CN104835880A - Application of Cr3+ doped PZT film in preparation of ferroelectric film solar cell - Google Patents
Application of Cr3+ doped PZT film in preparation of ferroelectric film solar cell Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 5
- 239000011521 glass Substances 0.000 claims abstract description 44
- 239000010409 thin film Substances 0.000 claims description 84
- 239000010408 film Substances 0.000 claims description 48
- 239000000463 material Substances 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 5
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 4
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 claims description 4
- 229940046892 lead acetate Drugs 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- FQHYQCXMFZHLAE-UHFFFAOYSA-N 25405-85-0 Chemical compound CC1(C)C2(OC(=O)C=3C=CC=CC=3)C1C1C=C(CO)CC(C(C(C)=C3)=O)(O)C3C1(O)C(C)C2OC(=O)C1=CC=CC=C1 FQHYQCXMFZHLAE-UHFFFAOYSA-N 0.000 claims description 3
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 3
- VEUACKUBDLVUAC-UHFFFAOYSA-N [Na].[Ca] Chemical compound [Na].[Ca] VEUACKUBDLVUAC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 230000010287 polarization Effects 0.000 abstract description 31
- 230000000694 effects Effects 0.000 abstract description 8
- 150000002500 ions Chemical class 0.000 abstract description 8
- 238000000137 annealing Methods 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 30
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 25
- 238000000151 deposition Methods 0.000 description 14
- 230000008021 deposition Effects 0.000 description 14
- 239000004065 semiconductor Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 238000003980 solgel method Methods 0.000 description 6
- 230000002269 spontaneous effect Effects 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- -1 Cr3+ ion Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000028161 membrane depolarization Effects 0.000 description 3
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000010748 Photoabsorption Effects 0.000 description 1
- PJILMBYYVIXWTK-UHFFFAOYSA-N [Bi]=O.[Fe] Chemical compound [Bi]=O.[Fe] PJILMBYYVIXWTK-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000019771 cognition Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [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
- 230000007423 decrease Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 210000004276 hyalin Anatomy 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 description 1
- 229910021424 microcrystalline silicon Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- 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
-
- 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
- H01L31/0248—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
- H01L31/0321—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 characterised by the doping material
-
- 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 application of a Cr3+ doped PZT film in preparation of a ferroelectric film solar cell. The mole percentage of Cr3+ in the Cr3+ doped PZT film ranges from 2 to 10%; the solar cell comprises glass, an ITO conductive layer, a Cr3+ doped PZT film layer and another ITO conductive layer successively from bottom to top; and the Cr3+ doped PZT film layer is arranged between the ITO conductive layers. Cr3+ doped ions of the mole percentage of 2 to 10 % is introduced into the PZT film layer for the first time to form the Cr3+ doped PZT film; a ferroelectric film of relatively high residual polarization is obtained at a relatively low annealing temperature; and compared with a ferroelectric film solar cell of a common PZT/ITO structure, the residual polarization is improved by 2 to 3 times, the photoelectric conversion efficiency is improved by 6 times, and the effects are better.
Description
Technical field
The invention belongs to ferroelectric thin film solar cell, be specifically related to a kind of Cr3+ of comprising ion doping pzt thin film and preparing the application in ferroelectric thin film solar cell.
Background technology
Solar energy is the regenerative resource that resource is the abundantest, and have unique advantage and huge developing and utilizingpotentiality, solar power generation is a new technology in Solar use approach.Traditional solid state solar cell mainly contains: crystalline silicon (monocrystalline and polycrystalline) solar cell, amorphous/microcrystalline silicon film solar cell and compound solar cell (GaAs, CIGS).The maximum voltage that conventional solid-state photoelectric device can produce equals its electronics energy gap, even so-called series connection cell---wherein there is the accumulation of the n-negative connection of some semiconductors, its photoelectricity voltage that can produce also is limited, because the degree of depth that light penetrates is limited.The photovoltaic effect of semiconductor is caused by macroheterogeneity, produces the energy gap (being generally the three ten-day period of hot season) that photovoltaic voltage is generally no more than semiconductor.In addition, the technology of producing the conventional solar cell such as crystalline silicon, GaAs is high energy consumption, high pollution, and therefore, cause the cost of current solar cell higher, generating price is far away higher than firepower or hydroelectric power generation price.
