CN103060887B - Method for preparing high-remanent-polarization BiFeO3 film with preferentially growing (110) crystal face by sol-gel process - Google Patents

Method for preparing high-remanent-polarization BiFeO3 film with preferentially growing (110) crystal face by sol-gel process Download PDF

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CN103060887B
CN103060887B CN201210441407.9A CN201210441407A CN103060887B CN 103060887 B CN103060887 B CN 103060887B CN 201210441407 A CN201210441407 A CN 201210441407A CN 103060887 B CN103060887 B CN 103060887B
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bifeo
bifeo3
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CN103060887A (en
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谈国强
薛旭
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Shaanxi University of Science and Technology
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Abstract

The invention provides a method for preparing a high-remanent-polarization BiFeO3 film with preferentially growing (110) crystal face by a sol-gel process, which comprises the following steps: dissolving bismuth nitrate, ferric nitrate, neodymium nitrate and cobalt nitrate used as raw materials in a mol ratio of 0.90:(1-x):0.15:x (x=0.01-0.03) in mixed ethylene glycol monomethyl ether and acetic anhydride (in a volume ratio of 3:1) to obtain a stable BiFeO3 precursor solution with the metal ion concentration of 0.3 mol/L, wherein bismuth ions are 5% excessive to compensate the volatilization in the film annealing process; and evenly coating the BiFeO3 precursor solution on an FTO (fluorine-doped tin oxide) substrate, drying to obtain a dry film, and carrying out layer-by-layer quick annealing at 550 DEG C to obtain the crystalline BiFeO3 film with expected thickness. The facility requests are simple, the experimental conditions can be easily achieved, and the BiFeO3 film with preferentially growing (110) crystal face, of which the remanent polarization is higher than 130 mu C/cm<2>, can be prepared by accurately controlling the solvent ratio of the precursor solution and the codoping of the A-B position.

