CN105859273A - 2-2 type BiFeO3-CuFe2O4 composite film and preparation method therefor - Google Patents
2-2 type BiFeO3-CuFe2O4 composite film and preparation method therefor Download PDFInfo
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- CN105859273A CN105859273A CN201610187898.7A CN201610187898A CN105859273A CN 105859273 A CN105859273 A CN 105859273A CN 201610187898 A CN201610187898 A CN 201610187898A CN 105859273 A CN105859273 A CN 105859273A
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Abstract
The invention provides a 2-2 type BiFeO3-CuFe2O4 composite film and a preparation method therefor. The preparation method comprises the steps: firstly, separately preparing a precursor solution of CuFe2O4 and a precursor solution of BiFeO3; and then, carrying out spin coating on a substrate so as to prepare multiple layers of CuFe2O4 films, and then, carrying out spin coating on the CuFe2O4 films so as to prepare multiple layers of BiFeO3 films, thereby obtaining the BiFeO3-CuFe2O4 composite film. According to the 2-2 type BiFeO3-CuFe2O4 composite film and the preparation method therefor, by adopting a sol-gel method, the prepared film is good in uniformity and accurate and controllable in chemical ingredient; the BiFeO3-CuFe2O4 composite film obtained through compounding the BiFeO3 films and ferromagnetic spinel-structured CuFe2O4 films has the saturation magnetization intensity Ms of 25.8emu/cm<3> and the remanent magnetization intensity Mr of 17.8emu/cm<3>; meanwhile, a dielectric loss frequency spectrum of the BiFeO3-CuFe2O4 composite film is in line with Maxwell-Wagner dielectric relaxation; and a leakage current of the film is subjected to resistance hysteresis under the condition of forward bias.
Description
Technical field
The invention belongs to field of functional materials, be specifically related to a kind of 2-2 type BiFeO3-CuFe2O4Laminated film and preparation method thereof.
Background technology
As the typical single phase multi-iron material of one, the secret (BiFeO of ferrous acid of pure phase3) there is perovskite structure, be minority at room temperature
Having one of ferroelectricity and anti-ferromagnetic multi-iron material, its ferroelectrie Curie temperature is 850 DEG C, anti-ferromagnetic Neel temperature simultaneously
It it is 370 DEG C.BiFeO3Thin film, as the typical iron store of one, has caused the concern of increasing researcher.Utilize
Its high-k and pcrmeability, it is possible to make high capacitance and the most inductor integrated electronic devices and components, be used for reducing high density
Number of devices on circuit board, solve perceptual device and capacitive device interferes problem.The magnetoelectric effect utilizing it likely sets
Count out the magneto-optic disk inverted with the fast-magnetic of fast electric polarization induction, thus replace the existing reading and writing memory material of magnetic at a slow speed.But
BiFeO3The ferromagnetic property of thin film is weak, hinders BiFeO3The actual application of thin film.
The thin film of spinel type ferrite shows many novel spies at numerous aspects such as optical property, electrical properties, magnetic properties
Property.CuFe2O4Belong to spinel type ferrite, be a kind of multifunctional semiconductor material, be a kind of important magnetic material.CuFe2O4
There is higher saturation magnetization, high magnetic permeability, big magnetocrystalline anisotropy, big magnetostriction and high chemically stable
Property.If the multiferroic film of excellent performance just can be obtained in conjunction with the advantage of both the above material, and do not has this respect at present
Relevant report.
Summary of the invention
It is an object of the invention to provide a kind of 2-2 type BiFeO3-CuFe2O4Laminated film and preparation method thereof, the method uses
2-2 type complex form, with BiFeO3As ferroelectric layer, CuFe2O4As magnetosphere, it is possible to improve BiFeO3Ferromagnetic property.