These solid state solar cell have n-negative pole to connect---the connection between positive pole semiconductor layer and negative electricity sublayer.These context layers are keys of photovoltaic effect, when solar cell absorbs the photon from the sun, the energy of photon can produce electron-hole pair, and these electron-hole pairs are separated in depletion region, namely small n-negative attachment section, is then collected as electric power.But this process need photon penetrates the material of depletion region.Their energy also accurately must mate the electronic energy band-gap energy of semiconductor, the gap namely between semiconductor valence band and conduction band, do not have electronic state between conduction band and valence band.
Ferroelectric material is as a kind of Novel photovoltaic material, there is the advantages such as cost is low, environmental friendliness, preparation technology are simple, there is the unusual photovoltaic effect being different from semiconductor completely: evenly the phenomenon of steady-state short-circuit photogenerated current or open circuit voltage appears in ferroelectric crystal under uniform illumination, photovoltaic voltage is not by the restriction of crystal energy gap (Eg), high 2 ~ 4 orders of magnitude of comparable Eg, reach 10
3~ 10
5v/cm.This output photoelectric exceeding kilovolt just because of ferroelectric material is pressed and is the character of electric energy by transform light energy, makes it have important application prospect in fields such as optical sensor, CD-ROM driver, ferroelectric photovoltaic cells.In addition, the photo-absorption region of ferroelectric material is whole material internal, and is not only confined to depletion region, considerably increases light absorption, is conducive to producing more electron-hole pair; The electron-hole pair that material internal produces can be separated by the depolarization field of ferroelectric material; The size of depolarization field is directly proportional to the size of residual polarization.
At present, in the ferroelectric materials such as barium titanate, lithium niobate, lead titanates, bismuth iron-oxygen, photovoltaic effect has been found.Traditional ferroelectric thin film solar battery structure is metal electrode/ferroelectric thin film/metal electrode structure; All there is metal/film Schottky barrier in upper and lower two interfaces of ferroelectric thin film, the direction of the internal electric field that this upper and lower interface Schottky barrier is formed is always contrary, thus causes the reduction of total internal electric field; Metal electrode is generally opaque or translucent, and incident ray can not be absorbed by ferroelectric thin film completely, reduces generating efficiency.
Lead zirconate titanate, be called for short PZT, solid solution is a kind of functional material of excellent performance, and having excellent ferroelectric, piezoelectricity and pyroelectric property, is a focus of research at present.The structure of spin coating PZT film on ITO substrate, can replace the performance study that expensive Pt substrate makes ferroelectric thin film, and considerably increase absorbing of incident ray.But deposition pzt thin film needs high annealing (general more than 600 degree), and in the process of high annealing, ito transparent electrode will decompose, the transparency and conductive capability is caused greatly to reduce; Owing to there is a large amount of Lacking oxygen (positively charged in the film of ITO, be similar to the hole in semiconductor), part Lacking oxygen during high annealing in ITO will to pzt thin film diffusion inside, these Lacking oxygen partially or completely will shield the spontaneous polarization of pzt thin film as space charge, residual polarization is caused greatly to reduce, depolarization field reduces, thus causes photoelectric conversion efficiency usually lower.Therefore, research and develop a kind of new ferroelectric thin film, there is high residual polarization, for ferroelectric thin film solar cell, effectively can improve the photovoltaic efficiency of battery, necessary.
Summary of the invention
The Cr3+ doped PZT film of high residual polarization that what the object of the invention was prepared under being to provide a kind of low deposition temperature have is preparing the application in ferroelectric thin film solar cell, effectively improves the luminous efficiency of ferroelectric thin film solar cell.
For achieving the above object, the technical solution used in the present invention is:
Cr3+ doped PZT film is preparing the application in ferroelectric thin film solar cell, and in described Cr3+ doped PZT film, the molar percentage of Cr3+ is 2% ~ 10%.
In technique scheme, the thickness of described Cr3+ doped PZT film is 400 nm.Film leakproof can be ensured, larger photoelectric current can be measured again; If film thickness is too small, film leaks electricity, and does not detect photovoltaic voltage; If film thickness is too thick, although can measure photovoltaic voltage, photovoltaic electric current is very little, and so electrical power is just little, is unfavorable for application.
