CN102723400A - Method for regulating and controlling multiferroic BiFeO3 epitaxial film band gap on SrTiO3 substrate - Google Patents

Method for regulating and controlling multiferroic BiFeO3 epitaxial film band gap on SrTiO3 substrate Download PDF

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CN102723400A
CN102723400A CN2011104582686A CN201110458268A CN102723400A CN 102723400 A CN102723400 A CN 102723400A CN 2011104582686 A CN2011104582686 A CN 2011104582686A CN 201110458268 A CN201110458268 A CN 201110458268A CN 102723400 A CN102723400 A CN 102723400A
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epitaxial film
substrate
bifeo
band gap
srtio
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付振
尹志岗
陈诺夫
张兴旺
吴金良
张汉
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Institute of Semiconductors of CAS
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Abstract

A method for regulating and controlling a multiferroic BiFeO3 epitaxial film band gap on a SrTiO3 substrate comprises the following steps: 1) Selecting a strontium titanate substrate; 2) Making a BiFeO3 epitaxial film rich in Bi component grow on the SrTiO3 substrate; 3) Controlling an atomic percent of the Bi and Fe in the BiFeO3 epitaxial film and regulating crystal lattice mismatching of the BiFeO3 epitaxial film and the SrTiO3 substrate; 4) Controlling thickness of the grown BiFeO3 epitaxial film rich in Bi component and regulating an in-plane bi-axis stress of the BiFeO3 epitaxial film.