To achieve these goals, the present invention adopts the following technical scheme that
A kind of 2-2 type BiFeO3-CuFe2O4Laminated film, including the upper layer film being combined with each other and lower membrane, wherein upper layer film
For BiFeO3Crystalline state film, lower membrane is CuFe2O4Crystalline state film；Described BiFeO3Crystalline state film is the perovskite structure of distortion, Pedicellus et Pericarpium Trapae
Shape crystallographic system, space group is R3c:H (161)；CuFe2O4Crystalline state film is Tetragonal, spinel structure, and space group is
I41/amd(141)。
Its saturation magnetization MsFor 25.8emu/cm3, remanent magnetization MrFor 17.8emu/cm3；-200kV/cm's
Under negative sense electric field bias, its leakage current density is 3.87 × 10-2A/cm2。
A kind of 2-2 type BiFeO3-CuFe2O4The preparation method of laminated film, comprises the following steps:
Step 1, is dissolved in copper nitrate and ferric nitrate in ethylene glycol monomethyl ether for 1:2 in molar ratio, adds acetic anhydride after stirring,
Obtain CuFe2O4Precursor liquid, CuFe2O4In precursor liquid, the concentration of Fe ion is 0.1～0.2mol/L；
Step 2, is dissolved in bismuth nitrate and ferric nitrate in solvent for 1:1 in molar ratio, obtains BiFeO3Precursor liquid, wherein BiFeO3
In precursor liquid, the total concentration of metal ion is 0.003～0.3mol/L, and solvent is the mixed liquor of ethylene glycol monomethyl ether and acetic anhydride；
Step 3, uses spin-coating method spin coating CuFe on substrate2O4Precursor liquid, obtains CuFe2O4Wet film, CuFe2O4Wet film is through even
At 250～300 DEG C, toast to obtain dry film after glue, anneal in atmosphere at 610～620 DEG C, obtain crystalline state CuFe2O4Thin film；
Step 4, treats crystalline state CuFe2O4After film cooling, in crystalline state CuFe2O4Step 3 is repeated, until it reaches required on thin film
Thickness, obtains CuFe2O4Crystalline state film；
Step 5, at CuFe2O4Spin coating BiFeO on crystalline state film3Precursor liquid, obtains BiFeO3Wet film, BiFeO3Wet film is after spin coating
At 220～250 DEG C, toast to obtain dry film, anneal in atmosphere at 555～565 DEG C, obtain crystalline state BiFeO3Thin film；
Step 6, treats crystalline state BiFeO3After film cooling, in crystalline state BiFeO3Step 5 is repeated, until it reaches required thickness on thin film
Degree, obtains 2-2 type BiFeO3-CuFe2O4Laminated film.
Described CuFe2O4In precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is (3.5～4.5): 1；The solvent of described step 2
The volume ratio of middle ethylene glycol monomethyl ether and acetic anhydride is (2.5～3.5): 1.
Described substrate is FTO/ glass substrate, Si substrate, SrTiO3Monocrystal chip or LaNiO3Monocrystal chip.
Substrate, before carrying out, is first carried out by described step 3, the most under ultraviolet light treatment with irradiation, makes substrate surface reach former
Sub-cleannes, then spin coating CuFe2O4Precursor liquid；
Described step 5 is before carrying out, first to CuFe2O4Crystalline film carries out ultraviolet light treatment with irradiation, makes CuFe2O4Crystalline state film table
Face reaches atomic cleanliness degree, then spin coating BiFeO3Precursor liquid.
In described step 3 and step 5, spin coating rotating speed during spin coating is 4200～4500r/min, and spin coating time is 7～10s.
In described step 3 and step 5, the baking time after spin coating is 10～15min.
Annealing time in described step 3 is 25～annealing time in 30min, step 5 is 8～12min.
Described 2-2 type BiFeO3-CuFe2O4Laminated film is by 1～6 layer crystal states CuFe2O4Thin film and 3～15 layer crystal states BiFeO3
Thin film is constituted.
Relative to prior art, the method have the advantages that
1. 2-2 type BiFeO that the present invention provides3-CuFe2O4The preparation method of laminated film, selects BiFeO3With CuFe2O4Multiple
Close, this is because CuFe2O4There is the strongest magnetic, be preferable magnetic composite.By BiFeO3And CuFe2O4Thin film
Carry out 2-2 type to be combined, it is possible to form 2-2 type BiFeO with ferroelectric properties and ferromagnetic property3-CuFe2O4Laminated film.
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 sedimentation (LPD), molecular beam epitaxy (MBE), pulsed laser deposition (PLD), sol-gel process (Sol-Gel) etc..Phase
Ratio additive method, Sol-Gel method is simple due to equipment, and reaction is easily carried out, and reaction temperature is relatively low, easily operates, suitably greatly
Surface and surface in irregular shape on prepare thin film, easily realize the Uniform Doped on molecular level, and chemical constituent accurately may be used
The advantages such as control and be widely used for preparing ferroelectric material.The present invention use sol-gal process prepare BiFeO3Thin film, and with
CuFe2O4Film laminated, is prepared for 2-2 type BiFeO on substrate3-CuFe2O4Laminated film, equipment requirements is simple, tests bar
Part easily reaches, 2-2 type BiFeO of preparation3-CuFe2O4Laminated film uniformity is good, has special leakage current density curve,
There is directric relaxation phenomenon in dielectric loss frequency spectrum, and improves BiFeO3Ferromagnetic property.
