CN109503151A - A kind of BaTiO3Base ferroelectric ceramic material and its preparation method and application - Google Patents

A kind of BaTiO3Base ferroelectric ceramic material and its preparation method and application Download PDF

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CN109503151A
CN109503151A CN201811542098.8A CN201811542098A CN109503151A CN 109503151 A CN109503151 A CN 109503151A CN 201811542098 A CN201811542098 A CN 201811542098A CN 109503151 A CN109503151 A CN 109503151A
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batio
ferroelectric
photovoltaic device
base ferroelectric
base
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张发强
刘志甫
李永祥
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Shanghai Institute of Ceramics of CAS
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Abstract

The present invention relates to a kind of BaTiO3Base ferroelectric ceramic material and its preparation method and application, the BaTiO3Base ferroelectric ceramic material is the BaTiO of Sm donor doping3Ferroelectric material, the doping content of Sm are 0 < x≤0.05mol%.

Description

A kind of BaTiO3Base ferroelectric ceramic material and its preparation method and application
Technical field
The present invention relates to a kind of BaTiO3Base ferroelectric ceramic material and its preparation method and application, and in particular to a kind of Sm mixes Miscellaneous BaTiO3Base ferroelectric ceramic material and its preparation method and application, belongs to photoelectric conversion and photovoltaic technology field.
Background technique
The photovoltaic effect of ferroelectric material is otherwise known as bulk photovoltaic effect (Bulk photovoltaic effect), or unusual Photovoltaic effect.The phenomenon is found in the sixties in last century, can be used for Photoelectric Detection and photovoltaic energy conversion.Compared to Other types of photovoltaic effect, ferroelectric photovoltaic device have the open-circuit voltage (V not limited by forbidden bandwidthOC), and with device The increase of thickness and linearly increase, even can reach 10 in some systems3The magnitude of V/cm.Meanwhile ferroelectric photovoltaic device is also With ultrafast current response rate, therefore, there is outstanding advantage under related application background.However, being limited by ferroelectric material Big interior resistance, photoelectric current is extremely low, usually in nA magnitude, it is difficult to meet practical application request.In recent years, ferroelectricity photovoltaic is studied As one emerging hot spot of photovoltaic art, the research of photovoltaic mechanism, material and device architecture is focused mainly on, to improve device The photogenerated current of the photoelectric conversion efficiency of part, especially device, to push the practical application of ferroelectric photovoltaic device.
As a kind of ferroelectric material of classics, BaTiO3(BT) in the fields such as nonlinear optics and multilayer ceramic capacitor It is widely used, and is found to have one of several material systems of ferroelectricity photovoltaic effect earliest.With other system materials one Sample, too low bulk conductivity are to restrict one of the key factor of BT base ferroelectric photovoltaic device photovoltaic performance.Studies have shown that alms giver or Acceptor doping (such as Bi, Na, K, La, Sm, Nb, Ta, W, Mo) can provide additional carrier for BT ceramics, to improve Its bulk conductivity is theoretically advantageous to its photoelectric current is promoted.However, existing alms giver or acceptor doping (such as Bi, Na, K, La, Sm, Nb, Ta, W, Mo etc.) the doping semiconductings of BT ceramics will lead to ferroelectricity and shield and form leakage and leads, therefore be commonly referred to be iron The adverse effect factor of electrical property and the polarization process for being unfavorable for material, are influenced by this understanding, in the research of ferroelectric photovoltaic device In, the relevant report still without promoting ferroelectric material photovoltaic effect using semiconducting.In addition, for BT base ferroelectric photovoltaic device, Noble metal (such as Pt, Au) is generallyd use as electrode material, Schottky energy barrier is formed, to obtain higher photovoltage.So And the formation of schottky junction, the appearance of space-charge region was not only induced, but also form energy barrier in ferroelectric material side, these are all right Carrier transporting between electrode and ferroelectric is totally unfavorable, certainly will substantially reduce the photoelectric current of device, instead to promoting iron The photoelectric conversion efficiency of electric photovoltaic device is unfavorable.