Description

At SrTiO 3The method of many iron of regulation and control ferrous acid bismuth epitaxial film band gap on the substrate
Technical field
The present invention relates to new material photovoltaic application technical field, particularly design a kind of ability and SrTiO 3Substrate forms the rich Bi B component iFeO of Macrolattice mismatch degree 3Epitaxial film removes the biaxial stress in the flexible pellicular front through changing film thickness, thereby effectively regulates and control the band gap of many iron ferrous acid bismuth epitaxial film.
Background technology
Many iron BiFeO 3Obtain to pay close attention to widely as a kind of room temperature multi-iron material.The two intercouple of its ferroelectricity and antiferromagnetic coexistence and this; Make this material change the iron electric polarization direction through its inherent antiferromagnetic arrangement of electric field energy control and through magnetic field energy, this is that the practical application of spintronics, polymorphic information stores, sensor component etc. provides a kind of brand-brand-new way.Except the application of aspects such as information stores, BiFeO 3(ferrous acid bismuth) also shows huge superiority aspect photovoltaic device, such as photo-induced telescopic effect, the ferroelectric diode of switch, photovoltaic effect etc.Wherein attracting is exactly photovoltaic effect; Its mechanism is different from traditional photovoltaic solar battery (like silica-based solar cell)--and it detaches the light induced electron hole is discontinuous formation the by domain wall place iron electric polarization to building electromotive force in required, greatly different with situation in the pn knot.As long as the domain wall type is identical, only depend on the quantity of domain wall or the size of material along the open circuit voltage that obtains perpendicular to the domain wall direction, so BiFeO 3This novel photovoltaic material can obtain much larger than its band gap (open circuit voltage 2.7eV).At present, BiFeO 3Open circuit voltage on the yardstick of 200um, can reach tens volts, and this photovoltaic effect can be regulated and control by its inherent iron electric polarization, promptly through changing BiFeO 3The iron electric polarization direction just can be controlled the polarity of its open circuit voltage.Blemish in an otherwise perfect thing be BiFeO 3The photovoltaic conversion efficiency is high not enough, and this has greatly restricted its practicalization.Cause BiFeO 3The major reason that the photovoltaic conversion efficiency is not high be its band gap (.7eV) bigger, can only produce response to the spectrum of ultraviolet to blue green light scope, and this part light only accounts for the seldom part of solar spectrum.For further improving BiFeO 3The photovoltaic conversion efficiency, a very effective method is to reduce its band gap, so that significantly widen its spectral response range.
For this reason, provided by the invention a kind of at SrTiO 3Regulate and control BiFeO on the substrate 3The method of film band gap, this method can be regulated BiFeO on a large scale 3The film band gap, thus make BiFeO 3The optic response of film expands to the red-light spectrum scope from blue green light wave band (perhaps more short wavelength), is to strengthen BiFeO 3The photovoltaic conversion efficiency of film provides a kind of practicable path.In addition, regulation and control BiFeO provided by the invention 3The method of epitaxial film band gap is simple and practical, is easy to wide-scale adoption, and this is for many iron BiFeO 3The exploitation of photovoltaic response device is extremely important.
Summary of the invention
To current many iron BiFeO 3Band gap is bigger, and the spectral region that is absorbed is narrow, thereby the lower shortcoming of photovoltaic conversion efficiency, and main purpose of the present invention is to provide a kind of and regulates BiFeO through stress 3Band gap, and then strengthen the method for its photovoltaic conversion efficiency.
For realizing above-mentioned target, it is a kind of at SrTiO that the present invention provides 3The method of many iron of regulation and control ferrous acid bismuth epitaxial film band gap comprises the steps: on the substrate
1) selects a strontium titanates substrate;
2) at SrTiO 3The BiFeO of a kind of rich Bi component of growth on the substrate 3Epitaxial film;
3) control BiFeO 3The atomic percent of Bi and Fe in the epitaxial film, the lattice mismatch of adjusting BiFeO3 epitaxial film and SrTiO3 substrate;
4) BiFeO of the rich Bi component of control growing 3The thickness of epitaxial film is regulated BiFeO 3Biaxial stress in the face of epitaxial film.
Can find out that through technique scheme the present invention has following beneficial effect:
1) through regulating BiFeO simply 3The thickness of epitaxial film can accurately be controlled the twin shaft compression size of film, thereby make its band gap adjustable flexibly in 2.0eV to 2.7eV scope.This method can be with BiFeO 3The optic response of film significantly extends to the red-light spectrum scope from the blue green light wave band, for strengthening its photovoltaic conversion efficiency brand-new approach is provided.
2) technological approaches method provided by the invention is simple, and is compatible fully with existing growth technique and aftertreatment technology, is easy to large-scale promotion application.
Description of drawings
For making the object of the invention, technical scheme, beneficial effect is obviously clear more, below in conjunction with specific embodiment, and with reference to accompanying drawing, to further explain of the present invention, wherein:
Fig. 1 is provided by the invention at SrTiO 3Many iron of regulation and control BiFeO on the substrate 3The principle schematic of epitaxial film band gap.
Fig. 2 is rich Bi B component iFeO provided by the present invention 3The x ray diffraction spectra of epitaxial film, interior slotting little figure is the phi scanning result.
Fig. 3 is rich Bi B component iFeO provided by the present invention 3The corresponding relation of biaxial stress in epitaxial film band gap and the face.
Embodiment
See also shown in Figure 1ly, it is a kind of at SrTiO that the present invention provides 3Many iron of regulation and control BiFeO on the substrate 3The method of epitaxial film band gap comprises the steps:
1) selects a SrTiO 3Substrate.Selected substrate is (001) orientation.At first, this SrTiO 3Substrate need carry out preannealing earlier to be handled, and the preannealing temperature is set at 850-1000 ℃, and preannealing carries out under an atmospheric mobile oxygen atmosphere, and the preannealing time set is 1-3 hour; Secondly, the SrTiO that handles through preannealing 3Substrate need pass through surface corrosion and handle, and corrosive liquid is the cushioning liquid of hydrofluoric acid and ammonium fluoride, and the PH of cushioning liquid is set at 3.5-5.5, and etching time is 20-60 second; At last, the SrTiO that corroded through buffered hydrofluoric acid solution 3Substrate need carry out after annealing and handle, and the after annealing temperature is set at 850-1000 ℃, and after annealing carries out under an atmospheric mobile oxygen atmosphere, and the after annealing time set is 1-3 hour.
2) at SrTiO 3The BiFeO of a kind of rich Bi component of growth on the substrate 3Epitaxial film.Many iron of this richness Bi component BiFeO 3Epitaxial film is to utilize the preparation of magnetron sputtering growing method.This BiFeO 3The atomic molar of epitaxial film is than being Bi: Fe=1.00-1.15: 1, and growth temperature is 500-780 ℃, and growth gasses is that volume ratio is 4: 1 argon gas and an oxygen, and the chamber is pressed and is 0.5Pa during growth, and growth power is 65-250W, BiFeO 3Target and SrTiO 3Substrate distance is 3-15cm, carries out the above hyperoxia atmosphere annealing of 10Pa after growth is accomplished.This richness Bi B component iFeO 3Epitaxial film and SrTiO 3Lattice mismatch between the substrate is not higher than 4%, and the scope of change in film thickness is 1nm-1 μ m, and its corresponding biaxial stress modification scope is 0-11GPa, and the band gap modification scope is 2.0-2.7eV.
3) control BiFeO 3The atomic percent of Bi and Fe in the epitaxial film reaches and regulates BiFeO 3Epitaxial film and SrTiO 3The lattice mismatch of substrate.The atomic percent of Bi and Fe is controlled through sputtering target component and growth temperature, and wherein the sputtering target atomic molar is than Bi: Fe=1.00-1.20: 1, and the growth temperature excursion is 500-780 ℃.
4) BiFeO of the rich Bi component of control growing 3The thickness of epitaxial film reaches and regulates BiFeO 3Biaxial stress in the face of epitaxial film.Thickness is controlled through growth rate and sputtering time, and wherein the growth rate excursion is 0.5 nm/minute to 5 nm/minute, and the sputtering time scope is 1 minute to 3 hours.
Implementation result
According to the process conditions of the foregoing description, through regulating SrTiO 3Rich Bi B component iFeO on the substrate 3The thickness of epitaxial film can significantly change this rich Bi B component iFeO 3The biaxial stress of epitaxial film size, the adjusting through this biaxial stress can realize the flexible regulation and control to its band gap.Regulation and control BiFeO provided by the invention 3The method of the band gap of film can be with BiFeO 3The red range that the Film Optics response extends to from blue green light is for strengthening BiFeO 3The photovoltaic conversion efficiency of film provides brand-new approach.
Be Bi below with the component 1.07Fe 0.93O 3Film be example, the practical implementation effect of method proposed by the invention is described.Concrete grammar is as shown in Figure 1, and method shown in Figure 1 can simply reduce: substrate is selected in (1); (2) utilize appropriate process to carry out film growth; (3) the control film composition is Bi: Fe=1.07: 0.93; (4) the control thickness is with biaxial stress in the adjusting range and then regulation and control band gap.
Fig. 2 is the SrTiO of being grown in provided by the present invention 3Bi on the substrate 1.07Fe 0.93O 3The XRD figure spectrum of epitaxial film.See our rich Bi B component iFeO from XRD result 3Film (001) preferred orientation, and do not have any other dephasign.Illustration is corresponding Ph scanning spectra, shows Bi 1.07Fe 0.93O 3Film and SrTiO 3Has definite epitaxial relationship between substrate.Although our BiFeO of above presentation of results 3Be rich Bi component, but crystal structure and for changing, crystal mass is still more satisfactory.
Fig. 3 is Bi provided by the invention 1.07Fe 0.93O 3The corresponding relation of biaxial stress in epitaxial film band gap and the face.As can be seen from the figure, along with the film biaxial stress changes between 0-10.8GPa, the band gap size at 2.0eV to adjustable flexibly between the 2.7eV.By obtaining Bi among the figure 1.07Fe 0.93O 3The stress coefficient of epitaxial film band gap is 67meV/GPa, explains that its counter stress is very responsive, and regulating and control band gap through stress is a very convenient effective method.
Above-described specific embodiment has carried out further explain to the object of the invention, technical scheme and beneficial effect.Institute it should be understood that the above is merely specific embodiment of the present invention, is not limited to the present invention, and is all within spirit of the present invention and principle, any modification of being made, is equal to replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (7)