Description

The BiFeO of the high remnant polarization of sol-gel method preparation (110) crystal face preferential growth 3the method of film
Technical field
The invention belongs to field of functional materials, particularly one prepares BiFeO 3the method of ferroelectric membranc.
Background technology
With BiFeO 3for the multiferroic compound system of representative, form the research boom of a worldwide single-phase multiferroic magnetoelectric material.Along with the development of microelectronics, photoelectron and sensor technology, more and more higher to the requirement of material property, ferroelectric membranc, with good ferroelectric, the character such as piezoelectricity, dielectric, becomes the critical function material that can be widely used in the fields such as microtronics, photoelectronics, integrated optics and microelectromechanical systems.
But, BiFeO 3nature determines it and is difficult to prepare pure phase, and observes saturated ferroelectric hysteresis loop.On the one hand, because the existence of Bi and Fe has influence on preparation pure phase BiFeO 3material.Traditional slow annealing technique prepares BiFeO 3time, Lacking oxygen is issued to running balance at high temperature annealing, and when annealing process terminates, part Lacking oxygen is detained wherein, forms the gathering of Lacking oxygen, causes the skew of oxygen dosage, and this skew makes iron valence state to fluctuate (Fe 3+be converted into Fe 2+).The fluctuation of iron valence state causes large leakage conductance, thus makes BiFeO 3leakage current is comparatively large, due to large leakage conductance makes its ferroelectricity cannot correct measurement and obtain saturated polarization.On the other hand, BiFeO 3the character such as the low-k itself had and low-resistivity cause and are difficult to observe ferroelectric hysteresis loop.These features all strongly limit its application.
Summary of the invention
A kind of sol-gel method is the object of the present invention is to provide to prepare the BiFeO of the high remnant polarization of (110) crystal face preferential growth 3the method of film, this kind of method can be prepared at (110) crystal face preferential growth and have higher remnant polarization (Pr > 130 μ C/cm 2) BiFeO 3film.
To achieve these goals, the present invention adopts following technical scheme:
A kind of BiFeO of high remnant polarization of sol-gel method preparation (110) crystal face preferential growth 3the method of film, comprises the following steps: step 1: by Bi (NO 3) 35H 2o, Fe (NO 3) 39H 2o, Nd (NO 3) 36H 2o and Co (NO 3) 26H 2o in molar ratio 0.90:1-x:0.15:x is dissolved in the mixed solution of ethylene glycol monomethyl ether and acetic anhydride, and wherein bismuth ion excessive 5% is with the volatilization in compensation film annealing process, stirs and obtains stable BiFeO 3precursor liquid; Wherein x=0.01 ~ 0.03, the volume ratio 3:1 of ethylene glycol monomethyl ether and acetic anhydride, BiFeO 3in precursor liquid, concentration of metal ions is 0.3mol/L; Step 2: adopt spin-coating method spin coating BiFeO on FTO/glass substrate 3precursor liquid, rotating speed is 4000 turns/s, obtains dry film, then obtain crystalline state BiFeO at 550 DEG C of short annealing 6 ~ 8min after even cementing bundle at 200 DEG C of baking 10 ~ 15min 3film.
The present invention further improves and is: further comprising the steps of: step 3: treat that film prepared by step 2 is cooled to room temperature, repeating step 2 ' spin coating-annealing ' process, one deck was as the Seed Layer of later layer in the past, induced the BiFeO of (110) crystal face preferential growth 3film, until the BiFeO reaching desired thickness 3film.
The present invention further improves and is: x=0.01,0.02 or 0.03.
Relative to prior art, the present invention has the following advantages: (1) is not high to equipment requirements, easy to operate, easily controls; (2) less demanding to the size and shape of substrate, easily control thin film composition; (3) sol-gel is chemical reaction, and synthesis temperature is lower; (4) obtain colloid through solution, because colloid ratio of mixture is comparatively even, be thus easy to Uniform Doped, institute's prepared material is also even.(5) after the codoped of A-B position, admittedly be melting into into lattice, make the approximate bismuth ferrite crystal lattices distortion in perovskite structure originally, structural aberration aggravates, and makes film preferential growth by the solvent ratio accurately controlling precursor liquid, thus drastically increases BiFeO 3the ferroelectric properties of film.
At present for the preparation of BiFeO 3the method of film has a lot, as chemical Vapor deposition process (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 method (Sol-Gel) etc.Compare additive method, Sol-Gel method, owing to not needing expensive vacuum apparatus, is suitable for preparing film on large surface and surface in irregular shape, 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 on FTO substrate 3film, by accurately controlling the solvent ratio of precursor liquid, carries out Nd, Co codoped, and the mode adopting high temperature successively to anneal fast, obtains the BiFeO of (110) crystal face preferential growth 3film, thus greatly improve BiFeO 3the ferroelectric properties of film.This method can be prepared residual polarization value and be greater than 130 μ C/cm 2biFeO 3film (test frequency is 1KHz).
Accompanying drawing explanation
Fig. 1 is Bi prepared by the present invention 0.85nd 0.15fe 1-xco xo 3the XRD figure of film;
Fig. 2 is Bi prepared by the present invention 0.85nd 0.15fe 0.97co 0.03o 3the ferroelectric hysteresis loop figure of film;
Embodiment
Embodiment 1
Step 1: by Bi (NO 3) 35H 2o, Fe (NO 3) 39H 2o, Nd (NO 3) 36H 2o and Co (NO 3) 26H 2o in molar ratio 0.90:0.99:0.15:0.01 is dissolved in the mixed solution of ethylene glycol monomethyl ether and acetic anhydride, and magnetic agitation 2h obtains the BiFeO that stable concentration of metal ions is 0.3mol/L 3precursor liquid, wherein the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 3:1.
Step 2: adopt spin-coating method spin coating BiFeO on FTO/glass substrate 3precursor liquid prepares film, and with the even glue 15s of 4000r/min, after even cementing bundle, obtain dry film at 200 DEG C of baking 10 ~ 15min, then at 550 DEG C of short annealing 6 ~ 8min, Temperature fall, repeats the film that above process obtains desired thickness.
At crystalline state BiFeO 30.502mm is prepared in film surface ion sputtering 2au electrode, 300 DEG C insulation 20min electrode is contacted completely with substrate.Adopt XRD determining BiFeO 3the thing phase composite structure of film, with TF2000 ferroelectric analyser test b iFeO 3the ferroelectric properties of film.
Embodiment 2
Step 1: by Bi (NO 3) 35H 2o, Fe (NO 3) 39H 2o, Nd (NO 3) 36H 2o and Co (NO 3) 26H 2o in molar ratio 0.90:0.98:0.15:0.02 is dissolved in the mixed solution of ethylene glycol monomethyl ether and acetic anhydride, and magnetic agitation 2h obtains the BiFeO that stable concentration of metal ions is 0.3mol/L 3precursor liquid, wherein the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 3:1.
Step 2: adopt spin-coating method spin coating BiFeO on FTO/glass substrate 3precursor liquid prepares film, and with the even glue 15s of 4000r/min, after even cementing bundle, obtain dry film at 200 DEG C of baking 10 ~ 15min, then at 550 DEG C of short annealing 6 ~ 8min, Temperature fall, repeats the film that above process obtains desired thickness.
At crystalline state BiFeO 30.502mm is prepared in film surface ion sputtering 2au electrode, 300 DEG C insulation 20min electrode is contacted completely with substrate.Adopt XRD determining BiFeO 3the thing phase composite structure of film, with TF2000 ferroelectric analyser test b iFeO 3the ferroelectric properties of film.
Embodiment 3
Step 1: by Bi (NO 3) 35H 2o, Fe (NO 3) 39H 2o, Nd (NO 3) 36H 2o and Co (NO 3) 26H 2o in molar ratio 0.90:0.97:0.15:0.03 is dissolved in the mixed solution of ethylene glycol monomethyl ether and acetic anhydride, and magnetic agitation 2h obtains the BiFeO that stable concentration of metal ions is 0.3mol/L 3precursor liquid, wherein the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 3:1.
Step 2: adopt spin-coating method spin coating BiFeO on FTO/glass substrate 3precursor liquid prepares film, and with the even glue 15s of 4000r/min, after even cementing bundle, obtain dry film at 200 DEG C of baking 10 ~ 15min, then at 550 DEG C of short annealing 6 ~ 8min, Temperature fall, repeats the film that above process obtains desired thickness.
At crystalline state BiFeO 30.502mm is prepared in film surface ion sputtering 2au electrode, 300 DEG C insulation 20min electrode is contacted completely with substrate.Adopt XRD determining BiFeO 3the thing phase composite structure of film, with TF2000 ferroelectric analyser test b iFeO 3the ferroelectric properties of film.
BiFeO is surveyed with XRD 3the thing phase composite structure of film, with TF2000 ferroelectric analyser test b iFeO 3the ferroelectric properties of film, carries out XRD test to embodiment 1,2,3, and carry out ferroelectric properties test to embodiment 3, result as shown in Figure 1 and Figure 2.As can be seen from Figure 1, the Bi for preparing of sol-gel method 0.90nd 0.15fe 1-xco xo 3it is better that film all coincide with PDF20-0169 standard card, is hexagonal structure, and exist without dephasign, main peak is the unimodal of (110) crystal face preferential growth.Bi as shown in Figure 2 0.90nd 0.15fe 0.97co 0.03o 3the residual polarization value of film is 134.3 μ C/cm 2.
The invention provides the BiFeO of the high remnant polarization of a kind of sol-gel method preparation (110) crystal face preferential growth 3the method of film, with Bismuth trinitrate (Bi (NO 3) 35H 2o), iron nitrate (Fe (NO 3) 39H 2o), neodymium nitrate (Nd (NO 3) 36H 2and Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES (Co (NO O) 3) 26H 2o) be raw material (Bismuth trinitrate excessive 5%), 0.90:1-x:0.15:(x=0.01 ~ 0.03 in molar ratio) be dissolved in mixing ethylene glycol monomethyl ether and acetic anhydride in (volume ratio is 3:1), abundant magnetic agitation, to dissolving completely, obtains the stable BiFeO that concentration of metal ions is 0.3mol/L 3precursor solution.With the even glue 15s of 4000r/min on FTO substrate, after even cementing bundle, obtain dry film at 200 DEG C of baking 10 ~ 15min, then at 550 DEG C of short annealing 6 ~ 8min, Temperature fall, repeats to be spin-coated to the BiFeO that annealing process obtains desired thickness 3film.Present device requires simple, and experiment condition easily reaches, and by accurately control Concentration of precursor solution and solvent when A-B position codoped prepare the BiFeO of the high remnant polarization of (110) crystal face preferential growth 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 (3)

