CN103060887A - 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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CN103060887A
CN103060887A CN2012104414079A CN201210441407A CN103060887A CN 103060887 A CN103060887 A CN 103060887A CN 2012104414079 A CN2012104414079 A CN 2012104414079A CN 201210441407 A CN201210441407 A CN 201210441407A CN 103060887 A CN103060887 A CN 103060887A
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film
bifeo
bifeo3
crystal face
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CN103060887B (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 a kind of BiFeO for preparing 3The method of ferroelectric membranc.
Background technology
With BiFeO 3Be many iron property compound system of representative, formed the research boom of worldwide single-phase many iron property magnetoelectric material.Development along with microelectronics, photoelectron and sensor technology, requirement to material property is more and more higher, ferroelectric membranc becomes the critical function material in fields such as can being widely used in microtronics, photoelectronics, integrated optics and microelectromechanical systems with character such as good ferroelectric, piezoelectricity, dielectrics.
Yet, BiFeO 3Nature has determined that it 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 3The time, the oxygen room is issued to running balance at high temperature annealing, and when the annealing process end, the partial oxygen room is detained wherein, forms the gathering in oxygen room, causes the skew of oxygen dosage, and this skew is (Fe so that the iron valence state fluctuates 3+Be converted into Fe 2+).The fluctuation of iron valence state causes large leakage conductance, thereby makes BiFeO 3Leakage current is larger, can't obtain saturated polarization by correct measurement owing to large leakage conductance makes its ferroelectricity.On the other hand, BiFeO 3The character such as the low-k that itself has and low-resistivity cause and are difficult to observe ferroelectric hysteresis loop.These characteristics have all limited its application widely.
Summary of the invention
The object of the present invention is to provide a kind of BiFeO of high remnant polarization of sol-gel method preparation (110) crystal face preferential growth 3The method of film, this kind 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 may further comprise the steps: step 1: with 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 the compensation film annealing process, and stirring obtains stable BiFeO 3Precursor liquid; X=0.01 ~ 0.03 wherein, the volume ratio 3:1 of ethylene glycol monomethyl ether and acetic anhydride, BiFeO 3Concentration of metal ions is 0.3mol/L in the precursor liquid; Step 2: adopt spin-coating method spin coating BiFeO on the FTO/glass substrate 3Precursor liquid, rotating speed are 4000 to turn/s, get dry film at 200 ℃ of baking 10 ~ 15min behind the even cementing bundle, then obtain crystalline state BiFeO at 550 ℃ of short annealing 6 ~ 8min 3Film.
The present invention further improves and is: further comprising the steps of: step 3: the film for the treatment of step 2 preparation is cooled to room temperature, repeating step 2 ' spin coating-annealing ' process, one deck induced the BiFeO of (110) crystal face preferential growth as the Seed Layer of later layer in the past 3Film is until reach the BiFeO of desired thickness 3Film.
The present invention further improves and is: x=0.01,0.02 or 0.03.
With respect to prior art, the present invention has the following advantages: (1) is not high to equipment requirements, and is easy to operate, easily control; (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 the colloid ratio of mixture is more even, thereby is easy to Uniform Doped, institute's prepared material is also even.(5) behind the codoped of A-B position, admittedly be melting into into lattice, make the originally approximate bismuth ferrite crystal lattices distortion that is perovskite structure, the structural aberration aggravation, and the solvent ratio by accurate control precursor liquid is so that the film preferential growth, thus greatly improved BiFeO 3The ferroelectric properties of film.
At present for the preparation of BiFeO 3The method of film has a lot, such 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, the Sol-Gel method suits to prepare film on large surface and surface in irregular shape owing to not needing expensive vacuum apparatus, and the accurate advantage such as controlled and be widely used for preparing ferroelectric material of chemical composition.
Adopt sol-gel method to prepare BiFeO at the FTO substrate among the present invention 3Film by the solvent ratio of accurate control precursor liquid, carries out Nd, Co codoped, adopts the quick successively mode of annealing of high temperature, obtains the BiFeO of (110) crystal face preferential growth 3Film, thus BiFeO improved greatly 3The ferroelectric properties of film.This method can be prepared the residual polarization value greater than 130 μ C/cm 2BiFeO 3Film (test frequency is 1KHz).
Description of drawings
Fig. 1 is the Bi that the present invention prepares 0.85Nd 0.15Fe 1-xCo xO 3The XRD figure of film;
Fig. 2 is the Bi that the present invention prepares 0.85Nd 0.15Fe 0.97Co 0.03O 3The ferroelectric hysteresis loop figure of film;
Embodiment
Embodiment 1
Step 1: with 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 the FTO/glass substrate 3Precursor liquid prepares film, with the even glue 15s of 4000r/min, behind the even cementing bundle, gets dry film at 200 ℃ of baking 10 ~ 15min, and then at 550 ℃ of short annealing 6 ~ 8min, cooling repeats the film that above process obtains desired thickness naturally.
At crystalline state BiFeO 3The film surface ion sputtering prepares 0.502mm 2The Au electrode, 300 ℃ the insulation 20min electrode is contacted fully with substrate.Adopt XRD determining BiFeO 3The phase of film forms structure, with the ferroelectric analyser test b of TF2000 iFeO 3The ferroelectric properties of film.
