxO3Film and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
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- 238000004528 spin coating Methods 0.000 claims abstract description 39
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 20
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000005415 magnetization Effects 0.000 claims abstract description 14
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000010287 polarization Effects 0.000 claims abstract description 9
- 238000000137 annealing Methods 0.000 claims abstract description 8
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 8
- YBYGDBANBWOYIF-UHFFFAOYSA-N erbium(3+);trinitrate Chemical compound [Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YBYGDBANBWOYIF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000005291 magnetic effect Effects 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 28
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 27
- 239000011521 glass Substances 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 9
- 230000003749 cleanliness Effects 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
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- 239000002994 raw material Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 95
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 78
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 4
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
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Abstract
Can be with the Bi of ferroelectric properties the invention provides a kind of high-ferromagnetic0.9Er0.1Fe1‑xCoxO3Film and preparation method thereof, Bi is prepared by raw material of bismuth nitrate, ferric nitrate, cobalt nitrate and erbium nitrate0.9Er0.1Fe1‑xCoxO3Precursor liquid, x=0.01~0.03, the spin coating Bi on substrate0.9Er0.1Fe1‑xCoxO3Precursor liquid, then through spin coating, drying, annealing, obtaining high-ferromagnetic can be with the Bi of ferroelectric properties0.9Er0.1Fe1‑xCoxO3Film.Present device requirement is simple, and experiment condition easily reaches, and doping is easily controlled, and can increase substantially BiFeO3The ferromagnetic property of film, obtained Bi0.9Er0.1Fe1‑xCoxO3Uniformity of film is good, and has the higher intensity of magnetization and remanent polarization.
Description
Technical field
The invention belongs to field of functional materials, and being related to a kind of high-ferromagnetic can be with the Bi of ferroelectric properties0.9Er0.1Fe1-xCoxO3
Film and preparation method thereof.
Background technology
Multi-iron material is to have ferroelectric order (antiferroelectric orderly), ferromagnetic ordering (antiferromagnetic order) simultaneously in same phase
Or iron bullet is orderly, and in certain temperature range, thus this several intercouples in order greatly changes multi-iron material
Performance.Multiferroic (magnetoelectricity) material can not only be used for the application field of single ferroic material as a kind of novel and multifunctional material,
Before more showing huge application in fields such as New Magnetic Field Controlled-electric sensor, spin electric device, novel information memory devices
Scape.BiFeO3It is unique 850 DEG C of Curie temperature and Neel temperature having higher than room temperature in current single-phase multiferroic magnetoelectric material
370 DEG C of material, therefore receive extensive research.
But due to BiFeO3Spiral magnetic structure so that BiFeO3In G type anti-ferromagnetism, only shown under existing fringing field
Faint ferromagnetism, its less magneto-electric coupled characteristic hinder its practical application in terms of more iron.General ABO3Perovskite
The ferroelectric of structure needs not having electronics to occupy on the d tracks of B positions ion and be in d0State.And for there is no electronics on d tracks
Structure, it can not form local magnetic moment, i.e., can not produce any kind of magnetic ordering structure.Both are entirely different physical
Matter is theoretically proved to be mutually exclusive.BiFeO3Material only has weak magnetic at room temperature, and it is further that this will limit its
Development.And if destroy BiFeO3Spin modulated structure, then can be strengthened magnetic.
The content of the invention
Can be with the Bi of ferroelectric properties it is an object of the invention to provide a kind of high-ferromagnetic0.9Er0.1Fe1-xCoxO3Film and
Its preparation method, doping is easily controlled in this method, the Bi of preparation0.9Er0.1Fe1-xCoxO3Uniformity of film is good, and with height
Ferromagnetic property and ferroelectric properties, it is possible to increase BiFeO3The ferromagnetic property of film.
To achieve these goals, the present invention adopts the following technical scheme that：
A kind of high-ferromagnetic can be with the Bi of ferroelectric properties0.9Er0.1Fe1-xCoxO3Film, its chemical formula are Bi0.9Er0.1Fe1- xCoxO3, wherein x=0.01~0.03, its crystal formation are water chestnut side R3c:H coexists with three oblique P1 phases.
