CN105271798A - Bi0.9Er0.1Fe1-xCoxO3 film with high ferromagnetism and ferroelectricity, and making method thereof - Google Patents
Bi0.9Er0.1Fe1-xCoxO3 film with high ferromagnetism and ferroelectricity, and making method thereof Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000005307 ferromagnetism Effects 0.000 title abstract 4
- 230000005621 ferroelectricity Effects 0.000 title abstract 3
- 239000000758 substrate Substances 0.000 claims abstract description 43
- 238000004528 spin coating Methods 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 20
- 238000000137 annealing Methods 0.000 claims abstract description 15
- 230000010287 polarization Effects 0.000 claims abstract description 11
- 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
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims abstract description 8
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 27
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 18
- 239000011521 glass Substances 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- 230000005415 magnetization Effects 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 12
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 9
- 239000003292 glue Substances 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 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 230000005855 radiation Effects 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 230000005684 electric field Effects 0.000 claims description 5
- 235000003283 Pachira macrocarpa Nutrition 0.000 claims description 4
- 241001083492 Trapa Species 0.000 claims description 4
- 235000014364 Trapa natans Nutrition 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 235000009165 saligot Nutrition 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 230000005291 magnetic effect Effects 0.000 abstract description 40
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000002474 experimental method Methods 0.000 abstract description 2
- 229910002902 BiFeO3 Inorganic materials 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 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 abstract 1
- 238000004513 sizing Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 96
- 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000003980 solgel method Methods 0.000 description 5
- 238000004506 ultrasonic cleaning Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000005294 ferromagnetic effect Effects 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 229910052797 bismuth Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
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- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000004549 pulsed laser deposition Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
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- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
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- 230000005302 magnetic ordering Effects 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
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- 238000001451 molecular beam epitaxy Methods 0.000 description 1
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- 239000010409 thin film Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Inorganic Insulating Materials (AREA)
- Thin Magnetic Films (AREA)
Abstract
The invention provides a Bi0.9Er0.1Fe1-xCoxO3 film with high ferromagnetism and ferroelectricity, and a making method thereof. The method comprises the following steps: preparing a Bi0.9Er0.1Fe1-xCoxO3 precursor solution from bismuth nitrate, iron nitrate, cobalt nitrate and erbium nitrate, spin-coating a substrate with the Bi0.9Er0.1Fe1-xCoxO3 (x is 0.01-0.03) precursor solution, uniformly sizing, drying, and annealing to obtain the Bi0.9Er0.1Fe1-xCoxO3 film with high ferromagnetism and ferroelectricity. The method has the advantages of simple device requirements, easy reaching of experiment conditions, easy control of the doping amount, and great improvement of the ferromagnetism of a BiFeO3 film, and the Bi0.9Er0.1Fe1-xCoxO3 film made in the invention has the advantages of good uniformity, high magnetic intensity and high remanent polarization.
Description
Technical field
The invention belongs to field of functional materials, relate to the Bi of a kind of high-ferromagnetic energy and ferroelectric properties
0.9er
0.1fe
1-xco
xo
3film and preparation method thereof.
Background technology
Multi-iron material for same mutually in have ferroelectric order (in order antiferroelectric), ferromagnetic ordering (antiferromagnetic order) or iron bullet orderly simultaneously, and in certain temperature range, this several intercoupling in order changes the performance of multi-iron material thus greatly.Multiferroic (magnetoelectricity) material is as a kind of Multifunction material, not only can be used for the Application Areas of single ferroic material, more show huge application prospect in fields such as New Magnetic Field Controlled-electric sensor, spin electric device, novel information memory devices.BiFeO
3be that uniquely there is in current single-phase multiferroic magnetoelectric material the Curie temperature 850 DEG C higher than room temperature and the material of Neel temperature 370 DEG C, therefore receive and study widely.