Preferably, in Cr3+ doped PZT film disclosed by the invention, the molar percentage of Cr3+ is 5%.Compared to non-doped PZT film, the residual polarization of this ferroelectric thin film improves 2.8 times, the photovoltaic efficiency of solar cell formed improves 6 times, overcomes prior art and thinks and the technology prejudice that Cr3+ doped PZT film can cause its residual polarization to reduce achieve beyond thought effect.
Ferroelectric thin film solar cell disclosed by the invention comprises base material, positive and negative electrode and Cr3+ doped PZT film; Described Cr3+ doped PZT film is located between positive and negative electrode.
Above-mentioned application specifically comprises the following steps: on base material, prepare positive electrode; Lead acetate, butyl titanate, tetrabutyl zirconate, chromic salts are dissolved in acetic acid and EGME mixed liquor, form colloidal sol; Cr3+ doped PZT film is prepared on the positive electrode again by sol-gal process; Then on Cr3+ doped PZT film, negative electrode is prepared.
In technique scheme, described chromic salts is chromic nitrate or chromic acetate; Described base material is clear glass, and such as sodium calcium base or silicon boryl clear glass, also can use other substrates, as Pt/Si; Described electrode is ito transparent electrode.Incident ray can efficiently be passed through.
Utilize the method for magnetron sputtering on base material, plate indium oxide layer tin (ITO) and form hyaline layer, as positive electrode; Magnetron sputtering is utilized to prepare indium tin oxide transparent layer, as negative electrode on Cr3+ doped PZT film; Light also can inject ferroelectric thin film from negative pole face from positive pole-face.
Ferroelectric thin film of the present invention, according to order during application, comprises substrate of glass, ITO transparency conducting layer, Cr3+ doped PZT thin layer and ITO transparency conducting layer from top to bottom successively; Described two-layer ITO conductive layer forms the positive-negative electrode structure of ferroelectric thin film.
There are three kinds of cations in pzt thin film, be Pb2+, Zr4+, Ti4+ respectively, their ionic radius is 0.119nm, 0.072nm, 0.061nm respectively, and Cr3+ ionic radius is 0.062nm.Prior art is thought: Cr3+ ion doping is in pzt thin film, and Cr3+ will as acceptor ion, Zr4+ or Ti4+ of the few size of substitution ion semidiameter; Because the valence state of Cr3+ is lower than Zr4+ or Ti4+, hole (positively charged) will be produced in pzt thin film; These holes partially or completely shield the spontaneous polarization of pzt thin film together with Lacking oxygen intrinsic in pzt thin film, thus cause the residual polarization of pzt thin film greatly to reduce.Therefore, prior art thinks that Cr3+ ion doping pzt thin film can cause the residual polarization of pzt thin film greatly to reduce, and causes ferroelectric thin film solar cell photovoltaic generating efficiency prepared therefrom greatly to reduce.
In pzt thin film, in order to obtain higher spontaneous polarization, the general way with improving annealing temperature (more than 600 degree) realizes.Because ITO can not bear the high temperature of more than 600 degree, therefore, ITO conductive layer deposits pzt thin film, the transparency and the conductive capability of ITO can be destroyed; In addition, the Lacking oxygen of ITO also to pzt thin film diffusion inside, thus can increase the space charge of pzt thin film inside, and these space charges will shield spontaneous polarization, thus greatly reduce the residual polarization of pzt thin film.
The present invention utilize molar percentage be 2% ~ 10% Cr3+ doped PZT film, effectively improve the residual polarization of pzt thin film; Even if under lower temperature annealing (520 degree), also higher residual polarization can be obtained; Avoid ITO conductive layer to be destroyed, the Lacking oxygen also in minimizing ITO conductive layer is to pzt thin film diffusion inside simultaneously.Use it for and prepare ferroelectric thin film solar cell, effectively improve photovoltaic efficiency, overcome prior art prejudice.