Its saturation magnetization is 2.36~17.1emu/cm3, remanent magnetization is 0.24~6.2emu/cm3。
Under 1kHz frequencies and 750kV/cm test electric fields, its saturated polarization is 70.77~141.81 μ C/cm2, it is surplus
Remaining polarization intensity is 57.72~126.67 μ C/cm2, coercive field be 384~622kV/cm.
High-ferromagnetic can be with the Bi of ferroelectric properties0.9Er0.1Fe1-xCoxO3The preparation method of film, comprises the following steps：
Step 1, it is in molar ratio 0.945:0.10:1-x:Bismuth nitrate, erbium nitrate, ferric nitrate and cobalt nitrate are dissolved in molten by x
In agent, stir, obtain Bi0.9Er0.1Fe1-xCoxO3Precursor liquid, wherein Bi0.9Er0.1Fe1-xCoxO3In precursor liquid metal from
The total concentration of son is 0.1~0.3mol/L, and x=0.01~0.03, solvent is the mixed liquor of ethylene glycol monomethyl ether and acetic anhydride；
Step 2, using spin-coating method on FTO/glass substrates spin coating Bi0.9Er0.1Fe1-xCoxO3Precursor liquid, wet film is obtained, it is wet
Film, in 180~200 DEG C of bakings, obtains dry film after spin coating, and dry film is annealed at 500~550 DEG C, obtains Bi0.9Er0.1Fe1-xCoxO3It is thin
Film；
Step 3, after cooling, in Bi0.9Er0.1Fe1-xCoxO3Repeat step 2 on film, until reaching required thickness, obtain
High-ferromagnetic can be with the Bi of ferroelectric properties0.9Er0.1Fe1-xCoxO3Film.
Ethylene glycol monomethyl ether and the volume ratio of acetic anhydride are (2.5~3.5) in the solvent:1.
Required time that stirred in the step 1 is 1.5~2.5h.
The step 2 is first cleaned before progress to FTO/glass substrates, then treatment with irradiation under ultraviolet light, is made
FTO/glass substrate surfaces reach atomic cleanliness degree, then spin coating Bi0.9Er0.1Fe1-xCoxO3Precursor liquid.
Spin coating rotating speed in the step 2 is 3500~4500r/min, and spin coating time is 10~20s.
Baking time in the step 2 is 5~8min.
Annealing time in the step 2 is 10~15min.
Relative to prior art, the invention has the advantages that：
1. high-ferromagnetic provided by the invention can be with the Bi of ferroelectric properties0.9Er0.1Fe1-xCoxO3The preparation method of film, with
Rare earth element er carries out BiFeO3A positions substitute, with transition metal Co carry out BiFeO3B positions substitute, prepare with compared with
The Bi of high magnetic intensity and remanent polarization0.9Er0.1Fe1-xCoxO3Film.Rare earth element er is selected to enter in A positions in the present invention
Row doping, because Er ionic radius are close with Bi ionic radius, and Er is the minimum rare earth element of radius, can after being dissolved into lattice
Effectively to increase the distortion of film lattice, the magnetic property of film is improved, and suppresses the volatilization of Bi elements, reduces Lacking oxygen, from
And effectively improve the magnetic electricity performance of film.Selection Co carry out B positions be co-doped with can suppress Fe3+To Fe2+Transformation, reduce in film
The defects of, magnetic electricity performance is improved, film is can obtain the hysteresis curve of saturation.
2. currently used for preparing 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..Compared to other method, sol-gal process (Sol-Gel) reacts and easily carried out because equipment is simple, reaction temperature
Spend it is relatively low, it is easy to operate, film is suitably prepared on big surface and surface in irregular shape, is easily realized equal on molecular level
Even doping, and be widely used for preparing ferroelectric material the advantages that chemical constituent controllable precise.Coagulated in the present invention using colloidal sol
Glue method prepares BiFeO3Film, by Er, Co codope, Bi is prepared on FTO substrates0.9Er0.1Fe1-xCoxO3Film, equipment
It is required that simple, experiment condition easily reaches, and doping is easily controlled, and Bi can be significantly increased by doping0.9Er0.1Fe1- xCoxO3The ferromagnetic property of film, obtained Bi0.9Er0.1Fe1-xCoxO3Uniformity of film is good, and strong with higher residual polarization
Degree.