Summary of the invention
In view of the above-mentioned problems, the object of the present invention is to provide a kind of BaTiO3Base ferroelectric ceramic material and its preparation side Method and application, and utilize gained BaTiO3The IBaTiO of base ferroelectric ceramic material preparation3The photovoltaic voltage of base ferroelectric photovoltaic device and Photovoltaic electric current is increased dramatically.
On the one hand, the present invention provides a kind of BaTiO3Base ferroelectric ceramic material, the BaTiO3Base ferroelectric ceramic material is The BaTiO of Sm donor doping3Ferroelectric material, the doping content of Sm are 0 < x≤0.05mol%.
In the present invention, BaTiO3Base ferroelectric ceramic material is the BaTiO of Sm donor doping3Ferroelectric material, specific doping content The Sm Doped ions of (doping total amount is 0 < x≤0.05mol%) can provide additional carrier, to improve its body conductance Rate, to being promoted, its photoelectric current is advantageous.And the present inventor has found the BaTiO of Sm donor doping for the first time3The resistivity of ferroelectric material is excellent Choosing belongs to 107~1013Between, it still is able to meet the BaTiO of Sm donor doping during subsequent polarization process3Ferroelectric material Polarization process achieves weak semiconducting, improves BaTiO3The bulk conductivity of base ferroelectric ceramic material, in BaTiO3Base ferroelectricity light It is had a good application prospect in volt device.
Preferably, 0 < x≤0.03mol%.
Also, preferably, the BaTiO3The resistivity of base ferroelectric ceramic material is 107~1013Between Ω cm.
On the other hand, the present invention also provides a kind of such as above-mentioned BaTiO3The preparation method of base ferroelectric ceramic material, packet It includes:
By Sm2O3Adulterated powder, BaTiO3Powder, solvent, dispersing agent and binder mixing, obtain casting slurry；
Gained casting slurry is cast on casting machine, obtains raw material band；
By multiple raw material bands through lamination and compression moulding, biscuit of ceramics is obtained；
It by biscuit of ceramics after plastic removal, is sintered at 1260~1300 DEG C, obtains the BaTiO3Base ferroelectric ceramic material.
Preferably, the Sm2O3The partial size of adulterated powder is 20~100nm, the BaTiO3The partial size of powder be 200~ 300nm。
Preferably, the solvent be ethyl alcohol, ethyl acetate, dimethylbenzene, in isopropanol at least two mixed liquor, gained stream The solid content for prolonging slurry is 55~70wt%；The dispersing agent be at least one of olein, fish oil, castor oil, Additional amount is Sm2O3Adulterated powder and BaTiO31~2wt% of powder gross mass；The binder is polyethylene glycol butyral, Additional amount is Sm2O3Adulterated powder and BaTiO35~8wt% of powder gross mass.
Preferably, the temperature of the plastic removal is 400~500 DEG C, the time is 30~120 minutes.
In another aspect, the present invention provides a kind of BaTiO3Base ferroelectric photovoltaic device, including top electrode, lower electrode and Ferroelectric layer between top electrode and lower electrode；The material of the ferroelectric layer is above-mentioned BaTiO3Base ferroelectric ceramic material. Wherein, the top electrode and lower electrode are that the metal electrode of same material weakens upper and lower electrode Xiao Te to form symmetrical structure The adverse effect of base photovoltaic effect.
In the present invention, the BaTiO of Sm donor doping is selected for the first time3Ferroelectric material is as BaTiO3Base ferroelectric photovoltaic device Ferroelectric layer, wherein the Doped ions of specific doping content (doping total amount is 0 < x≤0.05mol%) can provide additional load Stream, to improve its bulk conductivity, to being promoted, its photoelectric current is advantageous, and the resistivity of ferroelectric material ceramic sheet preferably belongs to 107-1013Between, it still is able to meet the polarization process of ferroelectric material ceramic sheet during subsequent polarization process, achieve Weak semiconducting improves BaTiO3The bulk conductivity of ceramics promotes the output of photovoltaic electric current, finally promotes BaTiO3Base ferroelectricity photovoltaic The photovoltaic effect of device.