But due to BiFeO
3spiral magnetic structure, make BiFeO
3in G type antiferromagnetism, under low electric field, only show faint ferromegnetism, its less magneto-electric coupled characteristic hinders its practical application in many iron.General ABO
3the ferroelectrics of perovskite structure needs the d track of B position ion not to have electrons occupy and is d
0state.And for d track not having the structure of electronics, it cannot form local magnetic moment, the magnetic ordering structure of any kind namely cannot be produced.These two kinds of diverse physical propertiess are proved to be repulsion mutually theoretically.BiFeO
3material at room temperature only has weak magnetic, and this will limit it and further develop.And if destroy BiFeO
3spin modulated structure, then magnetic can be made to be enhanced.
Summary of the invention
The object of the present invention is to provide the Bi of a kind of high-ferromagnetic energy and ferroelectric properties
0.9er
0.1fe
1-xco
xo
3film and preparation method thereof, in the method, doping easily controls, the Bi of preparation
0.9er
0.1fe
1-xco
xo
3uniformity of film is good, and has high-ferromagnetic energy and ferroelectric properties, can improve BiFeO
3the ferromagnetic property of film.
To achieve these goals, the present invention adopts following technical scheme:
The Bi of a kind of high-ferromagnetic energy and ferroelectric properties
0.9er
0.1fe
1-xco
xo
3film, its chemical formula is Bi
0.9er
0.1fe
1-xco
xo
3, wherein x=0.01 ~ 0.03, its crystal formation is that water chestnut side R3c:H coexists with three oblique P1 phases.
Its saturation magnetization is 2.36 ~ 17.1emu/cm
3, residual magnetization is 0.24 ~ 6.2emu/cm
3.
Under 1kHz frequency and 750kV/cm test electric field, its saturated polarization is 70.77 ~ 141.81 μ C/cm
2, remnant polarization is 57.72 ~ 126.67 μ C/cm
2, coercive field is 384 ~ 622kV/cm.
The Bi of high-ferromagnetic energy and ferroelectric properties
0.9er
0.1fe
1-xco
xo
3the preparation method of film, comprises the following steps:
Step 1, is dissolved in solvent for 0.945:0.10:1-x:x by Bismuth trinitrate, Erbium trinitrate, iron nitrate and Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES in molar ratio, stirs, and obtains Bi
0.9er
0.1fe
1-xco
xo
3precursor liquid, wherein Bi
0.9er
0.1fe
1-xco
xo
3in precursor liquid, the total concn of metal ion is 0.1 ~ 0.3mol/L, x=0.01 ~ 0.03, and solvent is the mixed solution of ethylene glycol monomethyl ether and acetic anhydride;
Step 2, adopts spin-coating method spin coating Bi on FTO/glass substrate
0.9er
0.1fe
1-xco
xo
3precursor liquid, obtains wet film, and wet film 180 ~ 200 DEG C of bakings, obtains dry film after even glue, and dry film, 500 ~ 550 DEG C of annealing, obtains Bi
0.9er
0.1fe
1-xco
xo
3film;
Step 3, after cooling, at Bi
0.9er
0.1fe
1-xco
xo
3repeating step 2 on film, until reach desired thickness, obtains the Bi of high-ferromagnetic energy and ferroelectric properties
0.9er
0.1fe
1-xco
xo
3film.
In described solvent, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is (2.5 ~ 3.5): 1.
Required time that stirs in described step 1 is 1.5 ~ 2.5h.
Described step 2 is first cleaned FTO/glass substrate before carrying out, then radiation treatment under ultraviolet light, makes FTO/glass substrate surface reach atomic cleanliness degree, then spin coating Bi
0.9er
0.1fe
1-xco
xo
3precursor liquid.
Even glue rotating speed in described step 2 is 3500 ~ 4500r/min, and spin coating time is 10 ~ 20s.
Baking time in described step 2 is 5 ~ 8min.
Annealing time in described step 2 is 10 ~ 15min.
