CN204243085U - Perovskite-based thin film solar cell - Google Patents

Perovskite-based thin film solar cell Download PDF

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CN204243085U
CN204243085U CN201420649588.9U CN201420649588U CN204243085U CN 204243085 U CN204243085 U CN 204243085U CN 201420649588 U CN201420649588 U CN 201420649588U CN 204243085 U CN204243085 U CN 204243085U
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perovskite
solar cell
layer
thin film
film solar
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孟庆波
李冬梅
肖俊彦
罗艳红
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Shenzhen Huayu Solar Technology Co ltd
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Institute of Physics of CAS
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • 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
    • Y02E10/549—Organic PV cells

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Abstract

The utility model discloses a kind of perovskite-based thin film solar cell.Comprise: transparent substrates; The conductive layer formed on a transparent substrate; The compacted zone of the semi-conducting material formed on the electrically conductive; The porous support layer that compacted zone is formed; The semiconductor light-absorption layer with perovskite structure of filling in the internal voids of porous support layer; The hole transmission layer that porous support layer is formed; Hole transmission layer is formed to electrode; Hole transmission layer is the conducting polymer composite material that can carry out hole transport.The utility model adopts conducting polymer composite material as the hole transmission layer of perovskite-based thin film solar cell, compared with traditional perovskite-based thin film solar cell only containing polymer hole transport layer, improve the hole migration ability of hole transmission layer, improve the conversion efficiency of battery.

