CN105702762B - A kind of method for preparing T-phase bismuth ferrite thin film - Google Patents
A kind of method for preparing T-phase bismuth ferrite thin film Download PDFInfo
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- CN105702762B CN105702762B CN201610040335.5A CN201610040335A CN105702762B CN 105702762 B CN105702762 B CN 105702762B CN 201610040335 A CN201610040335 A CN 201610040335A CN 105702762 B CN105702762 B CN 105702762B
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 64
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 50
- 239000010409 thin film Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 22
- 238000004528 spin coating Methods 0.000 claims description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 239000012692 Fe precursor Substances 0.000 claims description 11
- 229910002244 LaAlO3 Inorganic materials 0.000 claims description 11
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 230000001965 increasing effect Effects 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- 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 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 63
- 239000000463 material Substances 0.000 abstract description 41
- 230000028161 membrane depolarization Effects 0.000 abstract description 14
- 230000004888 barrier function Effects 0.000 abstract description 7
- 238000004549 pulsed laser deposition Methods 0.000 abstract description 3
- 230000010287 polarization Effects 0.000 description 20
- 230000005621 ferroelectricity Effects 0.000 description 15
- 239000010408 film Substances 0.000 description 15
- 230000005684 electric field Effects 0.000 description 8
- 238000005286 illumination Methods 0.000 description 8
- 230000007246 mechanism Effects 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 239000013078 crystal Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000005036 potential barrier Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
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- 239000003292 glue Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000013517 stratification Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 241000931526 Acer campestre Species 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 229910002353 SrRuO3 Inorganic materials 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
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- 229910052737 gold Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 235000021485 packed food Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a kind of method for preparing T-phase bismuth ferrite thin film, and using the T-phase bismuth ferrite thin film of sol-gal process preparation epitaxial growth, obtained bismuth ferrite thin film does not have dephasign, and method is simple, and cost is relatively low.And material identical central electrode and edge electrodes are prepared simultaneously with pulsed laser deposition on T-phase bismuth ferrite thin film, obtain the bismuth ferrite thin film device with bulk photovoltaic effect.The contribution of depolarization field in the photovoltaic effect of bismuth ferrite thin film device, the contribution of Schottky barrier and the contribution of domain wall can be eliminated, only intrinsic bulk photovoltaic effect.
Description
Technical field
The invention belongs to ferroelectric material field, and in particular to a kind of method for preparing T-phase bismuth ferrite thin film.
Background technology
Ferroelectric material due to abnormality photovoltaic effect (photovoltaic voltage is not limited by crystal energy gap (Eg),
Even than EgHigh 2~4 orders of magnitude, up to 103~105V/cm) receive much concern.
Before half a century, people have discovered that ferroelectricity photovoltaic is imitated in non-centrosymmetrical various ferroelectric materials
Should, stable photovoltaic effect can be produced along the direction of polarization.It is generally believed that the photovoltaic effect of ferroelectric material is spontaneous originating from its
Polarization, one of distinguishing feature of ferroelectricity photovoltaic be exactly when polarised direction changes under electric field action, photogenerated current also with
Change, and photoproduction sense of current is opposite with polarised direction all the time inside ferroelectric material.Ferroelectricity photovoltaic effect with
Traditional pn-junction except that：In traditional pn-junction, light activated electron hole pair is divided rapidly by the built in pn-junction
From making drift motion in the opposite direction, finally reach electrode, then collected by electrode.Therefore, in theory, pn-junction is too
Photovoltage caused by positive energy battery is limited by semiconductor band gap width, typically less than 1V.For ferroelectricity photovoltaic effect
For, the photovoltage experimentally obtained is proportional to the distance between polarization intensity and electrode, without being limited by band gap width
System, can reach 104V.The photovoltage of solar cell is higher, it is meant that caused electric energy is more, and efficiency is higher.