Preferably, described power on extremely electrode of metal, preferably Al electrode.
Preferably, the lower electrode is lower metal electrode, preferably Al electrode.
In the present invention, select the active metals such as Al by with oxygen atoms bond in BT, can be in the upper and lower electrode of metal and BT Between form one layer of very thin barrier layer, inhibit the formation of ferroelectric material side schottky junction, to show as a kind of special Europe Nurse contact.In addition, carrier transports usually a kind of migration of inverse potential energy from electrode between ferroelectric, need electric field, light, Hot equal excitation is referred to as photoelectron injection using the process of light as excitation.Relative to electrode materials such as Pt, Au, the active gold such as Al Belonging to usually has lesser work function, and energy needed for photoelectron injection is relatively low.Therefore, theoretically, living using Al etc. Bold and vigorous metal is advantageous to the comprehensive performance for promoting BT base ferroelectric photovoltaic device as electrode.
Also, preferably, the sheet resistance of the Al electrode is 50~1000 Ω/.
Preferably, the ferroelectric layer with a thickness of 0.1~500 μm.The ferroelectric layer is above-mentioned BaTiO3Base ferroelectric ceramics Ferroelectric material ceramic sheet made of material.
Preferably, the BaTiO3The preparation method of base ferroelectric photovoltaic device includes: that gained ferroelectric layer is put into plated film instrument In and be evacuated to 1 × 10-3Pa applies voltage and adds to 5~7kV hereinafter, then open ion gun power supply, and adjusting argon gas valve will be from Electron current is controlled in 150~350 μ A；Top electrode target or lower electrode target are finally pushed into working position, start 1~5 point of sputtering Clock is prepared top electrode and lower electrode in gained ferroelectric layer upper and lower surface, obtains BaTiO3Base ferroelectric photovoltaic device.
Preferably, by gained BaTiO3Base ferroelectric photovoltaic device is polarised, polarization used in the polarization process Electric field is 100~3000V/mm.As in the BaTiO by obtained by3Base ferroelectric photovoltaic device polarizes, so that resulting materials are low Resistivity under electric field promotes at least two magnitudes, while device being made to show apparent pressure-sensitive character.
The present invention is based on ferroelectricity photovoltaic effects to improve the photovoltaic property of this kind of device by design of material；By traditional ferroelectricity 10 times and 40 times have been respectively increased in the open-circuit voltage and short circuit current of photovoltaic device；Ferroelectric photovoltaic device has been pushed to lead in photoelectron The application in domain.
Detailed description of the invention
Fig. 1 show the structural schematic diagram that Sm in the specific embodiment of the invention adulterates BT ferroelectric photovoltaic device；
Fig. 2 show the Sm doping BT ferroelectric material sample prepared in the specific embodiment of the invention using tape casting and solid-phase sintering The XRD diagram of product (doping x=0%, 0.005%, 0.010%, 0.020% and 0.040%), wherein illustration is the material object of sample Photo and SEM figure；
Fig. 3 show the BaTiO of the preparation of the embodiment of the present invention 13The resistivity of base ferroelectric ceramic material with Sm doping x variation Relation curve；
Fig. 4 show the BaTiO of the preparation of the embodiment of the present invention 13Base ferroelectric ceramic material polarizes in Sm doping x=0.02% The resistivity of front and back is with test electric field change relation curve, and wherein illustration is the conductivity of sample after polarizing with the change of test electric field Change curve；
Fig. 5 show the preparation of the embodiment of the present invention 1 containing Sm doping x=0.0%, 0.005%, 0.01% and 0.02% BaTiO3Four kinds of BaTiO of base ferroelectric ceramic material3J-V curve of the base ferroelectric photovoltaic device under 405nm wavelength laser photograph；
Fig. 6 show five kinds of BaTiO in the specific embodiment of the invention3Base ferroelectric photovoltaic device is irradiated in 405nm wavelength laser Under, the photoswitch change curve of short circuit current.