Because technique scheme is used, the present invention compared with prior art has following advantages:
1. the present invention introduces at pzt thin film layer the Cr3+ Doped ions that molar percentage is 2% ~ 10% first, constitutes Cr3+ doped PZT film, compares common pzt thin film, and film excess polarization of the present invention improves nearly 3 times; Use it for and prepare ferroelectric thin film solar cell, photovoltaic efficiency improves about 6 times; Overcome prior art and think that Cr3+ ion doping pzt thin film can cause the residual polarization of pzt thin film greatly to reduce, thus reduce the technology prejudice of ferroelectric thin film solar battery efficiency.
2., when ferroelectric thin film of the present invention is for the preparation of ferroelectric thin film solar cell, be easy to preparation, annealing temperature is low, also can obtain higher residual polarization, substantially increase photovoltaic efficiency, achieves beyond thought effect, is suitable for applying.
Accompanying drawing explanation
Accompanying drawing 1 is the structural representation of ferroelectric thin film solar cell of the present invention;
Wherein: 1, glass; 2, ITO conductive layer; 3, Cr3+ doped PZT thin layer; 4, ITO conductive layer;
Accompanying drawing 2 is XRD figure (20-80 degree) of embodiment and comparative example pzt thin film;
Accompanying drawing 3 is XRD partial enlarged drawings (35-55 degree) of embodiment and comparative example pzt thin film;
Accompanying drawing 4 is electric leakage flow graphs of embodiment and comparative example ferroelectric thin film solar cell;
Accompanying drawing 5 is embodiment and comparative example ferroelectric thin film solar cell electric hysteresis loop figure;
Accompanying drawing 6 is photoelectric current-voltage characteristic curves of embodiment and comparative example ferroelectric thin film solar cell.
Embodiment
Below in conjunction with accompanying drawing, embodiment and comparative example, the invention will be further described:
In the embodiment of the present invention, being prepared as of Cr3+ doped PZT thin film sol: be dissolved in acetic acid and EGME mixed liquor by lead acetate, butyl titanate, tetrabutyl zirconate, chromic salts, forms colloidal sol; Table 1 is the pzt thin film colloidal sol raw material mol ratio of this comparative example of the present invention, embodiment.
Table 1 pzt thin film colloidal sol raw material mol ratio
| Lead acetate | Butyl titanate | Tetrabutyl zirconate | Chromic nitrate | Chromic acetate | |
| Embodiment one | 1.08 | 0.79 | 0.2 | 0 | 0.02 |
| Embodiment two | 1.05 | 0.76 | 0.19 | 0 | 0.05 |
| Embodiment three | 0.99 | 0.72 | 0.18 | 0.10 | 0 |
| Comparative example one | 1.1 | 0.8 | 0.2 | 0 | 0 |
| Comparative example two | 1.05 | 0.76 | 0.19 | 0.005 | 0 |
| Comparative example three | 1.09 | 0.79 | 0.2 | 0 | 0.01 |
Embodiment one
At deposition on glass ITO conductive layer, form transparent ITO electro-conductive glass (ITO/ glass), its light transmittance is greater than 85%, and surface resistivity is about 90 Ω/; ITO/ glass is the pzt thin film of 2% by the thick Cr3+ doping content of sol-gel method deposition 400nm, anneals under 520 DEG C of air, form the pzt thin film (PCZT2) of polycrystalline Cr3+ doping; Then, with magnetron sputtering ITO conductive layer on PCZT2/ITO/ glass, ITO/PCZT2/ITO/ glass structure is formed, i.e. the ferroelectric thin film solar cell of high residual polarization; Fig. 1 is its structural representation.
Embodiment two
At deposition on glass ITO conductive layer, form ITO electro-conductive glass, its light transmittance is greater than 85%, and surface resistivity is about 90 Ω/, forms the electroconductive ITO/glass of conductive, transparent; ITO/ glass is the pzt thin film of 5% by the thick Cr3+ doping content of sol-gel method deposition 400nm, anneals under 520 DEG C of air, form the pzt thin film (PCZT5) of polycrystalline Cr3+ doping; Then, with magnetron sputtering ITO conductive layer 2 on PCZT5/ITO/ glass, ITO/PCZT5/ITO/ glass structure is formed, i.e. the ferroelectric thin film solar cell of high residual polarization.