Although the existing decades of the research about ferroelectricity photovoltaic effect, up to now, also nobody can definitely point out
Also dispute always be present in the principle of this material photovoltaic process, the origin on ferroelectric material photovoltaic effect.In general,
Influenceing the factor of ferroelectric material photovoltage has a variety of, such as the distance between two electrodes, the intensity of light, the conduction of material
Property, remanent polarization, crystal orientation, crystallite dimension, Lacking oxygen, domain wall and interface etc..But essentially, ferroelectricity light
The mechanism of volt effect mainly has following several：
(1) bulk photovoltaic effect
This mechanism thinks that photovoltage results from the inside of ferroelectric material, therefore is referred to as " bulk photovoltaic effect ", ferroelectricity material
Material is then used as " current source ".Caused stabling current (photogenerated current under illumination：Js) with having non-centrosymmetry ferroelectric material
Property is relevant.In with noncentrosymmetric crystal, state that electronic driven amount is k is to the probability that momentum is the transition of k ' states institute
It is different from the state that momentum is k ' to the probability that momentum is k-state transition from it, it result in the MOMENTUM DISTRIBUTION of photo-generated carrier not
Symmetrically, so that stable electric current can be formed under light illumination.It can be expressed as by the total current density of ferroelectric material (J)：
J=Js+(σd+σph)E (1)
In formula, σdAnd σphConductance of the ferroelectric material under details in a play not acted out on stage, but told through dialogues and light field, i.e. dark conductance and photoconduction are represented respectively；E=
V/d is the electric field inside ferroelectric material under illumination, depending on the distance between applied voltage (V) and two electrodes (d).Due to electrode
The distance between it is generally all bigger, and the dark conductance of most of ferroelectric materials and photoconduction are all very low, therefore by ferroelectricity
The solar photovoltaic device that material is formed can be considered as current source.In ferroelectric material, the open-circuit voltage V under illuminationocCan be with table
It is shown as：
As can be seen from the above equation, if total electrical conductivity (σd+σph) unobvious depend on luminous intensity if, open-circuit voltage Voc
With circuit photocurrent density JscIt is linearly increasing, show that open-circuit voltage is proportional to short-circuit photocurrent Ioc(because short-circuit photocurrent IocDeng
In circuit photocurrent density JsIt is multiplied by the area of current flowing), the ratio of open-circuit voltage and short-circuit photocurrent is equal to sample
Thickness.That is, if the solar photovoltaic device being made up of ferroelectric material can be considered as into current source, photoelectric current is just
It is invariable, then the value of short-circuit photovoltage is just proportional to the thickness of material.
(2) domain wall is theoretical
Yang et al. has found when studying bismuth ferrite (bismuth ferrite, writing a Chinese character in simplified form BFO) film photovoltaic effect, photovoltage in BFO
As the increase of domain wall quantity in polarised direction is linearly increasing, obvious photovoltaic effect is then not observed in polarised direction
Should.Domain wall theory thinks, because polarization intensity can produce one-component at domain wall, its potential caused by the domain wall
For~10mV, domain wall width is about 2nm, therefore is polarized in electric field caused by domain wall and is up to 5 × 106V/m, this value are much larger than pn
Internal electric field in knot, it is considered as the origin that ferroelectric material produces photovoltaic effect, and the main drive of separation photo-generated carrier
Power.Due to there are many electricdomains in ferroelectric material, joined end to end after being polarized between farmland and farmland, and domain wall is just as being together in series
Nanoscale photovoltaic generator, photovoltage gradually adds up along polarised direction.This mechanism and the solar-electricity connected
The concept in pond is similar, and its output voltage is each unit sum.If the distance between two electrodes are bigger, electricdomain is got over
More, caused photovoltage is also higher between two electrodes under illumination, and this model can be very good to explain photovoltaic effect.
Further, since producing continuous photoelectric current under illumination, domain wall is then treated as current source, total open-circuit voltage in some documents
(photovoltage) VocBy the distance between the current density of ferroelectric material, electrical conductivity and electrode J under illuminationscDetermine.With body photovoltaic
Unlike effect, photovoltaic effect is attributed to exciting for carrier at domain wall by domain wall theory, it is believed that light swashs outside domain wall
The carrier recombination velocity of hair quickly, can ignore bulk photovoltaic effect.