Relative to prior art, the present invention has following beneficial effect:
1. the Bi of high-ferromagnetic energy provided by the invention and ferroelectric properties
0.9er
0.1fe
1-xco
xo
3the preparation method of film, carries out BiFeO with rare earth element er
3a position substitute, carry out BiFeO with transition metal Co
3b position substitute, prepare the Bi had compared with high magnetic intensity and remnant polarization
0.9er
0.1fe
1-xco
xo
3film.Rare earth element er is selected to adulterate in A position in the present invention, because Er ionic radius is close with Bi ionic radius, and the Er rare earth element that to be radius minimum, the distortion of film lattice effectively can be increased after lattice is entered in solid solution, improve the magnetic property of film, and suppress the volatilization of Bi element, reduce Lacking oxygen, thus effectively improve the magnetic electricity performance of film.Select Co to carry out mixing altogether of B position and can suppress Fe
3+to Fe
2+change, reduce the defect in film, improve magnetic electricity performance, make film can obtain saturated magnetic hysteresis loop.
2. at present for the preparation of BiFeO
3the method of film has a lot, as chemical Vapor deposition process (CVD), magnetron sputtering method (rfmagnetronsputtering), deposition of metal organic method (MOD), metal-organic chemical vapor deposition equipment method (MOCVD), liquid phase deposition (LPD), molecular beam epitaxy (MBE), pulsed laser deposition (PLD), sol-gel method (Sol-Gel) etc.Compare additive method, sol-gel method (Sol-Gel) due to equipment simple, reaction is easily carried out, temperature of reaction is lower, easy to operate, be suitable for preparing film on large surface and surface in irregular shape, easily realize the Uniform Doped on molecular level, and the advantage such as chemical composition controllable precise and be widely used for preparing ferroelectric material.Sol-gel method is adopted to prepare BiFeO in the present invention
3film, by Er, Co codoped, Bi is prepared by FTO substrate
0.9er
0.1fe
1-xco
xo
3film, equipment requirements is simple, and experiment condition easily reaches, and doping easily controls, and can improve Bi significantly by doping
0.9er
0.1fe
1-xco
xo
3the ferromagnetic property of film, obtained Bi
0.9er
0.1fe
1-xco
xo
3uniformity of film is good, and has higher remnant polarization.
3. the Bi of high-ferromagnetic energy provided by the invention and ferroelectric properties
0.9er
0.1fe
1-xco
xo
3film, being originally similar to doped with rare-earth elements Er and transition metal Co in the bismuth ferrite crystal lattices in perovskite structure, bismuth ferrite is undergone phase transition, lattice distortion, structural aberration aggravates, and can reduce the content of Lacking oxygen, suppresses Fe
3+to Fe
2+change, thus reduce the defect in film, effectively improve the magnetic property of film, make the Bi that the present invention obtains
0.9er
0.1fe
1-xco
xo
3film can obtain high magnetic property, has excellent ferromagnetic property and ferroelectric properties simultaneously.
Accompanying drawing explanation
Fig. 1 is Bi prepared by the embodiment of the present invention 2
0.9er
0.1fe
0.98co
0.02o
3the XRD figure of film;
Fig. 2 is Bi prepared by the embodiment of the present invention 2
0.9er
0.1fe
0.98co
0.02o
3the SEM figure of film;
Fig. 3 is Bi prepared by the present invention
0.9er
0.1fe
1-xco
xo
3the magnetic hysteresis loop figure of film; Wherein a is BiFeO
3the magnetic hysteresis loop of film, b is the Bi that embodiment 1 obtains
0.9er
0.1fe
0.99co
0.01o
3the magnetic hysteresis loop of film, c is the Bi that embodiment 2 obtains
0.9er
0.1fe
0.98co
0.02o
3the magnetic hysteresis loop of film, d is the Bi that embodiment 3 obtains
0.9er
0.1fe
0.97co
0.03o
3the magnetic hysteresis loop of film;
Fig. 4 is the partial enlarged drawing of Fig. 3; Wherein a is BiFeO
3the magnetic hysteresis loop of film, b is the Bi that embodiment 1 obtains
0.9er
0.1fe
0.99co
0.01o
3the magnetic hysteresis loop of film, c is the Bi that embodiment 2 obtains
0.9er
0.1fe
0.98co
0.02o
3the magnetic hysteresis loop of film, d is the Bi that embodiment 3 obtains
0.9er
0.1fe
0.97co
0.03o
3the magnetic hysteresis loop of film;
Fig. 5 is Bi prepared by the embodiment of the present invention 2
0.9er
0.1fe
0.98co
0.02o
3the ferroelectric hysteresis loop figure of film.