3. 2-2 type BiFeO that the present invention provides3-CuFe2O4Laminated film is made up of the upper layer film being combined with each other and lower membrane,
Wherein upper layer film is BiFeO3Crystalline state film, lower membrane is CuFe2O4Crystalline state film；BiFeO3Crystalline state film is the perovskite structure of distortion,
Rhombohedral system, space group is R3c:H (161)；CuFe2O4Crystalline state film is Tetragonal, spinel structure, and space group is
I41/amd(141)。
Accompanying drawing explanation
Fig. 1 is 2-2 type BiFeO prepared by the present invention3-CuFe2O4The XRD figure of laminated film；
Fig. 2 is 2-2 type BiFeO prepared by the present invention3-CuFe2O4The Raman collection of illustrative plates of laminated film；
Fig. 3 is 2-2 type BiFeO prepared by the present invention3-CuFe2O4The surface SEM figure of laminated film and section SEM figure；
Fig. 4 is 2-2 type BiFeO prepared by the present invention3-CuFe2O4The dielectric constant of laminated film and dielectric loss spectrogram；
Fig. 5 is 2-2 type BiFeO prepared by the present invention3-CuFe2O4The leakage conductance electric current of laminated film and the graph of a relation of electric field；
Fig. 6 (a) is 2-2 type BiFeO prepared by the present invention3-CuFe2O4The ferroelectric hysteresis loop figure of laminated film, Fig. 6 (b) is system of the present invention
Standby 2-2 type BiFeO3-CuFe2O4The hysteresis curve figure of laminated film.
Detailed description of the invention
Below in conjunction with the present invention preferably embodiment and accompanying drawing, the present invention is described in further details.
Embodiment 1
Step 1, is dissolved in ethylene glycol monomethyl ether for 1:2 in molar ratio by copper nitrate and ferric nitrate, after stirring 30min, adds vinegar
Anhydride, obtains the stable CuFe that Fe ion concentration is 0.1mol/L2O4Precursor liquid, CuFe2O4Ethylene glycol monomethyl ether in precursor liquid
It is 4:1 with the volume ratio of acetic anhydride；
Step 2, is dissolved in solvent (bismuth nitrate excess 5%) for 1:1 in molar ratio by bismuth nitrate and ferric nitrate, obtains metal ion
Total concentration is the stable BiFeO of 0.3mol/L3Precursor liquid；Wherein solvent be volume ratio be ethylene glycol monomethyl ether and the acetic anhydride of 3:1
Mixed liquor；
Step 3, is sequentially placed into ultrasonic waves for cleaning in detergent, acetone, ethanol, each ultrasonic waves for cleaning by FTO/ glass substrate
With a large amount of distilled water flushing FTO/ glass substrates after 10min, finally dry up with nitrogen.Then FTO/ glass substrate is put into baking oven
It is baked to be dried, takes out and stand to room temperature.Clean FTO/ glass substrate is placed in ultraviolet radiation instrument irradiation 40min again,
FTO/ glass substrate surface is made to reach " atomic cleanliness degree ".Then spin-coating method spin coating CuFe on FTO/ glass substrate is used2O4Before
Drive liquid, obtain CuFe2O4Wet film, to CuFe2O4Wet film spin coating, spin coating rotating speed is 4200r/min, and spin coating time is 10s,
After spin coating terminates, at a temperature of 250 DEG C, toast 12min obtain dry film, then the 25min that anneals layer by layer in air at a temperature of 620 DEG C,
Obtain crystalline state CuFe2O4Thin film；
Step 4, treats crystalline state CuFe2O4After film cooling, in crystalline state CuFe2O4Repeat step 3 on thin film, be repeated 2 times,
To CuFe2O4Crystalline state film；
Step 5, by CuFe2O4Crystalline state film is placed in ultraviolet radiation instrument irradiation 40min so that it is surface reaches atomic cleanliness degree；
Again at CuFe2O4Spin coating BiFeO on crystalline state film3Precursor liquid, obtains BiFeO3Wet film, to BiFeO3Wet film spin coating, spin coating turns
Speed is 4200r/min, and spin coating time is 10s, after spin coating terminates, toasts 12min and obtain dry film at 220 DEG C, then at 565 DEG C
Anneal in air 10min layer by layer, obtains crystalline state BiFeO3Thin film；
Step 6, treats crystalline state BiFeO3After film cooling, in crystalline state BiFeO3Repeat step 5 on thin film, be repeated 5 times, obtain
2-2 type BiFeO3-CuFe2O4Laminated film.