1. one kind at SrTiO 3The method of many iron of regulation and control ferrous acid bismuth epitaxial film band gap comprises the steps: on the substrate
1) selects a strontium titanates substrate;
2) at SrTiO 3The BiFeO of a kind of rich Bi component of growth on the substrate 3Epitaxial film;
3) control BiFeO 3The atomic percent of Bi and Fe in the epitaxial film, the lattice mismatch of adjusting BiFeO3 epitaxial film and SrTiO3 substrate;
4) BiFeO of the rich Bi component of control growing 3The thickness of epitaxial film is regulated BiFeO 3Biaxial stress in the face of epitaxial film.
2. according to claim 1 at SrTiO 3The method of many iron of regulation and control ferrous acid bismuth epitaxial film band gap on the substrate, wherein rich many iron of Bi component BiFeO 3Epitaxial film is to utilize the preparation of magnetron sputtering growing method.
3. according to claim 1 at SrTiO 3The method of many iron of regulation and control ferrous acid bismuth epitaxial film band gap, wherein BiFeO on the substrate 3The atomic molar of epitaxial thin film material is than being Bi: Fe=1.00-1.15: 1.
4. according to claim 2 at SrTiO 3The method of many iron of regulation and control ferrous acid bismuth epitaxial film band gap, wherein magnetron sputtering growth BiFeO on the substrate 3Epitaxial film, its growth temperature are 500-780 ℃, and growth gasses is 4: 1 argon gas of volume ratio and oxygen, and the chamber is pressed and is 0.5Pa during growth, and growth power is 65-250W, BiFeO 3Target and SrTiO 3Substrate distance is 3-15cm, carries out the above hyperoxia atmosphere annealing of 10Pa after growth is accomplished.
5. according to claim 1 at SrTiO 3The method of many iron of regulation and control ferrous acid bismuth epitaxial film band gap on the substrate, wherein rich Bi B component iFeO 3Epitaxial film and SrTiO 3The lattice mismatch that substrate forms is not higher than 4%.
6. according to claim 1 at SrTiO 3The method of many iron of regulation and control ferrous acid bismuth epitaxial film band gap, the wherein BiFeO of the rich Bi component of control growing on the substrate 3The scope that epitaxial film thickness changes is 1nm-1 μ m, and its corresponding biaxial stress modification scope is 0-11GPa.
7. according to claim 1 at SrTiO 3The method of many iron of regulation and control ferrous acid bismuth epitaxial film band gap, wherein BiFeO on the substrate 3The band gap modification scope of epitaxial film is 2.0-2.7eV.
CN2011104582686A 2011-12-31 2011-12-31 Method for regulating and controlling multiferroic BiFeO3 epitaxial film band gap on SrTiO3 substrate Pending CN102723400A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103066108A (en) * 2012-12-27 2013-04-24 浙江理工大学 Preparation method and application of ferrous acid terbium positive-negative (p-n) heterostructure
CN103066277A (en) * 2013-01-10 2013-04-24 西南大学 Preparation method of anode material of BiFeO3 lithium ion battery
CN103117322A (en) * 2013-02-01 2013-05-22 中国科学技术大学 Photovoltaic device based on polar/nonpolar heterojunctions and production method thereof
CN103588250A (en) * 2013-10-17 2014-02-19 河北师范大学 Method for preparing oriented La0.5Ba0.5MnO3 nanorod or nanobar growing on SrTiO3 substrate
CN104103752A (en) * 2013-04-15 2014-10-15 北京师范大学 Method of preparing oxide film material with shape memory effects and application thereof
CN106591781A (en) * 2017-01-10 2017-04-26 河北大学 Improvement method for interface dead layer of ultrathin lanthanum-strontium-manganese oxide film
WO2018161643A1 (en) * 2017-03-06 2018-09-13 清华大学 Stress control method
CN113594025A (en) * 2021-06-11 2021-11-02 河北大学 Preparation method of silicon-based molecular beam heteroepitaxial growth material, memristor and application