3. high-ferromagnetic provided by the invention can be with the Bi of ferroelectric properties0.9Er0.1Fe1-xCoxO3Film, it is in script approximation
Rare earth doped element Er and transition metal Co, undergo phase transition bismuth ferrite, lattice in the bismuth ferrite crystal lattices of perovskite structure
Distortion, structural aberration aggravation, the content of Lacking oxygen can be reduced, suppresses Fe3+To Fe2+Transformation, so as to reduce lacking in film
Fall into, effectively improve the magnetic property of film, make Bi produced by the present invention0.9Er0.1Fe1-xCoxO3Film can obtain high magnetic property,
There is excellent ferromagnetic property and ferroelectric properties simultaneously.
Brief description of the drawings
Fig. 1 is Bi prepared by the embodiment of the present invention 20.9Er0.1Fe0.98Co0.02O3The XRD of film；
Fig. 2 is Bi prepared by the embodiment of the present invention 20.9Er0.1Fe0.98Co0.02O3The SEM figures of film；
Fig. 3 is Bi prepared by the present invention0.9Er0.1Fe1-xCoxO3The hysteresis curve figure of film；Wherein a is BiFeO3Film
Hysteresis curve, b are Bi made from embodiment 10.9Er0.1Fe0.99Co0.01O3The hysteresis curve of film, c are made from embodiment 2
Bi0.9Er0.1Fe0.98Co0.02O3The hysteresis curve of film, d are Bi made from embodiment 30.9Er0.1Fe0.97Co0.03O3The magnetic of film
Hysteresis curves；
Fig. 4 is Fig. 3 partial enlarged drawing；Wherein a is BiFeO3The hysteresis curve of film, b are made from embodiment 1
Bi0.9Er0.1Fe0.99Co0.01O3The hysteresis curve of film, c are Bi made from embodiment 20.9Er0.1Fe0.98Co0.02O3The magnetic of film
Hysteresis curves, d are Bi made from embodiment 30.9Er0.1Fe0.97Co0.03O3The hysteresis curve of film；
Fig. 5 is Bi prepared by the embodiment of the present invention 20.9Er0.1Fe0.98Co0.02O3The ferroelectric hysteresis loop figure of film.
Embodiment
The present invention is described in further detail with currently preferred specific embodiment below in conjunction with the accompanying drawings.
High-ferromagnetic provided by the invention can be with the Bi of ferroelectric properties0.9Er0.1Fe1-xCoxO3Film (x=0.01~
0.03), its crystal formation is water chestnut side R3c:H coexists with three oblique P1 phases, under 1kHz frequencies and 750kV/cm test electric fields, its saturation pole
Change intensity is 70.77~141.81 μ C/cm2, remanent polarization be 57.72~126.67 μ C/cm2, coercive field be 384~
622kV/cm, and Bi0.9Er0.1Fe0.98Co0.02O3The saturation magnetization of film reaches 17.1emu/cm3, remanent magnetization is strong
Degree reaches 6.2emu/cm3, while Bi0.9Er0.1Fe0.99Co0.01O and Bi0.9Er0.1Fe0.97Co0.03O films have preferable magnetic
Can, its saturation magnetization is respectively 2.36emu/cm3And 5.68emu/cm3, remanent magnetization is respectively 0.24emu/cm3
And 2.2emu/cm3。
Embodiment 1
Step 1, it is in molar ratio 0.945:0.10:0.99:0.01 is molten by bismuth nitrate, erbium nitrate, ferric nitrate and cobalt nitrate
In solvent (bismuth nitrate is excessive, x=0.01), the stabilization that metal ion total concentration is 0.1mol/L is obtained after magnetic agitation 2.5h
Bi0.9Er0.1Fe0.99Co0.01O3Precursor liquid, wherein solvent are that volume ratio is 2.5:1 ethylene glycol monomethyl ether and acetic anhydride it is mixed
Close liquid；
Step 2, it is substrate to select FTO/glass substrates, and substrate is sequentially placed into detergent, acetone, ethanol, respectively with super
Sound wave cleans 10min, then cleans substrate with distilled water and is dried up with nitrogen；It is placed in again in 60 DEG C of baking oven and toasts 5min, it
Take out and stood to room temperature afterwards；Finally place the substrate in and 40min is irradiated in ultraviolet radiation instrument, reaching substrate surface, " atom is clear
Cleanliness ".Spin-coating method spin coating Bi on FTO/glass substrates is used again0.9Er0.1Fe0.99Co0.01O3Precursor liquid, obtain wet film, spin coating
Speed is 3500r/min, spin coating time 20s, and after spin coating terminates, 8min is toasted at 180 DEG C, obtains dry film, dry film uses again
Layer by layer annealing treating process 500 DEG C anneal 15min, obtain Bi0.9Er0.1Fe0.99Co0.01O3Film；
Step 3, after cooling, in Bi0.9Er0.1Fe0.99Co0.01O3Repeat step 2 on film, until reaching required thickness, obtain
Can be with the Bi of ferroelectric properties to high-ferromagnetic0.9Er0.1Fe1-xCoxO3Film.