Embodiment
Below in conjunction with accompanying drawing and the present invention's preferred specific embodiment, the present invention is described in further detail.
The Bi of high-ferromagnetic energy provided by the invention and ferroelectric properties
0.9er
0.1fe
1-xco
xo
3film (x=0.01 ~ 0.03), its crystal formation is that water chestnut side R3c:H coexists with three oblique P1 phases, and under 1kHz frequency and 750kV/cm test electric field, its saturated polarization is 70.77 ~ 141.81 μ C/cm
2, remnant polarization is 57.72 ~ 126.67 μ C/cm
2, coercive field is 384 ~ 622kV/cm, and Bi
0.9er
0.1fe
0.98co
0.02o
3the saturation magnetization of film reaches 17.1emu/cm
3, residual magnetization reaches 6.2emu/cm
3, Bi simultaneously
0.9er
0.1fe
0.99co
0.01o and Bi
0.9er
0.1fe
0.97co
0.03o film has good magnetic property, and its saturation magnetization is respectively 2.36emu/cm
3and 5.68emu/cm
3, residual magnetization is respectively 0.24emu/cm
3and 2.2emu/cm
3.
Embodiment 1
Step 1, for Bismuth trinitrate, Erbium trinitrate, iron nitrate and Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES are dissolved in solvent by 0.945:0.10:0.99:0.01, (Bismuth trinitrate is excessive in molar ratio, x=0.01), the stable Bi that metal ion total concn is 0.1mol/L is obtained after magnetic agitation 2.5h
0.9er
0.1fe
0.99co
0.01o
3precursor liquid, wherein solvent is volume ratio is the ethylene glycol monomethyl ether of 2.5:1 and the mixed solution of acetic anhydride;
Step 2, selects FTO/glass substrate to be substrate, substrate is placed in washing composition, acetone, ethanol successively, uses ultrasonic cleaning 10min respectively, then cleans substrate with distilled water and dries up with nitrogen; The baking oven being placed in 60 DEG C again toasts 5min, takes out afterwards and leaves standstill to room temperature; Finally substrate is placed in ultraviolet radiation instrument and irradiates 40min, substrate surface is reached " atomic cleanliness degree ".Adopt spin-coating method spin coating Bi on FTO/glass substrate again
0.9er
0.1fe
0.99co
0.01o
3precursor liquid, obtains wet film, and even glue speed is 3500r/min, and spin coating time is 20s, after even cementing bundle, toasts 8min, obtain dry film at 180 DEG C, and dry film adopts annealing treating process layer by layer at 500 DEG C of annealing 15min, to obtain Bi again
0.9er
0.1fe
0.99co
0.01o
3film;
Step 3, after cooling, at Bi
0.9er
0.1fe
0.99co
0.01o
3repeating step 2 on film, until reach desired thickness, obtains the Bi of high-ferromagnetic energy and ferroelectric properties
0.9er
0.1fe
1-xco
xo
3film.