Embodiment three
At deposition on glass ITO conductive layer 1, form ITO electro-conductive glass, its light transmittance is greater than 85%, and surface resistivity is about 90 Ω/, forms the electroconductive ITO/glass of conductive, transparent; ITO/ glass is the pzt thin film of 10% by the thick Cr3+ doping content of sol-gel method deposition 400nm, anneals under 520 DEG C of air, form the pzt thin film (PCZT10) of polycrystalline Cr3+ doping; Then, with magnetron sputtering ITO conductive layer 2 on PCZT10/ITO/ glass, ITO/PCZT10/ITO/ glass structure is formed, i.e. the ferroelectric thin film solar cell of high residual polarization.
Comparative example one
At deposition on glass ITO conductive layer 1, form transparent ITO electro-conductive glass (ITO/ glass), its light transmittance is greater than 85%, and surface resistivity is about 90 Ω/; With the pzt thin film that sol-gel method deposition 400nm is thick on ITO/ glass, anneal under 520 DEG C of air, form the pzt thin film (PCZT0) of polycrystalline; Then, magnetron sputtering ITO conductive layer on PCZT0/ITO/ glass, forms ITO/PCZT0/ITO/ glass structure, i.e. ferroelectric thin film solar cell.
Comparative example two
At deposition on glass ITO conductive layer, form ITO electro-conductive glass, its light transmittance is greater than 85%, and surface resistivity is about 90 Ω/, forms the electroconductive ITO/glass of conductive, transparent; ITO/ glass is the pzt thin film of 0.5% by the thick Cr3+ doping content of sol-gel method deposition 400nm, anneals under 520 DEG C of air, form the pzt thin film (PCZT0.5) of polycrystalline Cr3+ doping; Then, with magnetron sputtering ITO conductive layer 2 on PCZT0.5/ITO/ glass, ITO/PCZT0.5/ITO/ glass structure is formed, i.e. ferroelectric thin film solar cell.
Comparative example three
At deposition on glass ITO conductive layer, form ITO electro-conductive glass, its light transmittance is greater than 85%, and surface resistivity is about 90 Ω/, forms the electroconductive ITO/glass of conductive, transparent; ITO/ glass is the pzt thin film of 1% by the thick Cr3+ doping content of sol-gel method deposition 400nm, anneals under 520 DEG C of air, form the pzt thin film (PCZT1) of polycrystalline Cr3+ doping; Then, with magnetron sputtering ITO conductive layer 2 on PCZT1/ITO/ glass, ITO/PCZT1/ITO/ glass structure is formed, i.e. ferroelectric thin film solar cell.
Accompanying drawing 2 is the XRD curve chart of above-mentioned ferroelectric thin film, can find out that above-mentioned pzt thin film and Cr3+ doped PZT film are pure ferroelectric phase, not have obvious dephasign.
According to the position of the characteristic peak in XRD, the pzt thin film of calculating and the lattice constant of Cr3+ doped PZT film and unit cell volume parameter, in table 2; Can find out that the unit cell volume of the unit cell volume comparison comparative example film of embodiment film is little; The Lattice parameters Unit Cell volume of comparative example three film and the unit cell volume of PCZT0 film almost do not have difference, illustrate that the Cr3+ in pzt thin film replaces different.
Table 2 film lattice constant and unit cell volume parameter.
Accompanying drawing 3 is the XRD figure of partial enlargement, compared with comparative example film, distance between (200) and (002) characteristic peak of embodiment film diminishes, and the raising along with Cr3+ Doped ions concentration is described, PCZT film has the trend from Tetragonal to cubic phase transition.
Accompanying drawing 4 is the leakage current of pzt thin film and Cr3+ doped PZT film, the leakage current of the pzt thin film of embodiment is less than the leakage current of the film of comparative example, illustrate that in product of the present invention, Cr3+ is as donor ion, the electronics of generation neutralizes (or compensation) Lacking oxygen, and space charge is reduced; The leakage current of PCZT1 film, PCZT0.5 film is more much bigger than the leakage current of PCZT0 film simultaneously, and particularly the leakage current of doping 1% is maximum; Illustrate that in comparative example two, three, Cr3+ creates unnecessary hole as acceptor ion, makes space charge increase.