Embodiment 2
Step 1, is dissolved in ethylene glycol monomethyl ether for 1:2 in molar ratio by copper nitrate and ferric nitrate, after stirring 30min, adds vinegar
Anhydride, obtains the stable CuFe that Fe ion concentration is 0.14mol/L2O4Precursor liquid, CuFe2O4Ethylene glycol monomethyl ether in precursor liquid
It is 3.5:1 with the volume ratio of acetic anhydride；
Step 2, is dissolved in solvent (bismuth nitrate excess 5%) for 1:1 in molar ratio by bismuth nitrate and ferric nitrate, obtains metal ion
Total concentration is the stable BiFeO of 0.003mol/L3Precursor liquid；Wherein solvent be volume ratio be ethylene glycol monomethyl ether and the vinegar of 2.5:1
The mixed liquor of anhydride；
Step 3, is sequentially placed into ultrasonic waves for cleaning in detergent, acetone, ethanol, each ultrasonic waves for cleaning by FTO/ glass substrate
With a large amount of distilled water flushing FTO/ glass substrates after 10min, finally dry up with nitrogen.Then FTO/ glass substrate is put into baking oven
It is baked to be dried, takes out and stand to room temperature.Clean FTO/ glass substrate is placed in ultraviolet radiation instrument irradiation 40min again,
FTO/ glass substrate surface is made to reach " atomic cleanliness degree ".Then spin-coating method spin coating CuFe on FTO/ glass substrate is used2O4Before
Drive liquid, obtain CuFe2O4Wet film, to CuFe2O4Wet film spin coating, spin coating rotating speed is 4300r/min, and spin coating time is 9s, even
After cementing bundle, at a temperature of 260 DEG C, toast 15min obtain dry film, then the 26min that anneals layer by layer in air at a temperature of 610 DEG C,
To crystalline state CuFe2O4Thin film；
Step 4, treats crystalline state CuFe2O4After film cooling, in crystalline state CuFe2O4Repeat step 3 on thin film, be repeated 5 times,
To CuFe2O4Crystalline state film；
Step 5, by CuFe2O4Crystalline state film is placed in ultraviolet radiation instrument irradiation 40min so that it is surface reaches atomic cleanliness degree；
Again at CuFe2O4Spin coating BiFeO on crystalline state film3Precursor liquid, obtains BiFeO3Wet film, to BiFeO3Wet film spin coating, spin coating turns
Speed is 4300r/min, and spin coating time is 9s, after spin coating terminates, toasts 14min and obtain dry film at 230 DEG C, then at 555 DEG C
Anneal in air 12min layer by layer, obtains crystalline state BiFeO3Thin film；
Step 6, treats crystalline state BiFeO3After film cooling, in crystalline state BiFeO3Repeat step 5 on thin film, be repeated 6 times, obtain
2-2 type BiFeO3-CuFe2O4Laminated film.
Embodiment 3
Step 1, is dissolved in ethylene glycol monomethyl ether for 1:2 in molar ratio by copper nitrate and ferric nitrate, after stirring 30min, adds vinegar
Anhydride, obtains the stable CuFe that Fe ion concentration is 0.2mol/L2O4Precursor liquid, CuFe2O4Ethylene glycol monomethyl ether in precursor liquid
It is 4.5:1 with the volume ratio of acetic anhydride；
Step 2, is dissolved in solvent (bismuth nitrate excess 5%) for 1:1 in molar ratio by bismuth nitrate and ferric nitrate, obtains metal ion
Total concentration is the stable BiFeO of 0.05mol/L3Precursor liquid；Wherein solvent be volume ratio be ethylene glycol monomethyl ether and the acetic acid of 3.5:1
The mixed liquor of acid anhydride；
Step 3, is sequentially placed into ultrasonic waves for cleaning in detergent, acetone, ethanol, each ultrasonic waves for cleaning by FTO/ glass substrate
With a large amount of distilled water flushing FTO/ glass substrates after 10min, finally dry up with nitrogen.Then FTO/ glass substrate is put into baking oven
It is baked to be dried, takes out and stand to room temperature.Clean FTO/ glass substrate is placed in ultraviolet radiation instrument irradiation 40min again,
FTO/ glass substrate surface is made to reach " atomic cleanliness degree ".Then spin-coating method spin coating CuFe on FTO/ glass substrate is used2O4Before
Drive liquid, obtain CuFe2O4Wet film, to CuFe2O4Wet film spin coating, spin coating rotating speed is 4400r/min, and spin coating time is 8s, even
After cementing bundle, at a temperature of 270 DEG C, toast 14min obtain dry film, then the 27min that anneals layer by layer in air at a temperature of 612 DEG C,
To crystalline state CuFe2O4Thin film；
Step 4, treats crystalline state CuFe2O4After film cooling, in crystalline state CuFe2O4Repeat step 3 on thin film, be repeated 1 times,
To CuFe2O4Crystalline state film；
Step 5, by CuFe2O4Crystalline state film is placed in ultraviolet radiation instrument irradiation 40min so that it is surface reaches atomic cleanliness degree；
Again at CuFe2O4Spin coating BiFeO on crystalline state film3Precursor liquid, obtains BiFeO3Wet film, to BiFeO3Wet film spin coating, spin coating turns
Speed is 4400r/min, and spin coating time is 8s, after spin coating terminates, toasts 11min and obtain dry film at 240 DEG C, more empty at 560 DEG C
Anneal in gas 11min layer by layer, obtains crystalline state BiFeO3Thin film；
Step 6, treats crystalline state BiFeO3After film cooling, in crystalline state BiFeO3Repeat step 5 on thin film, be repeated 8 times, obtain
2-2 type BiFeO3-CuFe2O4Laminated film.