Embodiment 2
Step 1, it is in molar ratio 0.945:0.10:0.98:0.02 is molten by bismuth nitrate, erbium nitrate, ferric nitrate and cobalt nitrate
In solvent (bismuth nitrate is excessive, x=0.02), the stabilization that metal ion total concentration is 0.2mol/L is obtained after magnetic agitation 2h
Bi0.9Er0.1Fe0.98Co0.02O3Precursor liquid, wherein solvent are that volume ratio is 3:1 ethylene glycol monomethyl ether and the mixing of acetic anhydride
Liquid；
Step 2, it is substrate to select FTO/glass substrates, and substrate is sequentially placed into detergent, acetone, ethanol, respectively with super
Sound wave cleans 10min, then cleans substrate with distilled water and is dried up with nitrogen；It is placed in again in 60 DEG C of baking oven and toasts 5min, it
Take out and stood to room temperature afterwards；Finally place the substrate in and 40min is irradiated in ultraviolet radiation instrument, reaching substrate surface, " atom is clear
Cleanliness ".Spin-coating method spin coating Bi on FTO/glass substrates is used again0.9Er0.1Fe0.98Co0.02O3Precursor liquid, obtain wet film, spin coating
Speed is 4000r/min, spin coating time 15s, and after spin coating terminates, 5min is toasted at 200 DEG C, obtains dry film, dry film uses again
Layer by layer annealing treating process 550 DEG C anneal 10min, obtain Bi0.9Er0.1Fe0.98Co0.02O3Film；
Step 3, after cooling, in Bi0.9Er0.1Fe0.98Co0.02O3Repeat step 2 on film, until reaching required thickness, obtain
Can be with the Bi of ferroelectric properties to high-ferromagnetic0.9Er0.1Fe0.98Co0.02O3Film.
Using Bi made from the XRD determining embodiment of the present invention 20.9Er0.1Fe0.98Co0.02O3The thing phase composition structure of film,
As a result as shown in figure 1, identical fine of its diffraction maximum and standard card [JCPDS NO.86-1518], this shows preparation of the present invention
Bi0.9Er0.1Fe0.98Co0.02O3Film is still the perovskite structure of distortion, and crystal formation is water chestnut side R3c:H coexists with three oblique P1 phases.
The Bi made from the FE-SEM measure embodiment of the present invention 20.9Er0.1Fe0.98Co0.02O3The microscopic appearance of film, as a result
As shown in Figure 2, it can be seen that obtained Bi0.9Er0.1Fe0.98Co0.02O3Film has the grain size distribution of even compact, this
The magnetic domain reversion of the film is beneficial to, improves the ferroelectricity and ferromagnetic property of the film.