The electric hysteresis loop that accompanying drawing 5 is tested for battery sample, shows as the typical electric hysteresis loop of ferroelectric material; Can find out that the residual polarization of comparative example one sample is 43.8 μ C/cm2, the residual polarization of embodiment one, embodiment two, embodiment three sample is 102.1 μ C/cm2,124.4 μ C/cm2,98.8 μ C/cm2; Improve 2.3 times, 2.8 times, 2.2 times respectively, mainly because part is discharged by the spontaneous polarization of space-charge screening than the sample in comparative example one; Comparative example two can be found out simultaneously, the residual polarization of comparative example three sample is 32.8 μ C/cm2,28.6 μ C/cm2, lower than the sample in comparative example one, mainly because part spontaneous polarization is by space-charge screening, and the doping of doping result compared with 0.5% of 1% is lower, consistent with the cognition of prior art.
Under AM1.5 illumination is penetrated, light is from this side of ITO conductive layer 1(glass) incident, photoelectric current-the voltage curve (see accompanying drawing 6) of test ferroelectric thin film solar cell, can find out that comparative example one product short circuit current and open circuit voltage are respectively 0.011mA/cm2 and 0.13V, fill factor, curve factor is 0.34, and photovoltaic efficiency is 0.004%; Embodiment two product short circuit current and open circuit voltage are respectively 0.014mA/cm2 and 0.38V, and fill factor, curve factor is 0.45, and photovoltaic efficiency is 0.024%, and photoelectric conversion efficiency improves 6 times than the sample in comparative example one.
Test the photoelectric current-voltage performance of all the other products equally.Embodiment one product short circuit current and open circuit voltage are respectively 0.11mA/cm2 and 0.32V, and fill factor, curve factor is 0.42, and photovoltaic efficiency is 0.015%, and photoelectric conversion efficiency improves 3.8 times than the sample in comparative example one; Embodiment three products short circuit current and open circuit voltage are respectively 0.013mA/cm2 and 0.26V, and fill factor, curve factor is 0.40, and photovoltaic efficiency is 0.014%, and photoelectric conversion efficiency improves 3.5 times than the sample in comparative example one.Comparative example two product short circuit current and open circuit voltage are respectively 0.009 mA/cm2 and 0.10V, and fill factor, curve factor is 0.32, and photovoltaic efficiency is 0.003%; Comparative example three products short circuit current and open circuit voltage are respectively 0.01mA/cm2 and 0.11V, and fill factor, curve factor is 0.28, and photovoltaic efficiency is 0.002%.
Therefore, compared with comparative example one, ferroelectric thin film of the present invention has higher residual polarization, the residual polarization of embodiment two improves 2.8 times, solar cell photovoltaic generating efficiency prepared therefrom improves 6 times, overcome prior art and think that Cr3+ doped PZT film can cause its residual polarization to reduce, the technology prejudice causing solar battery efficiency to decline, achieves beyond thought effect.
Claims (10)
1.Cr3+ doped PZT film is preparing the application in ferroelectric thin film solar cell, it is characterized in that: in described Cr3+ doped PZT film, and the molar percentage of Cr3+ is 2% ~ 10%.
2. application according to claim 1, is characterized in that: the thickness of described Cr3+ doped PZT film is 400 nm.
3. application according to claim 1, is characterized in that: described ferroelectric thin film solar cell comprises base material, positive and negative electrode and Cr3+ doped PZT film; Described Cr3+ doped PZT film is located between positive and negative electrode.
4. application according to claim 1, is characterized in that: in described Cr3+ doped PZT film, and the molar percentage of Cr3+ is 5%.
5. application according to claim 1, is characterized in that, comprises the following steps: on base material, prepare positive electrode; Lead acetate, butyl titanate, tetrabutyl zirconate, chromic salts are dissolved in acetic acid and EGME mixed liquor, form colloidal sol; Cr3+ doped PZT film is prepared on the positive electrode again by sol-gal process; Then on Cr3+ doped PZT film, negative electrode is prepared.
6. application according to claim 5, is characterized in that: described chromic salts is chromic nitrate or chromic acetate.
7. application according to claim 5, is characterized in that: described base material is clear glass.
8. application according to claim 7, is characterized in that: described base material is sodium calcium base or silicon boryl clear glass.
9. application according to claim 5, is characterized in that: described electrode is ito transparent electrode.
10. application according to claim 5, is characterized in that: utilize magnetron sputtering to prepare positive pole or negative pole.
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