Embodiment 4
Step 1, is dissolved in ethylene glycol monomethyl ether for 1:2 in molar ratio by copper nitrate and ferric nitrate, after stirring 30min, adds vinegar
Anhydride, obtains the stable CuFe that Fe ion concentration is 0.12mol/L2O4Precursor liquid, CuFe2O4Ethylene glycol monomethyl ether in precursor liquid
It is 3.7:1 with the volume ratio of acetic anhydride；
Step 2, is dissolved in solvent (bismuth nitrate excess 5%) for 1:1 in molar ratio by bismuth nitrate and ferric nitrate, obtains metal ion
Total concentration is the stable BiFeO of 0.01mol/L3Precursor liquid；Wherein solvent be volume ratio be ethylene glycol monomethyl ether and the acetic acid of 2.7:1
The mixed liquor of acid anhydride；
Step 3, is sequentially placed into ultrasonic waves for cleaning in detergent, acetone, ethanol, each ultrasonic waves for cleaning 10min by Si substrate
Afterwards with a large amount of distilled water flushing Si substrates, finally dry up with nitrogen.Then Si substrate is put into baking oven to be baked to be dried, take out quiet
Put to room temperature.Clean Si substrate is placed in ultraviolet radiation instrument irradiation 40min again, makes Si substrate surface reach " atomic cleanliness
Degree ".Then spin-coating method spin coating CuFe on si substrates is used2O4Precursor liquid, obtains CuFe2O4Wet film, to CuFe2O4Wet film
Spin coating, spin coating rotating speed is 4500r/min, and spin coating time is 7s, after spin coating terminates, toasts 13min and must do at a temperature of 280 DEG C
Film, then the 30min that anneals layer by layer in air at a temperature of 618 DEG C, obtain crystalline state CuFe2O4Thin film；
Step 4, treats crystalline state CuFe2O4After film cooling, in crystalline state CuFe2O4Repeat step 3 on thin film, be repeated 3 times,
To CuFe2O4Crystalline state film；
Step 5, by CuFe2O4Crystalline state film is placed in ultraviolet radiation instrument irradiation 40min so that it is surface reaches atomic cleanliness degree；
Again at CuFe2O4Spin coating BiFeO on crystalline state film3Precursor liquid, obtains BiFeO3Wet film, to BiFeO3Wet film spin coating, spin coating turns
Speed is 4500r/min, and spin coating time is 7s, after spin coating terminates, toasts 10min and obtain dry film at 250 DEG C, then at 558 DEG C
Anneal in air 11.5min layer by layer, obtains crystalline state BiFeO3Thin film；
Step 6, treats crystalline state BiFeO3After film cooling, in crystalline state BiFeO3Repeat step 5 on thin film, be repeated 11 times, obtain
2-2 type BiFeO3-CuFe2O4Laminated film.
Embodiment 5
Step 1, is dissolved in ethylene glycol monomethyl ether for 1:2 in molar ratio by copper nitrate and ferric nitrate, after stirring 30min, adds vinegar
Anhydride, obtains the stable CuFe that Fe ion concentration is 0.18mol/L2O4Precursor liquid, CuFe2O4Ethylene glycol monomethyl ether in precursor liquid
It is 3.9:1 with the volume ratio of acetic anhydride；
Step 2, is dissolved in solvent (bismuth nitrate excess 5%) for 1:1 in molar ratio by bismuth nitrate and ferric nitrate, obtains metal ion
Total concentration is the stable BiFeO of 0.1mol/L3Precursor liquid；Wherein solvent be volume ratio be ethylene glycol monomethyl ether and the acetic acid of 2.9:1
The mixed liquor of acid anhydride；
Step 3, by SrTiO3Monocrystal chip is sequentially placed into ultrasonic waves for cleaning in detergent, acetone, ethanol, each ultrasonic waves for cleaning
With a large amount of distilled water flushing SrTiO after 10min3Monocrystal chip, finally dries up with nitrogen.Then by SrTiO3Monocrystal chip is put into
Baking oven is baked to be dried, and takes out and stands to room temperature.Again by clean SrTiO3Monocrystal chip is placed in ultraviolet radiation instrument irradiation
40min, makes SrTiO3Monocrystal chip surface reaches " atomic cleanliness degree ".Then use spin-coating method at SrTiO3Spin coating on monocrystal chip
CuFe2O4Precursor liquid, obtains CuFe2O4Wet film, to CuFe2O4Wet film spin coating, spin coating rotating speed is 4350r/min, during spin coating
Between be 8.5s, after spin coating terminates, at a temperature of 290 DEG C, toast 11min obtain dry film, then at a temperature of 616 DEG C, air moves back layer by layer
Fire 29min, obtains crystalline state CuFe2O4Thin film；
Step 4, treats crystalline state CuFe2O4After film cooling, in crystalline state CuFe2O4Repeat step 3 on thin film, be repeated 4 times,
To CuFe2O4Crystalline state film；
Step 5, by CuFe2O4Crystalline state film is placed in ultraviolet radiation instrument irradiation 40min so that it is surface reaches atomic cleanliness degree；
Again at CuFe2O4Spin coating BiFeO on crystalline state film3Precursor liquid, obtains BiFeO3Wet film, to BiFeO3Wet film spin coating, spin coating turns
Speed is 4350r/min, and spin coating time is 8.5s, after spin coating terminates, toasts 15min and obtain dry film at 225 DEG C, then at 562 DEG C
Anneal in air 9min layer by layer, obtains crystalline state BiFeO3Thin film；
Step 6, treats crystalline state BiFeO3After film cooling, in crystalline state BiFeO3Repeat step 5 on thin film, be repeated 14 times, obtain
2-2 type BiFeO3-CuFe2O4Laminated film.