Fig. 3 is Bi prepared by the present invention0.9Er0.1Fe1-xCoxO3The magnetic property of film, Fig. 4 are Fig. 3 partial enlarged drawing, are schemed
A is BiFeO in 3 and Fig. 43The hysteresis curve of film, b are Bi made from embodiment 10.9Er0.1Fe0.99Co0.01O3The magnetic of film
Hysteresis curves, c are Bi made from embodiment 20.9Er0.1Fe0.98Co0.02O3The hysteresis curve of film, d are made from embodiment 3
Bi0.9Er0.1Fe0.97Co0.03O3The hysteresis curve of film；It is can be seen that by Fig. 3 and Fig. 4 made from embodiment 2
Bi0.9Er0.1Fe0.98Co0.02O3Film has good magnetic property, and its saturation magnetization reaches 17.1emu/cm3, remanence
Change intensity and reach 6.2emu/cm3, far superior to BiFeO3The magnetic property of film；Bi made from embodiment 30.9Er0.1Fe0.97Co0.03O
Film has preferable magnetic property, and its saturation magnetization is 5.68emu/cm3, remanent magnetization 2.2emu/cm3, it is better than
BiFeO3The magnetic property of film；Bi made from embodiment 10.9Er0.1Fe0.99Co0.01O films have preferable magnetic property, its saturation
The intensity of magnetization is 2.36emu/cm3, remanent magnetization 0.24emu/cm3, equally better than BiFeO3The magnetic property of film；Say
Bright Bi produced by the present invention0.9Er0.1Fe1-xCoxO3Film can improve BiFeO3The magnetic property of film.
Fig. 5 is Bi made from the embodiment of the present invention 20.9Er0.1Fe0.98Co0.02O3Film is surveyed with TF2000 ferroelectricities test system
Try obtained thin-film ferroelectric performance, as seen in Figure 5, the film has the ferroelectric hysteresis loop of saturation, 1kHz frequencies,
Under 750kV/cm test electric field, it is 141.81 μ C/cm to measure its saturated polarization2, remanent polarization is 126.67 μ
C/cm2, coercive field 384kV/cm.
Embodiment 3
Step 1, it is in molar ratio 0.945:0.10:0.97:0.03 is molten by bismuth nitrate, erbium nitrate, ferric nitrate and cobalt nitrate
In solvent (bismuth nitrate is excessive, x=0.01), the stabilization that metal ion total concentration is 0.3mol/L is obtained after magnetic agitation 2h
Bi0.9Er0.1Fe0.97Co0.03O3Precursor liquid, wherein solvent are that volume ratio is 3:1 ethylene glycol monomethyl ether and the mixing of acetic anhydride
Liquid；
Step 2, it is substrate to select FTO/glass substrates, and substrate is sequentially placed into detergent, acetone, ethanol, respectively with super
Sound wave cleans 10min, then cleans substrate with distilled water and is dried up with nitrogen；It is placed in again in 60 DEG C of baking oven and toasts 5min, it
Take out and stood to room temperature afterwards；Finally place the substrate in and 40min is irradiated in ultraviolet radiation instrument, reaching substrate surface, " atom is clear
Cleanliness ".Spin-coating method spin coating Bi on FTO/glass substrates is used again0.9Er0.1Fe0.97Co0.03O3Precursor liquid, obtain wet film, spin coating
Speed is 4000r/min, spin coating time 15s, and after spin coating terminates, 5min is toasted at 200 DEG C, obtains dry film, dry film uses again
Layer by layer annealing treating process 550 DEG C anneal 10min, obtain Bi0.9Er0.1Fe0.97Co0.03O3Film；
Step 3, after cooling, in Bi0.9Er0.1Fe0.97Co0.03O3Repeat step 2 on film, until reaching required thickness, obtain
Can be with the Bi of ferroelectric properties to high-ferromagnetic0.9Er0.1Fe0.97Co0.03O3Film.