Specific embodiment
The present invention is further illustrated below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this Invention, is not intended to limit the present invention.
In the disclosure, BaTiO3Base ferroelectric ceramic material is the BaTiO of Sm donor doping3The doping of ferroelectric material, Sm contains Amount is 0 < x≤0.05mol%.Illustrate to following exemplary provided by the invention, BaTiO3The preparation side of base ferroelectric ceramic material Method.
By Sm2O3Adulterated powder, BaTiO3Powder, solvent, dispersing agent and binder mixing, obtain casting slurry.Wherein, Sm2O3The partial size of adulterated powder can be 20~100nm.BaTiO3The partial size of powder can be 200~300nm.Solvent is ethyl alcohol, second Acetoacetic ester, dimethylbenzene, in isopropanol at least two mixed liquor, the solid content of gained casting slurry is 55~70wt%.Dispersion Agent can be at least one of olein, fish oil, castor oil.The additional amount of dispersing agent can be adulterated powder and BaTiO3 1~2wt% of powder gross mass.Binder can be polyethylene glycol butyral.The additional amount of binder can for adulterated powder and BaTiO35~8wt% of powder gross mass.
Casting slurry is cast on casting machine, obtains raw material band (thickness can be 10-100 μm).
By multiple raw material bands through lamination and compression moulding, biscuit of ceramics is obtained.
By biscuit of ceramics after plastic removal, it is sintered at 1260~1300 DEG C, obtains BaTiO3Base ferroelectric ceramic material.It is excellent Choosing, the temperature of plastic removal are 400~500 DEG C, and the time is 30~120 minutes.
As the example of a Sm doping BT ferroelectric ceramic material preparation, preparation method includes: using nanometer BaTiO3、 Nanometer Sm2O3For raw material, by chemical formula: BaSmxTiO3Counterweight is carried out, wherein 0 < x < 0.05% (for example, 0.005%, 0.010%, 0.020% and 0.040%).Then by nanometer BaTiO3With nanometer Sm2O3Powder and ethyl alcohol, ethyl acetate, three oil The ball milling mixings such as acid glyceride, butyl benzyl phthalate, polyethylene glycol 400 are uniform, obtain casting slurry.It is being cast later Be cast on machine, obtain raw material band in homogeneous thickness, and through lamination, etc. static pressure, cutting obtain flaky pottery biscuit.Finally will Biscuit is put into plastic removal in Muffle furnace and calcines, and plastic removal temperature is 450 DEG C, and the plastic removal time is 60min, and sintering temperature is 1300 ± 30 DEG C, sintering time 30min.After sintered sample is cooling, twin polishing obtains the Sm doping BaTiO of different-thickness3Base ferroelectricity material Material is (that is, directly obtain for BaTiO3The ferroelectric material ceramic sheet of the ferroelectric layer of base ferroelectric photovoltaic device).
In the disclosure, BaTiO3The structure of base ferroelectric photovoltaic device (BT base ferroelectric photovoltaic device) packet (as shown in Figure 1) Include the ferroelectric layer 2 (ferroelectric material ceramic sheet) between two electrode of upper electrode layer 1, lower electrode layer 3 and position.Wherein, it powers on Pole layer can be electrode of metal.Lower electrode layer can be lower metal electrode.Wherein, the material of ferroelectric layer is Sm donor doping BaTiO3Ceramic material is (for example, the BaTiO of flake Sm donor doping3Ceramic material), doping total content be 0 < x≤ 0.05mol%.In alternative embodiments, the thickness of ferroelectric layer can be 0.1~500 μm.
In alternative embodiments, the upper (lower) electrode of metal can be that such as Al, Ti, Ni can be with BaTiO3Ohm is formed to connect The metal of touching, preferably translucent Al electrode.Wherein, the sheet resistance of Al electrode can be 50~1000 Ω/.