Embodiment 2
Step 1, is dissolved in (Bismuth trinitrate is excessive, x=0.02) in solvent for 0.945:0.10:0.98:0.02 in molar ratio by Bismuth trinitrate, Erbium trinitrate, iron nitrate and Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, obtain the stable Bi that metal ion total concn is 0.2mol/L after magnetic agitation 2h
0.9er
0.1fe
0.98co
0.02o
3precursor liquid, wherein solvent is volume ratio is the ethylene glycol monomethyl ether of 3:1 and the mixed solution of acetic anhydride;
Step 2, selects FTO/glass substrate to be substrate, substrate is placed in washing composition, acetone, ethanol successively, uses ultrasonic cleaning 10min respectively, then cleans substrate with distilled water and dries up with nitrogen; The baking oven being placed in 60 DEG C again toasts 5min, takes out afterwards and leaves standstill to room temperature; Finally substrate is placed in ultraviolet radiation instrument and irradiates 40min, substrate surface is reached " atomic cleanliness degree ".Adopt spin-coating method spin coating Bi on FTO/glass substrate again
0.9er
0.1fe
0.98co
0.02o
3precursor liquid, obtains wet film, and even glue speed is 4000r/min, and spin coating time is 15s, after even cementing bundle, toasts 5min, obtain dry film at 200 DEG C, and dry film adopts annealing treating process layer by layer at 550 DEG C of annealing 10min, to obtain Bi again
0.9er
0.1fe
0.98co
0.02o
3film;
Step 3, after cooling, at Bi
0.9er
0.1fe
0.98co
0.02o
3repeating step 2 on film, until reach desired thickness, obtains the Bi of high-ferromagnetic energy and ferroelectric properties
0.9er
0.1fe
0.98co
0.02o
3film.
Adopt the Bi that the XRD determining embodiment of the present invention 2 is obtained
0.9er
0.1fe
0.98co
0.02o
3the thing phase composite structure of film, as shown in Figure 1, its diffraction peak and identical fine of standard card [JCPDSNO.86-1518], this shows Bi prepared by the present invention to result
0.9er
0.1fe
0.98co
0.02o
3film is still the perovskite structure of distortion, and crystal formation is that water chestnut side R3c:H coexists with three oblique P1 phases.
The obtained Bi of the embodiment of the present invention 2 is measured with FE-SEM
0.9er
0.1fe
0.98co
0.02o
3the microscopic appearance of film, result as shown in Figure 2, can find out obtained Bi
0.9er
0.1fe
0.98co
0.02o
3film has the grain size distribution of even compact, and this will be conducive to the magnetic domain reversion of this film, improve the ferroelectric of this film and ferromagnetic property.
Fig. 3 is Bi prepared by the present invention
0.9er
0.1fe
1-xco
xo
3the magnetic property of film, Fig. 4 is the partial enlarged drawing of Fig. 3, and in Fig. 3 and Fig. 4, a is BiFeO
3the magnetic hysteresis loop of film, b is the Bi that embodiment 1 obtains
0.9er
0.1fe
0.99co
0.01o
3the magnetic hysteresis loop of film, c is the Bi that embodiment 2 obtains
0.9er
0.1fe
0.98co
0.02o
3the magnetic hysteresis loop of film, d is the Bi that embodiment 3 obtains
0.9er
0.1fe
0.97co
0.03o
3the magnetic hysteresis loop of film; Can be found out by Fig. 3 and Fig. 4, the Bi that embodiment 2 is obtained
0.9er
0.1fe
0.98co
0.02o
3film has good magnetic property, and its saturation magnetization reaches 17.1emu/cm
3, residual magnetization reaches 6.2emu/cm
3, be far superior to BiFeO
3the magnetic property of film; The Bi that embodiment 3 is obtained
0.9er
0.1fe
0.97co
0.03o film has good magnetic property, and its saturation magnetization is 5.68emu/cm
3, residual magnetization is 2.2emu/cm
3, be better than BiFeO
3the magnetic property of film; The Bi that embodiment 1 is obtained
0.9er
0.1fe
0.99co
0.01o film has good magnetic property, and its saturation magnetization is 2.36emu/cm
3, residual magnetization is 0.24emu/cm
3, be better than BiFeO equally
3the magnetic property of film; The Bi that the present invention obtains is described
0.9er
0.1fe
1-xco
xo
3film can improve BiFeO
3the magnetic property of film.