Although can be very good to illustrate photovoltaic effect with domain wall theory, i.e. it is wide can be much larger than forbidden band for photovoltage
Degree, however, it is only at all unaccountable with neticdomain wall theory to have some experimental phenomenas, it is necessary to consider that bulk photovoltaic effect is managed
By.For example, according to domain wall model, caused by the landing of potential is polarization charge at domain wall, therefore photoelectric current independent of
In the polarization direction of light.However, researchers observe photoelectric current with incident light polarization direction in the ferroelectric materials such as BFO
The phenomenon for changing and changing, shows that the origin of ferroelectric material photovoltaic effect is more complicated than what everybody envisioned.In ferroelectricity light
Lie prostrate in effect, because electricdomain and bulk effect all contribute to photogenerated current, therefore, if both mutually grow, photogenerated current is larger,
Conversely, photogenerated current is smaller, this can explain why do not observed parallel to domain wall direction in yang et al. experiment
To photoelectric current.
(3) schottky junction effect
When ferroelectric material contacts to form Schottky barrier with electrode, interface energy band will be bent, caused by under illumination
Electron hole pair will be driven by internal field near electrode, and caused photoelectric current is largely by Schottky barrier and depletion layer
Depth determine.According to this model, the size of photovoltage is still confined to ferroelectricity produced by inside the Schottky barrier
The band gap of material, research ferroelectricity photovoltaic effect early stage Schottky effect caused by voltage be often ignored, be because
It is well below the unusual photovoltage in most of ferroelectric crystal.But Schottky effect becomes in ferroelectric thin film photovoltaic device
It is more and more important, because the photovoltaic voltage output in these devices is generally smaller.In general, by identical electrodes and ferroelectricity material
In the ferroelectric photovoltaic device with sandwich structure for expecting composition, the contribution that Schottky barrier produces photoelectric current is not present,
Because by upper and lower two identical electrodes with two schottky junctions that ferroelectric material is formed being back-to-back, mutually containment, because
This caused photovoltage and electric current offset.However, according to different types of electrode, it is possible to achieve have vertical stratification
Ferroelectric photovoltaic device in photovoltaic effect enhancing.Because schottky junction effect is unrelated with the polarised direction of ferroelectric material, according to
This feature can distinguishes the contribution of schottky junction and bulk photovoltaic effect to photoelectric current.But some researchers think, Xiao Te
The height of base potential barrier can change its polarised direction to regulate and control by applying electric field to ferroelectric material.Also, work as Schottky
When potential barrier and the polarised direction of ferroelectric material change, the symbol of photovoltage also changes therewith.For example, by
In the ferroelectricity diode with vertical stratification that Au/BFO/Au is formed, photogenerated current and photovoltage are all with polarised direction
Change and change.The main reason for initially BFO film bulk photovoltaic effects being considered to produce this phenomenon, but subsequent research table
Bright, the change of Schottky barrier of the BFO films in polarization process is caused by mainly due to the migration of Lacking oxygen, and it is empty to work as oxygen
When position migration is frozen at low temperature, photovoltaic effect no longer changes with the transformation of polarised direction.
(4) depolarization field effect
For the ferroelectric thin film in polarized state, film surface has the polarization charge of high concentration, if do not examined
Consider screen effect, these highdensity polarization charges will produce a huge electric field in ferroelectric layer.Using BFO films as
Example, its remanent polarization is about 100 μ C/ ㎝2, electric field is up to 3 × 10 caused by the polarization charge that is not shielded10V/m.When
When ferroelectric thin film is with metal or semiconductor contact, surface charge caused by residual polarization will be by the freedom in metal or semiconductor
Charged moiety shields.Generally, why surface charge not exclusively compensates charge centroid not by shielding because of polarization charge and freely
Overlap, electric field, i.e. depolarization field are just produced inside whole ferroelectric thin film.Depolarization field may be very big, such as is for thickness
For 10 to 30nm BTO films, by BTO and SrRuO3Depolarization field in the sandwich structure that electrode is formed is about 45 ×
106V/m.So high depolarization field is considered as to separate the main drive of photo-generated carrier, while also indicates that unusual photovoltaic
The shield degree of effect and polarization charge is closely related.The distribution of shielded packaged food depends on ferroelectric material and metal (or semiconductor)
Property, such as remanent polarization, free charge density and dielectric constant etc..On the other hand the polarization charge pair not shielded
The influence of depolarization field depends primarily on the thickness of ferroelectric layer：The small ferroelectric layer result depolarization field of thickness is big.In general, half
Conductor contacted with ferroelectric material caused by depolarization field contacted than metal with ferroelectric material caused by depolarization field it is big, this be by
There is less free charge density and larger dielectric constant in semi-conducting material, so as to produce weaker screen effect.