Embodiment 2
Step 1: with 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 the FTO/glass substrate 3Precursor liquid prepares film, with the even glue 15s of 4000r/min, behind the even cementing bundle, gets dry film at 200 ℃ of baking 10 ~ 15min, and then at 550 ℃ of short annealing 6 ~ 8min, cooling repeats the film that above process obtains desired thickness naturally.
At crystalline state BiFeO 3The film surface ion sputtering prepares 0.502mm 2The Au electrode, 300 ℃ the insulation 20min electrode is contacted fully with substrate.Adopt XRD determining BiFeO 3The phase of film forms structure, with the ferroelectric analyser test b of TF2000 iFeO 3The ferroelectric properties of film.
Embodiment 3
Step 1: with 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 the FTO/glass substrate 3Precursor liquid prepares film, with the even glue 15s of 4000r/min, behind the even cementing bundle, gets dry film at 200 ℃ of baking 10 ~ 15min, and then at 550 ℃ of short annealing 6 ~ 8min, cooling repeats the film that above process obtains desired thickness naturally.
At crystalline state BiFeO 3The film surface ion sputtering prepares 0.502mm 2The Au electrode, 300 ℃ the insulation 20min electrode is contacted fully with substrate.Adopt XRD determining BiFeO 3The phase of film forms structure, with the ferroelectric analyser test b of TF2000 iFeO 3The ferroelectric properties of film.
Survey BiFeO with XRD 3The phase of film forms structure, with the ferroelectric analyser test b of TF2000 iFeO 3The ferroelectric properties of film carries out the XRD test to embodiment 1,2,3, and embodiment 3 is carried out the ferroelectric properties test, and the result as shown in Figure 1 and Figure 2.As can be seen from Figure 1, the Bi of sol-gel method preparation 0.90Nd 0.15Fe 1-xCo xO 3Film all with PDF20-0169 standard card coincide better, be hexagonal structure, 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 a kind of BiFeO of high remnant polarization of sol-gel method preparation (110) crystal face preferential growth 3The method of film is with Bismuth trinitrate (Bi (NO 3) 35H 2O), iron nitrate (Fe (NO 3) 39H 2O), neodymium nitrate (Nd (NO 3) 36H 2O) and Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES (Co (NO 3) 26H 2O) be raw material (Bismuth trinitrate excessive 5%), 0.90:1-x:0.15:(x=0.01～0.03 in molar ratio) is dissolved in the ethylene glycol monomethyl ether and acetic anhydride of mixing (volume ratio is 3:1), fully magnetic agitation is to fully dissolving, and obtaining concentration of metal ions is the stable BiFeO of 0.3mol/L 3Precursor solution.With the even glue 15s of 4000r/min, behind the even cementing bundle, get dry film at 200 ℃ of baking 10 ~ 15min on the FTO substrate, then at 550 ℃ of short annealing 6 ~ 8min, cooling repeats to be spin-coated to the BiFeO that annealing process obtains desired thickness naturally 3Film.Present device requires simple, and experiment condition easily reaches, and can by accurate 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 above only is one embodiment of the present invention, it or not whole or unique embodiment, the conversion of any equivalence that those of ordinary skills take technical solution of the present invention by reading specification sheets of the present invention 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, may further comprise the steps:
Step 1: with 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 to obtain stable BiFeO 3Precursor liquid; X=0.01 ~ 0.03 wherein, the volume ratio 3:1 of ethylene glycol monomethyl ether and acetic anhydride;
Step 2: adopt spin-coating method spin coating BiFeO on the FTO/glass substrate 3Precursor liquid gets dry film at 200 ℃ of baking 10 ~ 15min behind the even cementing bundle, then obtains crystalline state BiFeO at 550 ℃ of short annealing 6 ~ 8min 3Film.
2. method according to claim 1 is characterized in that, and is further comprising the steps of:
Step 3: the film for the treatment of step 2 preparation is cooled to room temperature, and repeating step 2 is spin-coated to annealing process, and former one deck induces the BiFeO of (110) crystal face preferential growth as the Seed Layer of later layer 3Film is until reach the BiFeO of desired thickness 3Film.
3. method according to claim 1 is characterized in that, x=0.01,0.02 or 0.03.
CN201210441407.9A 2012-11-07 2012-11-07 Method for preparing high-remanent-polarization BiFeO3 film with preferentially growing (110) crystal face by sol-gel process Active CN103060887B (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103613144A (en) * 2013-11-04 2014-03-05 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
CN106939415A (en) * 2017-04-14 2017-07-11 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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CN101367671A (en) * 2008-09-12 2009-02-18 济南大学 Leadless double-layer ferro-electricity compound film for high temperature piezoelectric device and method of manufacturing the same
CN102534588A (en) * 2012-02-27 2012-07-04 陕西科技大学 Method for preparing Nd/Co-codoped BiFeO3 film on FTO (fluorine-doped tin oxide)/glass substrate surface

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103613144A (en) * 2013-11-04 2014-03-05 陕西科技大学 B-site Mn and Cu codoped high remanent polarization BiFeO3 film and preparation method
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
CN106939415A (en) * 2017-04-14 2017-07-11 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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