Embodiment 6
Step 1, is dissolved in ethylene glycol monomethyl ether for 1:2 in molar ratio by copper nitrate and ferric nitrate, after stirring 30min, adds vinegar
Anhydride, obtains the stable CuFe that Fe ion concentration is 0.16mol/L2O4Precursor liquid, CuFe2O4Ethylene glycol monomethyl ether in precursor liquid
It is 4.2:1 with the volume ratio of acetic anhydride；
Step 2, is dissolved in solvent (bismuth nitrate excess 5%) for 1:1 in molar ratio by bismuth nitrate and ferric nitrate, obtains metal ion
Total concentration is the stable BiFeO of 0.2mol/L3Precursor liquid；Wherein solvent be volume ratio be ethylene glycol monomethyl ether and the acetic acid of 3.2:1
The mixed liquor of acid anhydride；
Step 3, by LaNiO3Monocrystal chip is sequentially placed into ultrasonic waves for cleaning in detergent, acetone, ethanol, and each ultrasound wave is clear
Wash after 10min with a large amount of distilled water flushing LaNiO3Monocrystal chip, finally dries up with nitrogen.Then by LaNiO3Monocrystal chip
Put into baking oven to be baked to be dried, take out and stand to room temperature.Again by clean LaNiO3Monocrystal chip is placed in ultraviolet radiation instrument photograph
Penetrate 40min, make LaNiO3Monocrystal chip surface reaches " atomic cleanliness degree ".Then use spin-coating method at LaNiO3On monocrystal chip
Spin coating CuFe2O4Precursor liquid, obtains CuFe2O4Wet film, to CuFe2O4Wet film spin coating, spin coating rotating speed is 4250r/min, even
The glue time is 7.5s, after spin coating terminates, toasts 10min and obtain dry film, then air middle level at a temperature of 614 DEG C at a temperature of 300 DEG C
Layer annealing 28min, obtains CuFe2O4Crystalline state film；
Step 4, by CuFe2O4Crystalline state film is placed in ultraviolet radiation instrument irradiation 40min so that it is surface reaches atomic cleanliness degree；
Again at CuFe2O4Spin coating BiFeO on crystalline state film3Precursor liquid, obtains BiFeO3Wet film, to BiFeO3Wet film spin coating, spin coating turns
Speed is 4250r/min, and spin coating time is 7.5s, after spin coating terminates, toasts 13min and obtain dry film at 235 DEG C, then at 563 DEG C
Anneal in air 8min layer by layer, obtains crystalline state BiFeO3Thin film；
Step 5, treats crystalline state BiFeO3After film cooling, in crystalline state BiFeO3Repeat step 5 on thin film, be repeated 2 times, obtain
2-2 type BiFeO3-CuFe2O4Laminated film.
Use 2-2 type BiFeO that the XRD determining present invention prepares3-CuFe2O4The thing phase composition structure of laminated film, uses FE-SEM
Measure 2-2 type BiFeO that the present invention prepares3-CuFe2O4The microscopic appearance interracial contact situation of laminated film, uses TF2000 ferroelectricity
2-2 type BiFeO that the test system and test present invention prepares3-CuFe2O4The ferroelectric properties of laminated film, uses Agilent E4980A
2-2 type BiFeO that the accurate LCR table test present invention prepares3-CuFe2O4The dielectric properties of laminated film, use Agilent B2900
2-2 type BiFeO that the test present invention prepares3-CuFe2O4The leakage conductance current characteristics of laminated film, uses SQUID MPMS-XL-7
2-2 type BiFeO that the test present invention prepares3-CuFe2O4Ferromagnetic property under laminated film room temperature, result is as shown in figures 1 to 6.