Generally speaking, influenceing the mechanism of ferroelectric thin film photovoltaic effect has a variety of, bulk effect, depolarization field, electricdomain, interfacial potential
Influence colleague of the factors such as base to photovoltaic effect is present, and certain contact between each other be present.Therefore, how to distinguish every kind of
Contribution of the mechanism to ferroelectricity photovoltaic effect, understand fully that any mechanism is occupied an leading position to photovoltaic effect with weight in ferroelectric material
The meaning wanted.
In numerous ferroelectric materials, bismuth ferrite (BFO) is due to larger polarization intensity, relatively small optical ribbon
Gap and receive much concern.Due to lattice mismatch between BFO films and substrate be present, therefore BFO films will be stressed effect.When should
When power is smaller, BFO belongs to diamond structure (rhombohedral Structure, i.e. R phases).If the BFO films of R phases
The face internal pressure stress being subject to continues to increase, then its lattice constant and structure will become different, so as to influence its physical property.c
The lattice constant in direction increases with the increase of stress, and when stress reaches to a certain degree, R phase in version is the four directions distorted
Crystal structure (tetragonal structure, i.e. T-phase).Lattice constant in face and outside face is respectivelyC/a=1.26, belong to P4mm point groups.
For R phases BFO, its polarised direction is diagonally.Therefore, when BFO photovoltaic effects are studied, due to
There is component (parallel to surface) in face and outside face in polarised direction (opposite direction of depolarization field), therefore right (perpendicular to surface)
Photovoltaic effect just has a contribution.The sheet of bulk photovoltaic effect is thus hardly resulted on the occasion of because measured bulk photovoltaic effect
In just contain the contribution of depolarization field.In addition, the electrode of BFO two sides if (upper/lower electrode or left and right electrode) is asymmetric
Words, resulting photovoltaic effect include the contribution of interface potential barrier in addition to bulk photovoltaic effect.Unlike R phases, T-phase
BFO polarised direction is perpendicular to its surface.
T-phase BFO polarised direction is perpendicular to its surface.Therefore, it is contemplated that, the BFO films of T-phase are prepared first, so
Plate identical electrode on the surface afterwards, just do not include the contribution of depolarization field in resulting photovoltaic effect so (because table
Connecting line between the electrode of two, face is vertical with depolarization field), the contribution of Schottky barrier (interface potential barrier) can also be deducted
(because surface is identical electrode).Again because polarised direction is all the time perpendicular to surface, therefore for T-phase BFO, only
180 degree domain wall, domain wall are also vertical with surface.So the photovoltaic effect of measurement is naturally also free of the contribution of domain wall, it is only
Intrinsic bulk photovoltaic effect.
The content of the invention
In order to measure the intrinsic photovoltaic effect of bismuth ferrite thin film, the invention provides a kind of T-phase bismuth ferrite thin film for preparing
Method, the T-phase bismuth ferrite thin film of epitaxial growth is prepared using sol-gel process, obtained bismuth ferrite thin film does not have dephasign, the system
Preparation Method is simple, and cost is relatively low.