In alternative embodiments, in above-mentioned BT base ferroelectric photovoltaic device, the ferroelectric material ceramic sheet can be The BaTiO of Sm donor doping3The BT ceramic sheet for mixing samarium (Sm) of ferroelectric material preparation, doping content can be 0 < x < 0.03mol%.
Illustrate to following exemplary BT base ferroelectric photovoltaic device provided by the invention (Sm adulterates BT base ferroelectric photovoltaic device) Preparation method.
Upper electrode layer and lower electrode layer are prepared in ferroelectric layer (ferroelectric material ceramic sheet) upper and lower surface.Wherein upper and lower electricity The preparation method of pole includes but are not limited to magnetically controlled sputter method, pulsed laser deposition method, atom deposition method etc..To be adulterated in Sm Electrode under translucent Al top electrode, Al is sputtered on BT ceramic sheet as an example, preparation method includes: by Sm doping BT ceramics Thin slice is cleaned by ultrasonic twice in ethanol, and each 10min is put into plated film instrument after drying, is evacuated to 1 × 10-3Pa is hereinafter, so Ion gun power supply is opened afterwards, and voltage adds to 5~7kV, adjusts argon gas valve and controls ionic current in 150~350 μ A.Later by Al Target is pushed into working position, with plasma cleaning 30s, opens sample protective cover, sputters 1~5min.After the completion of to be sputtered, close Power supply stops gas supply, takes out sample.Preferably, in the Al electrode preparation of above-mentioned Sm doping BT ferroelectric photovoltaic device, voltage is 6kV, electric current are 250 μ A, time 3.5min.
The Sm doping BT base ferroelectric photovoltaic device prepared is polarised, polarizing voltage is 100~3000V/mm, It is preferred that polarizing voltage is 1000V/mm.
Compared with prior art, effect specific manifestation of the present invention are as follows:
The present invention provides a kind of method of above-mentioned steps preparation ferroelectric photovoltaic device, the open-circuit voltages of the ferroelectric photovoltaic device Up to 4.3V, greater than the forbidden bandwidth of ferroelectric material used；
The bulk conductivity for improving ferroelectric material is adulterated by alms giver Sm, additional carrier is provided for photovoltaic conversion, thus substantially Improve the performance of BT base ferroelectric photovoltaic device；
It is polarized by the device adulterated to alms giver Sm, resistivity of the material under existing fringing field is made to promote at least two magnitudes, Device is set to show apparent pressure-sensitive character, pressure sensitive voltage~700V/mm simultaneously.
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair Some nonessential modifications and adaptations that bright above content is made all belong to the scope of protection of the present invention.Following examples are specific Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper In the range of select, and do not really want to be defined in hereafter exemplary specific value.
Embodiment 1
As shown in Figure 1, BaTiO prepared in the embodiment of the present invention 13Base ferroelectric photovoltaic device includes upper electrode layer 1, lower electrode Ferroelectric layer 2 between layer 3 and two electrode of position.Upper electrode layer 1 and lower electrode layer 3 are translucent Al electrode.Ferroelectric layer 2 is Sm adulterates BT ceramic sheet, wherein Sm doping x can for 0mol%, 0.005mol%, 0.010mol%, 0.020mol% and 0.040mol%；
The size of Sm doping BT thin slice: length × width x thickness=4 × 4 × 0.2mm3.Wherein, Sm adulterates BT thin slice using curtain coating lamination Technique is prepared by solid-phase sintering method.With high-purity nanometer BaTiO3Powder (partial size 200-300nm), nanometer Sm2O3Powder Body (partial size 20-100nm) is raw material, by chemical formula: BaSmxTiO3(0 < x < 0.0.05%), with x=0mol%, 0.005mol%, 0.010mol%, 0.020mol% and 0.040mol% carry out counterweight.First by nanometer BaTiO3(100g) with Nanometer Sm2O3Powder and ethyl alcohol (30g), ethyl acetate (30g), olein (1.6g), polyethylene glycol butyral (7g), The ball milling mixings such as