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101859779A (en) * 2010-05-13 2010-10-13 复旦大学 Polarized tuning ferroelectric film diode memory

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101859779A (en) * 2010-05-13 2010-10-13 复旦大学 Polarized tuning ferroelectric film diode memory

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
唐兆俊等: "多铁性BiFeO3/SrTiO3多层膜的透射电镜研究", 《电子显微学报》 *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103066108B (en) * 2012-12-27 2015-11-18 浙江理工大学 A kind of ferrous acid terbium p-n heterojunction, preparation method and application
CN103066108A (en) * 2012-12-27 2013-04-24 浙江理工大学 Preparation method and application of ferrous acid terbium positive-negative (p-n) heterostructure
CN103066277A (en) * 2013-01-10 2013-04-24 西南大学 Preparation method of anode material of BiFeO3 lithium ion battery
CN103066277B (en) * 2013-01-10 2015-07-08 西南大学 Preparation method of anode material of BiFeO3 lithium ion battery
CN103117322A (en) * 2013-02-01 2013-05-22 中国科学技术大学 Photovoltaic device based on polar/nonpolar heterojunctions and production method thereof
CN104103752A (en) * 2013-04-15 2014-10-15 北京师范大学 Method of preparing oxide film material with shape memory effects and application thereof
CN104103752B (en) * 2013-04-15 2017-03-29 北京师范大学 A kind of preparation method and applications of the oxide film material with shape memory effect
CN103588250A (en) * 2013-10-17 2014-02-19 河北师范大学 Method for preparing oriented La0.5Ba0.5MnO3 nanorod or nanobar growing on SrTiO3 substrate
CN103588250B (en) * 2013-10-17 2014-12-10 河北师范大学 Method for preparing oriented La0.5Ba0.5MnO3 nanorod or nanobar growing on SrTiO3 substrate
CN106591781A (en) * 2017-01-10 2017-04-26 河北大学 Improvement method for interface dead layer of ultrathin lanthanum-strontium-manganese oxide film
WO2018161643A1 (en) * 2017-03-06 2018-09-13 清华大学 Stress control method
CN113594025A (en) * 2021-06-11 2021-11-02 河北大学 Preparation method of silicon-based molecular beam heteroepitaxial growth material, memristor and application
CN113594025B (en) * 2021-06-11 2023-07-28 河北大学 Preparation method of silicon-based molecular beam heteroepitaxial growth material, memristor and application

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Application publication date: 20121010