The present invention is achieved through the following technical solutions：
A kind of method for preparing T-phase bismuth ferrite thin film, comprises the following steps：
The preparation of iron precursor liquid：Appropriate glacial acetic acid is added in ferric nitrate, is placed in 70-90 DEG C of thermostat water bath and adds
Heat of solution, it is transferred to after being cooled to room temperature in volumetric flask, then ethylene glycol ethyl ether constant volume is added dropwise and produces iron precursor liquid；
The preparation of bismuth precursor liquid：Glacial acetic acid and ethylene glycol ethyl ether are added in bismuth nitrate as mixed solvent, through dissolving
After be transferred in volumetric flask, instill ethylene glycol ethyl ether constant volume produce bismuth precursor liquid；
Iron precursor liquid is added drop-wise in bismuth precursor liquid, acetylacetone,2,4-pentanedione is added after dropwise addition to adjust dissolved adhesiveness, is well mixed
By the 24 hours colloidal sol for producing pure bismuth ferrite；
By LaAlO3Substrate is cleaned with alcohol and acetone in ultrasonic wave respectively, is dried；It is positioned over the suction of sol evenning machine
On piece；The air humidity around sol evenning machine is reduced to 20%-50% with dehumidifier；
Bismuth ferrite colloidal sol is taken, LaAlO is dropped in dropper3Substrate, place 5-20 seconds, the then spin coating on sol evenning machine；
After sol evenning machine stops, by LaAlO3Substrate is removed, with hair-dryer from the back side of substrate by hot blast drying, then
Tube furnace is put into be sintered；The pressure of oxygen is maintained at 0.01-0.03M Pa in tube furnace, will with 2-5 ° per minute of speed
Temperature is increased to 200-300 °, is incubated 10-30 minutes, is then raised to 550-620 ° with identical programming rate, insulation is 1-3 small
When；Room temperature is naturally rung to afterwards；T-phase bismuth ferrite thin film is made.
Further, it is added drop-wise in iron precursor liquid in bismuth precursor liquid sol-process, it is molten to control can also adds ethanol in proper amount amine
The viscosity of glue, the uniformity of film that viscosity obtains greatly very much afterwards is bad and thicker, uneven after sintering, out-of-flatness.
Further, the LaAlO3The substrate that (001) that sizes of substrate is 10 × 10 × 0.5mm is orientated.
Further, bismuth ferrite colloidal sol drops in LaAlO3Spin coating process of the substrate on sol evenning machine includes, and first turns in 150-250
Spin coating 5-15 seconds under speed per minute, spin coating 10-30 seconds when then spin coating machine speed brings up to 2500-4000 rpms.
Beneficial effects of the present invention：
A kind of method for preparing T-phase bismuth ferrite thin film of the present invention, prepare epitaxial growth using sol-gel process first
T-phase bismuth ferrite thin film, this preparation method is simple, cost is low, and the chemical composition of material is easily controlled.Obtained bismuth ferrite thin film
There is no dephasign generation, preparing central electrode and edge electrodes with pulsed laser deposition on T-phase bismuth ferrite thin film is made tool
There is the bismuth ferrite thin film device of bulk photovoltaic effect, be advantageous to test the intrinsic bulk photovoltaic effect of ferroelectric thin film.For how to distinguish
Contribution of the different mechanisms to ferroelectricity photovoltaic effect, understand fully that in ferroelectric material any mechanism is occupied an leading position tool to photovoltaic effect
There is important meaning.
Brief description of the drawings
Fig. 1 is the XRD diffracting spectrums of obtained T-phase bismuth ferrite thin film in embodiment；
Fig. 2 is that the structural representation of film membrane module made from obtained T iron acid bismuth thin film is utilized in embodiment；
Fig. 3 is that the mask plate used during the thin-film device depositing electrode in Fig. 2 is prepared in embodiment；
Fig. 4 is numbering of the photovoltaic effect to electrode for measuring bismuth ferrite thin film device；
Fig. 5 is the tendency chart of short-circuit photocurrent value between central electrode and different edge electrodes.
Reference
1- substrates；2- bismuth ferrite thin films；3- central electrodes；4- edge electrodes.
Embodiment
The invention will be further described with reference to the accompanying drawings and examples.
A kind of method for preparing T-phase bismuth ferrite thin film, comprises the following steps：
The preparation of iron precursor liquid：Appropriate glacial acetic acid is added in ferric nitrate, is placed in 70-90 DEG C of thermostat water bath and adds
Heat of solution, preferably 80 DEG C, it is transferred to after being cooled to room temperature (general 23 degree) in volumetric flask, ethylene glycol ethyl ether is added dropwise using buret
Constant volume produces iron precursor liquid.