As can be known from Fig. 1,2-2 type BiFeO that prepared by the present invention3-CuFe2O4Laminated film, in 2 θ=22 °, 32 °, 39 °, 46 °
With the corresponding BiFeO of diffraction maximum at 56 °3(012), (104) and (110), (006) and (202), (024), (018) and (300) crystal face
Characteristic peak (JCPDS No.86-1518), show BiFeO3Having the perovskite structure of distortion, rhombohedral system, space group is
R3c:H (161), also can observe diffraction maximum at 2 θ=18.3 °, 30.5 °, 34.7 ° and 37.1 ° simultaneously, and that corresponding is CuFe respectively2O4
The characteristic peak (JCPDS No.34-0425) of (100), (200), (103) and (202) crystal face, this shows CuFe2O4Thin film is that point is brilliant
Stone structure, Tetragonal, space group is I41/ amd (141), does not has the appearance of other impurity in thin film.
Fig. 2 is 141,171,218 and 260cm simultaneously-1Vibration mould correspondence BiFeO at place3A1-1、A1-2、A1-3 and E-3
Vibration mould, 496 and 701cm-1There is faint vibration mould correspondence CuFe at place2O4T2gAnd A1gVibration mould, further demonstrate,proves
The thin film that the clear present invention prepares is BiFeO3-CuFe2O4Laminated film.
2-2 type BiFeO that the present invention prepares as can be seen from Figure 33-CuFe2O4Film surface is smooth, and crystal grain is uniform, and it is overall thick
Degree is 540nm, wherein BiFeO3The thickness of layer is 360nm, CuFe2O4The thickness of layer is 180nm.
Fig. 4 is 2-2 type BiFeO that the present invention prepares3-CuFe2O4The dielectric and magnetic figure of laminated film, wherein BiFeO3-CuFe2O4
It is abbreviated as BFO-CuFO, BiFeO3It is abbreviated as BFO, CuFe2O4It is abbreviated as CuFO.From fig. 4, it can be seen that the present invention
2-2 type BiFeO prepared3-CuFe2O4Laminated film shows obvious dielectric dispersion phenomenon, and dielectric loss is 10kHz in frequency
Time dielectric loss peak occurs, meet Maxwell Wagner directric relaxation.
As can be seen from Figure 5, under the negative sense electric field bias of-200kV/cm, 2-2 type BiFeO that the present invention prepares3-CuFe2O4Multiple
The leakage current density closing thin film is 3.87 × 10-2A/cm2, leakage current density curve asymmetric measured under positive back bias voltage, and just
To bias one resistance hysteresis of lower existence.
Fig. 6 (a) is 2-2 type BiFeO that the present invention prepares3-CuFe2O4Laminated film at room temperature, frequency 1kHz, electric field 20V
Time the ferroelectric hysteresis loop that records, can be seen that, from Fig. 6 (a), 2-2 type BiFeO that the present invention prepares3-CuFe2O4What laminated film obtained is
Ring-type ferroelectric hysteresis loop, 2-2 type BiFeO3-CuFe2O4The ferroelectric properties of laminated film is less.
Fig. 6 (b) is 2-2 type BiFeO obtained under room temperature3-CuFe2O4The hysteresis curve of laminated film, understands from Fig. 6 (b), this
2-2 type BiFeO that invention prepares3-CuFe2O4Saturation magnetization M of laminated films=25.8emu/cm3, remanent magnetization
Mr=17.8emu/cm3；Illustration in Fig. 6 (b) is BiFeO3The hysteresis curve of thin film, it can be seen that BiFeO3Satisfying of thin film
And magnetization MsFor 0.67emu/cm3, remanent magnetization MrFor only 0.12emu/cm3.The 2-2 type that the present invention prepares
BiFeO3-CuFe2O4The magnetic property of laminated film is BiFeO340 times of thin film.
Present device requires simple, and experiment condition easily reaches, 2-2 type BiFeO prepared3-CuFe2O4Laminated film can be big
Amplitude improves BiFeO3The ferromagnetic property of thin film, obtains special leakage current density curve chart simultaneously.
Above said content is to combine concrete preferred implementation further description made for the present invention, is not all of or only
The embodiment of one, it is any etc. that technical solution of the present invention is taked by those of ordinary skill in the art by reading description of the invention
The conversion of effect, the claim being the present invention is contained.