Fig. 5 is the Bi that the embodiment of the present invention 2 obtains
0.9er
0.1fe
0.98co
0.02o
3the thin-film ferroelectric performance that the ferroelectric test system and test of film TF2000 obtains, as seen in Figure 5, this film has saturated ferroelectric hysteresis loop, and under the test electric field of 1kHz frequency, 750kV/cm, recording its saturated polarization is 141.81 μ C/cm
2, remnant polarization is 126.67 μ C/cm
2, coercive field is 384kV/cm.
Embodiment 3
Step 1, is dissolved in (Bismuth trinitrate is excessive, x=0.01) in solvent for 0.945:0.10:0.97:0.03 in molar ratio by Bismuth trinitrate, Erbium trinitrate, iron nitrate and Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, obtain the stable Bi that metal ion total concn is 0.3mol/L after magnetic agitation 2h
0.9er
0.1fe
0.97co
0.03o
3precursor liquid, wherein solvent is volume ratio is the ethylene glycol monomethyl ether of 3:1 and the mixed solution of acetic anhydride;
Step 2, selects FTO/glass substrate to be substrate, substrate is placed in washing composition, acetone, ethanol successively, uses ultrasonic cleaning 10min respectively, then cleans substrate with distilled water and dries up with nitrogen; The baking oven being placed in 60 DEG C again toasts 5min, takes out afterwards and leaves standstill to room temperature; Finally substrate is placed in ultraviolet radiation instrument and irradiates 40min, substrate surface is reached " atomic cleanliness degree ".Adopt spin-coating method spin coating Bi on FTO/glass substrate again
0.9er
0.1fe
0.97co
0.03o
3precursor liquid, obtains wet film, and even glue speed is 4000r/min, and spin coating time is 15s, after even cementing bundle, toasts 5min, obtain dry film at 200 DEG C, and dry film adopts annealing treating process layer by layer at 550 DEG C of annealing 10min, to obtain Bi again
0.9er
0.1fe
0.97co
0.03o
3film;
Step 3, after cooling, at Bi
0.9er
0.1fe
0.97co
0.03o
3repeating step 2 on film, until reach desired thickness, obtains the Bi of high-ferromagnetic energy and ferroelectric properties
0.9er
0.1fe
0.97co
0.03o
3film.
Embodiment 4
Step 1, for Bismuth trinitrate, Erbium trinitrate, iron nitrate and Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES are dissolved in solvent by 0.945:0.10:0.985:0.015, (Bismuth trinitrate is excessive in molar ratio, x=0.015), the stable Bi that metal ion total concn is 0.15mol/L is obtained after magnetic agitation 1.5h
0.9er
0.1fe
0.985co
0.015o
3precursor liquid, wherein solvent is volume ratio is the ethylene glycol monomethyl ether of 3.5:1 and the mixed solution of acetic anhydride;
Step 2, selects FTO/glass substrate to be substrate, substrate is placed in washing composition, acetone, ethanol successively, uses ultrasonic cleaning 10min respectively, then cleans substrate with distilled water and dries up with nitrogen; The baking oven being placed in 60 DEG C again toasts 5min, takes out afterwards and leaves standstill to room temperature; Finally substrate is placed in ultraviolet radiation instrument and irradiates 40min, substrate surface is reached " atomic cleanliness degree ".Adopt spin-coating method spin coating Bi on FTO/glass substrate again
0.9er
0.1fe
0.985co
0.015o
3precursor liquid, obtains wet film, and even glue speed is 4500r/min, and spin coating time is 10s, after even cementing bundle, toasts 7min, obtain dry film at 190 DEG C, and dry film adopts annealing treating process layer by layer at 520 DEG C of annealing 13min, to obtain Bi again
0.9er
0.1fe
0.985co
0.015o
3film;
Step 3, after cooling, at Bi
0.9er
0.1fe
0.985co
0.015o
3repeating step 2 on film, until reach desired thickness, obtains the Bi of high-ferromagnetic energy and ferroelectric properties
0.9er
0.1fe
0.985co
0.015o
3film.