Embodiment 4
Step 1, it is in molar ratio 0.945:0.10:0.985:0.015 by bismuth nitrate, erbium nitrate, ferric nitrate and cobalt nitrate
It is dissolved in solvent (bismuth nitrate is excessive, x=0.015), it is 0.15mol/L's that metal ion total concentration is obtained after magnetic agitation 1.5h
Stable Bi0.9Er0.1Fe0.985Co0.015O3Precursor liquid, wherein solvent are that volume ratio is 3.5:1 ethylene glycol monomethyl ether and acetic anhydride
Mixed liquor；
Step 2, it is substrate to select FTO/glass substrates, and substrate is sequentially placed into detergent, acetone, ethanol, respectively with super
Sound wave cleans 10min, then cleans substrate with distilled water and is dried up with nitrogen；It is placed in again in 60 DEG C of baking oven and toasts 5min, it
Take out and stood to room temperature afterwards；Finally place the substrate in and 40min is irradiated in ultraviolet radiation instrument, reaching substrate surface, " atom is clear
Cleanliness ".Spin-coating method spin coating Bi on FTO/glass substrates is used again0.9Er0.1Fe0.985Co0.015O3Precursor liquid, obtain wet film, spin coating
Speed is 4500r/min, spin coating time 10s, and after spin coating terminates, 7min is toasted at 190 DEG C, obtains dry film, dry film uses again
Layer by layer annealing treating process 520 DEG C anneal 13min, obtain Bi0.9Er0.1Fe0.985Co0.015O3Film；
Step 3, after cooling, in Bi0.9Er0.1Fe0.985Co0.015O3Repeat step 2 on film, until reach required thickness,
Obtaining high-ferromagnetic can be with the Bi of ferroelectric properties0.9Er0.1Fe0.985Co0.015O3Film.
Embodiment 5
Step 1, it is in molar ratio 0.945:0.10:0.975:0.025 by bismuth nitrate, erbium nitrate, ferric nitrate and cobalt nitrate
It is dissolved in solvent (bismuth nitrate is excessive, x=0.025), it is 0.25mol/L's that metal ion total concentration is obtained after magnetic agitation 2.2h
Stable Bi0.9Er0.1Fe0.975Co0.025O3Precursor liquid, wherein solvent are that volume ratio is 2.8:1 ethylene glycol monomethyl ether and acetic anhydride
Mixed liquor；
Step 2, it is substrate to select FTO/glass substrates, and substrate is sequentially placed into detergent, acetone, ethanol, respectively with super
Sound wave cleans 10min, then cleans substrate with distilled water and is dried up with nitrogen；It is placed in again in 60 DEG C of baking oven and toasts 5min, it
Take out and stood to room temperature afterwards；Finally place the substrate in and 40min is irradiated in ultraviolet radiation instrument, reaching substrate surface, " atom is clear
Cleanliness ".Spin-coating method spin coating Bi on FTO/glass substrates is used again0.9Er0.1Fe0.975Co0.025O3Precursor liquid, obtain wet film, spin coating
Speed is 3800r/min, spin coating time 18s, and after spin coating terminates, 6min is toasted at 195 DEG C, obtains dry film, dry film uses again
Layer by layer annealing treating process 530 DEG C anneal 12min, obtain Bi0.9Er0.1Fe0.975Co0.025O3Film；
Step 3, after cooling, in Bi0.9Er0.1Fe0.975Co0.025O3Repeat step 2 on film, until reach required thickness,
Obtaining high-ferromagnetic can be with the Bi of ferroelectric properties0.9Er0.1Fe0.975Co0.025O3Film.
One embodiment of the present invention is the foregoing is only, is not all of or unique embodiment, this area is common
Technical staff is the present invention by reading description of the invention any equivalent conversion for taking technical solution of the present invention
Claim covered.
Claims (8)
1. a kind of high-ferromagnetic can be with the Bi of ferroelectric properties0.9Er0.1Fe1-xCoxO3Film, it is characterised in that：Its chemical formula is
Bi0.9Er0.1Fe1-xCoxO3, wherein x=0.01~0.03, its crystal formation are water chestnut side R3c:H coexists with three oblique P1 phases；Its saturated magnetization
Intensity is 2.36~17.1emu/cm3, remanent magnetization is 0.24~6.2emu/cm3；Surveyed in 1kHz frequencies and 750kV/cm
Try under electric field, its saturated polarization is 70.77~141.81 μ C/cm2, remanent polarization be 57.72~126.67 μ C/
cm2, coercive field be 384~622kV/cm.