Claims (10)
1. 2-2 type BiFeO3-CuFe2O4Laminated film, it is characterised in that: include upper layer film and the lower floor being combined with each other
Film, wherein upper layer film is BiFeO3Crystalline state film, lower membrane is CuFe2O4Crystalline state film；Described BiFeO3Crystalline state film is distortion
Perovskite structure, rhombohedral system, space group is R3c:H (161)；CuFe2O4Crystalline state film is Tetragonal, spinel structure, empty
Between point group be I41/amd(141)。
2-2 type BiFeO the most according to claim 13-CuFe2O4Laminated film, it is characterised in that: its saturated magnetization is strong
Degree MsFor 25.8emu/cm3, remanent magnetization MrFor 17.8emu/cm3；Under the negative sense electric field bias of-200kV/cm,
Its leakage current density is 3.87 × 10-2A/cm2。
3. 2-2 type BiFeO3-CuFe2O4The preparation method of laminated film, it is characterised in that comprise the following steps:
Step 1, is dissolved in copper nitrate and ferric nitrate in ethylene glycol monomethyl ether for 1:2 in molar ratio, adds acetic anhydride after stirring,
Obtain CuFe2O4Precursor liquid, CuFe2O4In precursor liquid, the concentration of Fe ion is 0.1～0.2mol/L；
Step 2, is dissolved in bismuth nitrate and ferric nitrate in solvent for 1:1 in molar ratio, obtains BiFeO3Precursor liquid, wherein BiFeO3
In precursor liquid, the total concentration of metal ion is 0.003～0.3mol/L, and solvent is the mixed liquor of ethylene glycol monomethyl ether and acetic anhydride；
Step 3, uses spin-coating method spin coating CuFe on substrate2O4Precursor liquid, obtains CuFe2O4Wet film, CuFe2O4Wet film is through even
At 250～300 DEG C, toast to obtain dry film after glue, anneal in atmosphere at 610～620 DEG C, obtain crystalline state CuFe2O4Thin film；
Step 4, treats crystalline state CuFe2O4After film cooling, in crystalline state CuFe2O4Step 3 is repeated, until it reaches required on thin film
Thickness, obtains CuFe2O4Crystalline state film；
Step 5, at CuFe2O4Spin coating BiFeO on crystalline state film3Precursor liquid, obtains BiFeO3Wet film, BiFeO3Wet film is after spin coating
At 220～250 DEG C, toast to obtain dry film, anneal in atmosphere at 555～565 DEG C, obtain crystalline state BiFeO3Thin film；
Step 6, treats crystalline state BiFeO3After film cooling, in crystalline state BiFeO3Step 5 is repeated, until it reaches required thickness on thin film
Degree, obtains 2-2 type BiFeO3-CuFe2O4Laminated film.
2-2 type BiFeO the most according to claim 33-CuFe2O4The preparation method of laminated film, it is characterised in that: institute
The CuFe stated2O4In precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is (3.5～4.5): 1；Second two in the solvent of described step 2
The volume ratio of alcohol methyl ether and acetic anhydride is (2.5～3.5): 1.
2-2 type BiFeO the most according to claim 33-CuFe2O4The preparation method of laminated film, it is characterised in that: institute
The substrate stated is FTO/ glass substrate, Si substrate, SrTiO3Monocrystal chip or LaNiO3Monocrystal chip.
2-2 type BiFeO the most according to claim 33-CuFe2O4The preparation method of laminated film, it is characterised in that: institute
State step 3 before carrying out, first substrate is carried out, the most under ultraviolet light treatment with irradiation, makes substrate surface reach atomic cleanliness
Degree, then spin coating CuFe2O4Precursor liquid；
Described step 5 is before carrying out, first to CuFe2O4Crystalline film carries out ultraviolet light treatment with irradiation, makes CuFe2O4Crystalline state film table
Face reaches atomic cleanliness degree, then spin coating BiFeO3Precursor liquid.
2-2 type BiFeO the most according to claim 33-CuFe2O4The preparation method of laminated film, it is characterised in that: institute
Spin coating rotating speed when stating spin coating in step 3 and step 5 is 4200～4500r/min, and spin coating time is 7～10s.
2-2 type BiFeO the most according to claim 33-CuFe2O4The preparation method of laminated film, it is characterised in that: institute
Stating in step 3 and step 5 baking time after spin coating is 10～15min.
2-2 type BiFeO the most according to claim 33-CuFe2O4The preparation method of laminated film, it is characterised in that: institute
Stating the annealing time in step 3 is 25～annealing time in 30min, step 5 is 8～12min.
2-2 type BiFeO the most according to claim 33-CuFe2O4The preparation method of laminated film, it is characterised in that:
Described 2-2 type BiFeO3-CuFe2O4Laminated film is by 1～6 layer crystal states CuFe2O4Thin film and 3～15 layer crystal states BiFeO3Thin
Film is constituted.
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