The preparation of bismuth precursor liquid：Glacial acetic acid and ethylene glycol ethyl ether are added in bismuth nitrate as mixed solvent, through dissolving
After be transferred in volumetric flask, using buret instill ethylene glycol ethyl ether constant volume produce bismuth precursor liquid；
Iron precursor liquid is added drop-wise in bismuth precursor liquid, acetylacetone,2,4-pentanedione is added after dropwise addition to adjust dissolved adhesiveness, is well mixed
By the 24 hours colloidal sol for producing pure bismuth ferrite.
By LaAlO3Substrate is cleaned with alcohol and acetone in ultrasonic wave respectively, is dried, and is positioned over the suction of sol evenning machine
On piece, the air humidity around sol evenning machine is reduced to 20%-50%, preferably 45% with dehumidifier.
Bismuth ferrite colloidal sol is taken, drops in what (001) that size is 10 × 10 × 0.5mm was orientated with dropper dropper drop one
LaAlO3Substrate, place the 5-20 seconds, preferably 10 seconds, the then spin coating on sol evenning machine：First under 150-250 rpms of speed
Spin coating 5-15 seconds, spin coating 10-30 seconds when then spin coating machine speed brings up to 2500-4000 rpms；It is it is preferred that first every at 200 turns
Spin coating 8 seconds, spin coating 20 seconds when then spin coating machine speed brings up to 3200 rpms under the speed of minute.
After sol evenning machine stops, by LaAlO3Substrate is removed, with hair-dryer from the back side of substrate by hot blast drying, then
Tube furnace is put into be sintered；The pressure of oxygen is maintained at 0.01-0.03M Pa in tube furnace, will with 2-5 ° per minute of speed
Temperature is increased to 200-300 °, is incubated 10-30 minutes, is then raised to 550-620 ° with identical programming rate, insulation is 1-3 small
When.It is preferred that the pressure of oxygen is maintained at 0.01M Pa in tube furnace, temperature is increased to 250 ° with 3 ° per minute of speed, insulation
20 minutes, 580 ° then are raised to identical programming rate, room temperature is naturally rung to after being incubated 2 hours；T-phase ferrous acid is made
Bismuth thin film.
Optimization, it is added drop-wise in iron precursor liquid in bismuth precursor liquid sol-process, it is molten to control can also adds ethanol in proper amount amine
The viscosity of glue, the uniformity of film that viscosity obtains greatly very much afterwards is bad and thicker, uneven after sintering, out-of-flatness.
XRD diffraction is carried out to obtained T-phase bismuth ferrite thin film, as shown in figure 1, the bismuth ferrite prepared as can be known from Fig. 1 is thin
Film is T-phase, is epitaxial growth, and only (00L) L can take 1,2,3... diffraction maximums, and be produced without other dephasigns.
Ag electrodes as shown in Figure 4 are deposited in obtained T-phase bismuth ferrite thin film using pulsed laser deposition, are made as schemed
The bismuth ferrite thin film device with bulk photovoltaic effect shown in 2 and Fig. 3, including sequentially consist of bed course 1, ferroelectric thin film 2
And electrode, electrode include the edge electrodes 4 central electrode 3 and array around central electrode 3, depositing electrode process is as follows：
Chip bench is polished with sand paper first, and cleaned up.Then T-phase bismuth ferrite thin film will be prepared
(001) the LAO substrates of orientation are bonded on chip bench with heat conduction elargol, and then the mask plate of shape shown in Fig. 2 blocks substrate
Center, only reserve side upper part.It is put into after drying in cavity on warm table, starts to vacuumize.Treat that air pressure is extracted into 10-4Below Pa
When, substrate is blocked with baffle plate.The energy and frequency parameter of laser are set, carry out pre-sputtering (can also select to remove Ag targets
Select other conductive films, Au, Cu, Pt, ITO etc.) dirt on surface, target is exposed fresh surface, the pre-sputtering time is general
For 2~5 minutes；During pre-sputtering, the parameter such as adjustment laser optical path, range, so that plumage brightness end and chip bench are tangent.Rotate
Chip bench and target, and make laser in X, Y-direction particles；Afterwards, baffle plate is removed, is deposited.According to required film
Thickness selects suitable sedimentation time.The bismuth ferrite thin film device with bulk photovoltaic effect is just made after having deposited.