Embodiment 5
Step 1, for Bismuth trinitrate, Erbium trinitrate, iron nitrate and Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES are dissolved in solvent by 0.945:0.10:0.975:0.025, (Bismuth trinitrate is excessive in molar ratio, x=0.025), the stable Bi that metal ion total concn is 0.25mol/L is obtained after magnetic agitation 2.2h
0.9er
0.1fe
0.975co
0.025o
3precursor liquid, wherein solvent is volume ratio is the ethylene glycol monomethyl ether of 2.8:1 and the mixed solution of acetic anhydride;
Step 2, selects FTO/glass substrate to be substrate, substrate is placed in washing composition, acetone, ethanol successively, uses ultrasonic cleaning 10min respectively, then cleans substrate with distilled water and dries up with nitrogen; The baking oven being placed in 60 DEG C again toasts 5min, takes out afterwards and leaves standstill to room temperature; Finally substrate is placed in ultraviolet radiation instrument and irradiates 40min, substrate surface is reached " atomic cleanliness degree ".Adopt spin-coating method spin coating Bi on FTO/glass substrate again
0.9er
0.1fe
0.975co
0.025o
3precursor liquid, obtains wet film, and even glue speed is 3800r/min, and spin coating time is 18s, after even cementing bundle, toasts 6min, obtain dry film at 195 DEG C, and dry film adopts annealing treating process layer by layer at 530 DEG C of annealing 12min, to obtain Bi again
0.9er
0.1fe
0.975co
0.025o
3film;
Step 3, after cooling, at Bi
0.9er
0.1fe
0.975co
0.025o
3repeating step 2 on film, until reach desired thickness, obtains the Bi of high-ferromagnetic energy and ferroelectric properties
0.9er
0.1fe
0.975co
0.025o
3film.
The foregoing is only one embodiment of the present invention, it not whole or unique embodiment, the conversion of those of ordinary skill in the art by reading specification sheets of the present invention to any equivalence that technical solution of the present invention is taked, is claim of the present invention and contains.
Claims (10)
1. the Bi of a high-ferromagnetic energy and ferroelectric properties
0.9er
0.1fe
1-xco
xo
3film, is characterized in that: its chemical formula is Bi
0.9er
0.1fe
1-xco
xo
3, wherein x=0.01 ~ 0.03, its crystal formation is that water chestnut side R3c:H coexists with three oblique P1 phases.
2. the Bi of high-ferromagnetic energy according to claim 1 and ferroelectric properties
0.9er
0.1fe
1-xco
xo
3film, is characterized in that: its saturation magnetization is 2.36 ~ 17.1emu/cm
3, residual magnetization is 0.24 ~ 6.2emu/cm
3.
3. the Bi of high-ferromagnetic energy according to claim 1 and ferroelectric properties
0.9er
0.1fe
1-xco
xo
3film, is characterized in that: under 1kHz frequency and 750kV/cm test electric field, its saturated polarization is 70.77 ~ 141.81 μ C/cm
2, remnant polarization is 57.72 ~ 126.67 μ C/cm
2, coercive field is 384 ~ 622kV/cm.