2. the high-ferromagnetic described in claim 1 can be with the Bi of ferroelectric properties0.9Er0.1Fe1-xCoxO3The preparation method of film, its
It is characterised by, comprises the following steps：
Step 1, it is in molar ratio 0.945:0.10:1-x:Bismuth nitrate, erbium nitrate, ferric nitrate and cobalt nitrate are dissolved in solvent by x,
Stir, obtain Bi0.9Er0.1Fe1-xCoxO3Precursor liquid, wherein Bi0.9Er0.1Fe1-xCoxO3Metal ion is total in precursor liquid
Concentration is 0.1~0.3mol/L, and x=0.01~0.03, solvent is the mixed liquor of ethylene glycol monomethyl ether and acetic anhydride；
Step 2, using spin-coating method on FTO/glass substrates spin coating Bi0.9Er0.1Fe1-xCoxO3Precursor liquid, obtain wet film, wet film warp
In 180~200 DEG C of bakings after spin coating, dry film is obtained, dry film is annealed at 500~550 DEG C, obtains Bi0.9Er0.1Fe1-xCoxO3Film；
Step 3, after cooling, in Bi0.9Er0.1Fe1-xCoxO3Repeat step 2 on film, until reaching required thickness, obtain high ferro
The Bi of magnetic property and ferroelectric properties0.9Er0.1Fe1-xCoxO3Film.
3. high-ferromagnetic according to claim 2 can be with the Bi of ferroelectric properties0.9Er0.1Fe1-xCoxO3The preparation side of film
Method, it is characterised in that：Ethylene glycol monomethyl ether and the volume ratio of acetic anhydride are (2.5~3.5) in the solvent:1.
4. high-ferromagnetic according to claim 2 can be with the Bi of ferroelectric properties0.9Er0.1Fe1-xCoxO3The preparation side of film
Method, it is characterised in that：Required time that stirred in the step 1 is 1.5~2.5h.
5. high-ferromagnetic according to claim 2 can be with the Bi of ferroelectric properties0.9Er0.1Fe1-xCoxO3The preparation side of film
Method, it is characterised in that：The step 2 is first cleaned before progress to FTO/glass substrates, then under ultraviolet light at irradiation
Reason, makes FTO/glass substrate surfaces reach atomic cleanliness degree, then spin coating Bi0.9Er0.1Fe1-xCoxO3Precursor liquid.
6. high-ferromagnetic according to claim 2 can be with the Bi of ferroelectric properties0.9Er0.1Fe1-xCoxO3The preparation side of film
Method, it is characterised in that：Spin coating rotating speed in the step 2 is 3500~4500r/min, and spin coating time is 10~20s.
7. high-ferromagnetic according to claim 2 can be with the Bi of ferroelectric properties0.9Er0.1Fe1-xCoxO3The preparation side of film
Method, it is characterised in that：Baking time in the step 2 is 5~8min.
8. high-ferromagnetic according to claim 2 can be with the Bi of ferroelectric properties0.9Er0.1Fe1-xCoxO3The preparation side of film
Method, it is characterised in that：Annealing time in the step 2 is 10~15min.
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| CN109772348A (en) * | 2017-11-13 | 2019-05-21 | 广州中国科学院沈阳自动化研究所分所 | A kind of erbium-codoped bismuth ferrite photocatalyst of solid-carrying type copper and its preparation method and application |
| CN109772349A (en) * | 2017-11-13 | 2019-05-21 | 广州中国科学院沈阳自动化研究所分所 | A kind of erbium-codoped bismuth ferrite photocatalyst of solid-carrying type zinc and its preparation method and application |
| CN109133667B (en) * | 2018-09-18 | 2021-09-21 | 陕西科技大学 | BEFMO/ZCO composite heterojunction with resistance switching effect and preparation method thereof |
| CN109133668B (en) * | 2018-09-18 | 2021-07-27 | 陕西科技大学 | La, Er, Co and Mn Co-doped BFO film with resistance switching effect and preparation method thereof |
| CN111074244A (en) * | 2018-10-19 | 2020-04-28 | 营口理工学院 | Nickel-cerium co-doped bismuth ferrite film material and preparation method thereof |
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