The test of photovoltaic effect is carried out to the bismuth ferrite thin film device with bulk photovoltaic effect is made：Optical maser wavelength used
For 408nm, power is 50mW linearly polarized light.Measuring instrument is digital sourcemeter keithley2611.Measure result such as Fig. 5
It is shown, Fig. 5 be different angle (i.e. a-b1 (with horizontal direction in 0 °), a-b2 (45 °) ... b-b8 (315 °)) when, center
The size of short-circuit photocurrent between electrode and corresponding edge electrode.It can be seen that in the case where not changing incident light, it is resulting
Short-circuit photocurrent and angle there is certain dependence (equivalent to not changing angle, and to change the polarization side of incident light
To).Because polarised direction in the bismuth ferrite thin film device and domain wall are perpendicular to bismuth ferrite thin film surface, bismuth ferrite thin film surface
Electrode is same electrode, therefore it is the photoelectric current as caused by bulk photovoltaic effect that experimental result, which directly demonstrates,.
Claims (4)
- A kind of 1. method for preparing T-phase bismuth ferrite thin film, it is characterised in that：Comprise the following steps：The preparation of iron precursor liquid：Glacial acetic acid is added in ferric nitrate, is placed in 70-90 DEG C of thermostat water bath and dissolves by heating, it is cold But to being transferred in volumetric flask after room temperature, then ethylene glycol ethyl ether constant volume is added dropwise and produces iron precursor liquid；The preparation of bismuth precursor liquid：Glacial acetic acid and ethylene glycol ethyl ether are added in bismuth nitrate as mixed solvent, turned after dissolving Move on in volumetric flask, instill ethylene glycol ethyl ether constant volume and produce bismuth precursor liquid；Iron precursor liquid is added drop-wise in bismuth precursor liquid, acetylacetone,2,4-pentanedione is added after dropwise addition to adjust dissolved adhesiveness, is passed through after well mixed The 24 hours colloidal sol for producing pure bismuth ferrite；By LaAlO3Substrate is cleaned with alcohol and acetone in ultrasonic wave respectively, is dried；It is positioned on the suction piece of sol evenning machine； The air humidity around sol evenning machine is reduced to 20%-50% with dehumidifier；Bismuth ferrite colloidal sol is taken, LaAlO is dropped in dropper3Substrate, place 5-20 seconds, the then spin coating on sol evenning machine；After sol evenning machine stops, by LaAlO3Substrate is removed, and is then placed in hair-dryer from the back side of substrate by hot blast drying Tube furnace is sintered；The pressure of oxygen is maintained at 0.01-0.03M Pa in tube furnace, with 2-5 ° per minute of speed by temperature 200-300 ° is increased to, is incubated 10-30 minutes, is then raised to 550-620 ° with identical programming rate, is incubated 1-3 hour； Room temperature is naturally rung to afterwards；T-phase bismuth ferrite thin film is made.
- A kind of 2. method for preparing T-phase bismuth ferrite thin film according to claim 1, it is characterised in that：In iron forerunner's drop It is added in bismuth precursor liquid sol-process, can also adds ethanol in proper amount amine to control the viscosity of colloidal sol.
- A kind of 3. method for preparing T-phase bismuth ferrite thin film according to claim 1, it is characterised in that：The LaAlO3Substrate The substrate that (001) that size is 10 × 10 × 0.5mm is orientated.
- A kind of 4. method for preparing T-phase bismuth ferrite thin film according to claim 1, it is characterised in that：Bismuth ferrite colloidal sol drips In LaAlO3Spin coating process of the substrate on sol evenning machine includes, first the spin coating 5-15 seconds under 150-250 rpms of speed, so Spin coating 10-30 seconds when spin coating machine speed brings up to 2500-4000 rpms afterwards.
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