butyl benzyl phthalate (1.6g), polyethylene glycol 400 (1.6g) are uniform, obtain casting slurry (solid content About 58wt%).Be cast on casting machine later, obtain raw material band in homogeneous thickness, and through lamination, etc. static pressure, cutting Obtain biscuit of ceramics.Biscuit is finally put into plastic removal in Muffle furnace and is calcined, plastic removal temperature is 450 DEG C, and the plastic removal time is 60min, sintering temperature are 1300 ± 30 DEG C, and sintering time is 30 minutes.After the sample of sintering is cooling, its macroscopical color is photographed to record Pool variation, and its XRD and surface SEM are tested, as a result as shown in Figure 2.As can be seen that the Sm obtained adulterates BT ceramic thin in Fig. 2 Piece 2 is polycrystalline structure, gradually dimmed with the increase gray scale of doping x, and grain size is 3~6 microns；
Sm doping BT ceramic sheet is cleaned by ultrasonic twice in ethanol, each 10min is put into plated film instrument after drying, is taken out true Sky is to 1 × 10-3For Pa hereinafter, then opening ion gun power supply, voltage adds to 5~7kV, adjusts argon gas valve and controls ionic current 150~350 μ A.Al target is pushed into working position later, with plasma cleaning 30s, opens sample protective cover, sputtering 1~ 5min.After the completion of to be sputtered, power supply is closed, stops gas supply, takes out sample.Sample top electrode and the size of lower electrode are asymmetric, Lower electrode is covered on Sm doping BT ceramic sheet, and top electrode is less than Sm and adulterates BT thin slice, is 2 × 2mm2Square region, obtain Al/BT/Al sample；
The Al/BT/Al sample prepared is placed in homemade test fixture, the resistivity of test material, as a result such as Fig. 3 and figure Shown in 4.As seen from Figure 3, Sm doping can regulate and control the resistance of BT ferroelectric ceramic material on a large scale, and the resistivity of sample is from 1013 Magnitude is reduced to 103Magnitude.In addition, polarization has significant impact to the resistivity of sample, with doping x=shown in Fig. 4 For 0.02% sample, high electric field test will lead to sample polarization, and resistivity of the sample under existing fringing field is promoted after polarization More than at least two magnitude, and significant pressure-sensitive character is shown, pressure sensitive voltage is about 700V/mm；
The Al/BT/Al sample prepared is polarized.The two poles of the earth of source of stable pressure and the upper and lower electrode of sample in fixture are linked, Top electrode connects positive pole, and lower electrode connects power cathode.Slowly to 200V, (i.e. electric field is 1000V/ to the voltage of adjusting source of stable pressure Mm), pressure maintaining 15min closes power supply after the completion of polarizing, and takes out sample, obtains BaTiO3Base ferroelectric photovoltaic device.
Sample (the BaTiO that will have been polarized3Base ferroelectric photovoltaic device) carry out photoelectric properties test.By the both ends of Al/BT/Al Electrode is connected with electrochemical workstation both ends, is put to light source, is 405nm, power density 1000mW/cm with wavelength2Light The operating mode of electrochemical workstation is switched to I-V mode, opens light source, start recording data, this value is after converting by irradiation For the J-V curve of sample；The operating mode of electrochemical workstation is switched to i-t mode, start recording data, and was being tested It periodically opened in journey, close light source, test result is as illustrated in Figures 5 and 6.From Fig. 5 and Fig. 6: (1) Sm adulterates semiconducting There is significant optimization function to the photovoltaic performance of BT ceramics.(2) as x=0.005%, the open-circuit voltage ratio of Al/BT/Al is not mixed Miscellaneous sample improves 10 times.(3) as x=0.01%, the short circuit current ratio of Al/BT/Al improves 40 times undoped with sample.This Outside, as x=0.02%, the short circuit current ratio of Al/BT/Al improves nearly 20 times undoped with sample.As x=0.04%, Al/ The short circuit current ratio of BT/Al improves nearly 20 times undoped with sample.