4. the high-ferromagnetic energy in claim 1-3 described in any one and the Bi of ferroelectric properties
0.9er
0.1fe
1-xco
xo
3the preparation method of film, is characterized in that, comprises the following steps:
Step 1, is dissolved in solvent for 0.945:0.10:1-x:x by Bismuth trinitrate, Erbium trinitrate, iron nitrate and Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES in molar ratio, stirs, and obtains Bi
0.9er
0.1fe
1-xco
xo
3precursor liquid, wherein Bi
0.9er
0.1fe
1-xco
xo
3in precursor liquid, the total concn of metal ion is 0.1 ~ 0.3mol/L, x=0.01 ~ 0.03, and solvent is the mixed solution of ethylene glycol monomethyl ether and acetic anhydride;
Step 2, adopts spin-coating method spin coating Bi on FTO/glass substrate
0.9er
0.1fe
1-xco
xo
3precursor liquid, obtains wet film, and wet film 180 ~ 200 DEG C of bakings, obtains dry film after even glue, and dry film, 500 ~ 550 DEG C of annealing, obtains Bi
0.9er
0.1fe
1-xco
xo
3film;
Step 3, after cooling, at Bi
0.9er
0.1fe
1-xco
xo
3repeating step 2 on film, until reach desired thickness, obtains the Bi of high-ferromagnetic energy and ferroelectric properties
0.9er
0.1fe
1-xco
xo
3film.
5. the Bi of high-ferromagnetic energy according to claim 4 and ferroelectric properties
0.9er
0.1fe
1-xco
xo
3the preparation method of film, is characterized in that: in described solvent, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is (2.5 ~ 3.5): 1.
6. the Bi of high-ferromagnetic energy according to claim 4 and ferroelectric properties
0.9er
0.1fe
1-xco
xo
3the preparation method of film, is characterized in that: the required time that stirs in described step 1 is 1.5 ~ 2.5h.
7. the Bi of high-ferromagnetic energy according to claim 4 and ferroelectric properties
0.9er
0.1fe
1-xco
xo
3the preparation method of film, is characterized in that: described step 2 is first cleaned FTO/glass substrate before carrying out, then radiation treatment under ultraviolet light, makes FTO/glass substrate surface reach atomic cleanliness degree, then spin coating Bi
0.9er
0.1fe
1-xco
xo
3precursor liquid.
8. the Bi of high-ferromagnetic energy according to claim 4 and ferroelectric properties
0.9er
0.1fe
1-xco
xo
3the preparation method of film, is characterized in that: the even glue rotating speed in described step 2 is 3500 ~ 4500r/min, and spin coating time is 10 ~ 20s.
9. the Bi of high-ferromagnetic energy according to claim 4 and ferroelectric properties
0.9er
0.1fe
1-xco
xo
3the preparation method of film, is characterized in that: the baking time in described step 2 is 5 ~ 8min.
10. the Bi of high-ferromagnetic energy according to claim 4 and ferroelectric properties
0.9er
0.1fe
1-xco
xo
3the preparation method of film, is characterized in that: the annealing time in described step 2 is 10 ~ 15min.
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| CN107619272A (en) * | 2017-09-15 | 2018-01-23 | 六盘水师范学院 | A kind of iron-based perovskite magnetic material containing B positions room and preparation method thereof |
| CN109133668A (en) * | 2018-09-18 | 2019-01-04 | 陕西科技大学 | A kind of BFO film and preparation method thereof that La, Er, Co, Mn with resistance switch effect are co-doped with |
| CN109133667A (en) * | 2018-09-18 | 2019-01-04 | 陕西科技大学 | A kind of BEFMO/ZCO composite heterogenous junction and preparation method thereof with resistance switch effect |
| 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 |
| 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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| CN107619272A (en) * | 2017-09-15 | 2018-01-23 | 六盘水师范学院 | A kind of iron-based perovskite magnetic material containing B positions room and preparation method thereof |
| CN107619272B (en) * | 2017-09-15 | 2022-04-01 | 六盘水师范学院 | Iron-based perovskite magnetic material containing B-site vacancies and preparation method thereof |
| 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 |
| CN109133668A (en) * | 2018-09-18 | 2019-01-04 | 陕西科技大学 | A kind of BFO film and preparation method thereof that La, Er, Co, Mn with resistance switch effect are co-doped with |
| CN109133667A (en) * | 2018-09-18 | 2019-01-04 | 陕西科技大学 | A kind of BEFMO/ZCO composite heterogenous junction and preparation method thereof with resistance switch effect |
| 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 |
| 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 |
| 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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