1. the BiFeO of the high remnant polarization of sol-gel method preparation (110) crystal face preferential growth 3the method of film, is characterized in that, comprises the following steps:
Step 1: by Bi (NO 3) 35H 2o, Fe (NO 3) 39H 2o, Nd (NO 3) 36H 2o and Co (NO 3) 26H 2o in molar ratio 0.90:1-x:0.15:x is dissolved in the mixed solution of ethylene glycol monomethyl ether and acetic anhydride, stirs and obtains stable BiFeO 3precursor liquid; Wherein x=0.01 ~ 0.03, the volume ratio 3:1 of ethylene glycol monomethyl ether and acetic anhydride;
Step 2: adopt spin-coating method spin coating BiFeO on FTO/glass substrate 3precursor liquid, obtains dry film at 200 DEG C of baking 10 ~ 15min after even cementing bundle, then obtains crystalline state BiFeO at 550 DEG C of short annealing 6 ~ 8min 3film.
2. method according to claim 1, is characterized in that, further comprising the steps of:
Step 3: treat that film prepared by step 2 is cooled to room temperature, repeating step 2 is spin-coated to annealing process, former one deck, as the Seed Layer of later layer, induces the BiFeO of (110) crystal face preferential growth 3film, until the BiFeO reaching desired thickness 3film.
3. method according to claim 1, is characterized in that, x=0.01,0.02 or 0.03.
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CN103613144B (en) * 2013-11-04 2015-04-22 陕西科技大学 B-site Mn and Cu codoped high remanent polarization BiFeO3 film and preparation method
CN104591294A (en) * 2015-01-14 2015-05-06 陕西科技大学 Bismuth ferrite based two-phase magnetic composite powder and preparation method thereof
CN106939415B (en) * 2017-04-14 2019-04-02 中国计量大学 A kind of Au modified by nano particles Nd doping BiFeO3Film photoelectric electrode and preparation method thereof
CN113149080A (en) * 2021-06-11 2021-07-23 中国科学技术大学 Multiferroic bismuth ferrite nano-particle and preparation method thereof
CN115432738A (en) * 2022-09-05 2022-12-06 南京理工大学 BiFeO for depositing amorphous layer 3 Film and method for producing same

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