Claims (14)

1. a kind of BaTiO3Base ferroelectric ceramic material, which is characterized in that the BaTiO3Base ferroelectric ceramic material is Sm donor doping BaTiO3Ferroelectric material, the doping content of Sm are 0 < x≤0.05mol%.
2. BaTiO according to claim 13Base ferroelectric ceramic material, which is characterized in that 0 < x≤0.03mol%.
3. BaTiO according to claim 23Base ferroelectric ceramic material, which is characterized in that the BaTiO3Base ferroelectric ceramics The resistivity of material is 107~1013Between Ω cm.
4. a kind of BaTiO as claimed in any one of claims 1-33The preparation method of base ferroelectric ceramic material, feature exist In, comprising:
By Sm2O3Adulterated powder, BaTiO3Powder, solvent, dispersing agent and binder mixing, obtain casting slurry；
Gained casting slurry is cast on casting machine, obtains raw material band；
By multiple raw material bands through lamination and compression moulding, biscuit of ceramics is obtained；
It by biscuit of ceramics after plastic removal, is sintered at 1260~1300 DEG C, obtains the BaTiO3Base ferroelectric ceramic material.
5. the preparation method according to claim 4, which is characterized in that the Sm2O3The partial size of adulterated powder be 20~ 100nm, the BaTiO3The partial size of powder is 200~300nm.
6. preparation method according to claim 4 or 5, which is characterized in that the solvent is ethyl alcohol, ethyl acetate, diformazan At least two mixed liquor in benzene, isopropanol, the solid content of gained casting slurry are 55~70wt%；The dispersing agent is three oil At least one of acid glyceride, fish oil, castor oil, additional amount Sm2O3Adulterated powder and BaTiO3The 1 of powder gross mass~ 2wt%；The binder is polyethylene glycol butyral, additional amount Sm2O3Adulterated powder and BaTiO3The 5 of powder gross mass~ 8wt%。
7. the preparation method according to any one of claim 4-6, which is characterized in that the temperature of the plastic removal be 400~ 500 DEG C, the time is 30~120 minutes.
8. a kind of BaTiO3Base ferroelectric photovoltaic device, which is characterized in that including top electrode, lower electrode and be located at top electrode and under Ferroelectric layer between electrode；The material of the ferroelectric layer is BaTiO of any of claims 1-33Base ferroelectric ceramics Material.
9. BaTiO according to claim 83Base ferroelectric photovoltaic device, which is characterized in that the extremely metal that powers on powers on Pole, preferably Al electrode.
10. BaTiO according to claim 8 or claim 93Base ferroelectric photovoltaic device, which is characterized in that the lower electrode is metal Lower electrode, preferably Al electrode.
11. according to BaTiO described in claim 8-103Base ferroelectric photovoltaic device, which is characterized in that the sheet resistance of the Al electrode For 50~1000 Ω/.
12. the BaTiO according to any one of claim 8-113Base ferroelectric photovoltaic device, which is characterized in that the ferroelectricity Layer with a thickness of 0.1~500 μm.
13. the BaTiO according to any one of claim 8-123Base ferroelectric photovoltaic device, which is characterized in that described BaTiO3The preparation method of base ferroelectric photovoltaic device includes: that the ferroelectric layer is put into plated film instrument and is evacuated to 1 × 10-3 Pa applies voltage and adds to 5~7 kV hereinafter, then open ion gun power supply, adjust argon gas valve ionic current controlled 150~ 350 μA；Top electrode target or lower electrode target are finally pushed into working position, start sputtering 1~5 minute, in gained ferroelectric layer Top electrode and lower electrode is prepared in upper and lower surface, obtains BaTiO3Base ferroelectric photovoltaic device.
14. the BaTiO according to any one of claim 8-133Base ferroelectric photovoltaic device, which is characterized in that by gained BaTiO3Base ferroelectric photovoltaic device is polarised, and polarized electric field used in the polarization process is 100~3000 V/mm.
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