Description

Perovskite-based thin film solar cell
Technical field
The utility model relates to perovskite-based technical field of solar cells, especially relates to a kind of perovskite-based thin film solar cell.
Background technology
Solar cell is the device directly light energy conversion being become electric energy by photoelectric effect or Photochemical effects, is also called photovoltaic cell.Its gas-to electricity photovoltaic effect of particular semiconductor material, specifically, the interaction of light and semiconductor produces photo-generated carrier, and photo-generate electron-hole arrives the two poles of the earth respectively to the internal electric field formed by semiconductor inside again, produces electromotive force.When being connected with external circuit, just can continuously generation current.This semiconductor photoelectric device should meet following two conditions: 1) energy of incident light should be greater than semiconductor energy gap, and semi-conducting material has enough large absorption coefficient to incident light; 2) semiconductor has photovoltaic structure, must can form internal electric field.
Conversion efficiency of solar cell is the technical indicator of solar cell most critical, and the height of battery efficiency depends on the characteristic of battery material and the framework of whole system.Current silica-based solar cell technology is photovoltaic technology the most ripe, most widely used.But along with the day by day maturation of silica-based solar cell technology, its defect is also day by day obvious, and one is that conversion ratio is restricted, and two is that cost of manufacture is high.Therefore, people start the solar cell material and the technology that sight are turned to low cost.Novel thin film solar cell is more and more subject to people's attention due to its cheap cost and simple preparation technology.Improve one of key of thin film solar cell efficiency and be to seek that low cost, light absorption range are wide, the light absorbent of high absorption coefficient.The organic and inorganic lead semiconductor material with Ca-Ti ore type layer structure, as the light absorbent of a kind of cheapness, high absorption coefficient, receives publicity.
Development over the past two years based on perovskite thin film solar cell is very fast.Perovskite solar cell is a class solar cell comparatively novel at present, mainly utilizes similar ABX 3(A=CH 3nH 3 +deng; B=Pb 2+, Sn 2+deng; X=Cl -, I -deng) there is the photovoltaic material of perovskite structure to realize opto-electronic conversion, such cell making process is simple, raw material sources is extensive, cheap.
The general structure of perovskite-based thin film solar cell is: compacted zone, shelf layer, light-absorption layer, hole transmission layer and to electrode.Wherein, light-absorption layer is formed by the material with perovskite structure.Transform light energy becomes electric energy can be divided into three main process by perovskite solar cell: 1) light-absorption layer absorbs the photon of certain energy and produces electron hole pair (exciton); 2) there is separation of charge to during material interface place in exciton diffusion; 3) electronics enters external circuit along electron transport material through electrode, and hole enters external circuit along hole mobile material through electrode, completes the conversion of luminous energy to electric energy by load.
Based on different types of shelf layer, this type of battery is divided into again two kinds: one is to receiving porous polycrystalline wide bandgap semiconductor film (as TiO based on perovskite 2, ZnO, SnO 2) hull cell of sensitization, another kind is (as Al with cellular insulant material film 2o 3, ZrO 2, SiO 2deng) be the body heterojunction hull cell of shelf layer.The photoelectric conversion efficiency of the perovskite solar cell of these two kinds of structures is all more than 15%.At present, no matter any structure, hole transmission layer is all very important for acquisition high efficiency.Be generally used for hole mobile material and comprise small molecule hole transport material (as spiro-OMeTAD), polymeric hole transport material (P3HT) and inorganic hole transporter (as CuI, CuSCN).Wherein, polymeric hole transport stability of material is good, but hole mobility is on the low side, if can improve hole transport performance to its modification, extremely important for the efficiency and stability improving perovskite solar cell.
Utility model content
The purpose of this utility model is to provide a kind of perovskite-based thin film solar cell, adopts the polymer being dispersed with graphite alkene to make hole transmission layer, improves the hole migration ability of the polymer for hole transport, improve the performance of battery.
To achieve these goals, the utility model provides a kind of perovskite-based thin film solar cell, comprising: transparent substrates; The conductive layer formed on a transparent substrate; The compacted zone of the semi-conducting material formed on the electrically conductive; The porous support layer that compacted zone is formed; The semiconductor light-absorption layer with perovskite structure of filling in the internal voids of porous support layer; The hole transmission layer that porous support layer is formed; And formed on hole transmission layer to electrode; Hole transmission layer is the graphite alkene-polymer composites that can carry out hole transport.
Further, perovskite-based thin film solar cell also comprises the cap layer be formed between porous support layer and hole transmission layer.
Further, graphite alkene has large pi-conjugated structure.
Further, graphite alkene be 1,3-bis-acetylene bond phenyl ring is linked together composition structure.
Further, graphite alkene is nano-sheet, nano strip, Nanoparticulate, nanometer wire or nano tubular structure.
Further, when graphite alkene is Nanoparticulate, the particle diameter of the graphite alkene of Nanoparticulate is 30 ~ 300nm.
Further, the particle diameter of the graphite alkene of Nanoparticulate is 30 ~ 100nm.
Further, the thickness of hole transmission layer is 10 ~ 500nm.
Further, the thickness of hole transmission layer is 50 ~ 300nm.
Application the technical solution of the utility model, graphite alkene is distributed to and can carries out in the polymeric material of hole transport by inventor, forms polymer-graphite alkynes composite material, and using the hole transmission layer of composite material as perovskite-based thin film solar cell.In perovskite-based thin film solar cell, perovskite material for absorbed layer produces exciton by absorbing sunlight and is separated into electronics and hole, electronics is collected by the compacted zone (being generally titanium dioxide) of semi-conducting material, and exports to external circuit by conductive layer; Hole is collected by hole transmission layer (generally adopting P3HT) and is derived by electrode.Owing to being dispersed with graphite alkene in polymeric material, polymer and graphite alkene produce π-π and act on, and its highest occupied energy level (HOMO) reduces, and can mate better with the valence band location of perovskite material, substantially increase the transfer ability of hole transmission layer, and then improve the performance of battery.
The polymer being dispersed with graphite alkene is adopted to prepare hole transmission layer as perovskite-based thin film solar cell, compared with only containing the perovskite-based thin film solar cell of tradition of polymer hole transport layer, improve the hole migration ability of hole transmission layer, improve the conversion efficiency of battery.Simultaneously, this preparation method just adds graphite alkene on existing basis of preparing hole transmission layer, do not need consider due to the dispersion doping of graphite alkene and additionally increase other special solvent and special instruments and equipment, also can not need high-temperature process because of the doping of graphite alkene, only need drying at room temperature can obtain eligible and that thickness is adjustable hole transmission layer.Manufacturing process provided by the utility model is simple, is easy to operation, graphite alkene can be distributed to multiple in the polymeric material of hole transport, and matching is wide, has expanded the range of application of the hole mobile material for perovskite-based thin film solar cell.
According to hereafter by reference to the accompanying drawings to the detailed description of the utility model specific embodiment, those skilled in the art will understand above-mentioned and other objects, advantage and feature of the present utility model more.
Accompanying drawing explanation
Hereinafter describe specific embodiments more of the present utility model with reference to the accompanying drawings by way of example, and not by way of limitation in detail.Reference numeral identical in accompanying drawing denotes same or similar parts or part.It should be appreciated by those skilled in the art that these accompanying drawings may not be drawn in proportion.In accompanying drawing:
The geometry schematic diagram of the graphite alkene that Fig. 1 adopts for the utility model; And
Fig. 2 is the structural representation of the perovskite-based thin film solar cell of a kind of exemplary embodiments of the utility model.
Embodiment
In perovskite-based thin film solar cell, although for the polymeric material good stability of hole transport, but its hole mobility is on the low side, make the transformation efficiency of solar cell on the low side, and it is little for the method improving polymeric material hole transport performance at present, mainly by designing novel polymer molecular structure to obtain, its complicated process of preparation, and considerably increase cost.Therefore, in order to make perovskite-based thin film solar cell under the prerequisite keeping its stability, improving its transformation efficiency, the utility model proposes a kind of perovskite-based thin film solar cell, comprise hole transmission layer 60.This hole transmission layer is the graphite alkene-polymer composites that can carry out hole transport.
In this application, " graphite alkene-polymer composites " refers to the material be made up of the polymeric material and dispersion graphite alkene within it that can be used in hole transport.
Graphite alkene is the allotrope of the New Type of Carbon that scientists is prepared by multiple synthetic method, the electronic structure special due to it and be similar to the semiconductor property of silicon excellence, graphite alkene may be applied to the research fields such as electronics, semiconductor, material and opto-electronic conversion future widely.Graphite alkene be first with sp, sp 2and sp 3the Two-dimensional Carbon allotrope of three kinds of morphogenetic a kind of monoatomic layer structures of hydridization, and may be one the most stable in the carbon allotrope of Prof. Du Yucang by prophesy.There is in the graphite alkene Shi Tan family of carbon carbon triple bond (s-p hydridization) material of new unique texture, and to be described as may be one the most stable in Prof. Du Yucang, non-natural carbon allotrope.
Graphite alkene in the utility model preferably has the graphite alkene of large pi-conjugated structure, namely by s pand s p 2the two-dimensional rigid carbon allotrope of the carbon atom formation of hydridization.Fig. 1 shows geometry and the construction unit thereof of the graphite alkene in exemplary embodiments.As can be seen from Figure 1, this graphite alkene is 1, phenyl ring conjugation is connected to form the full carbon molecular structure of two dimensional surface network configuration by 3-bis-acetylene bond, has abundant carbon chemical bond, large conjugated system, wide interplanar distance, also has excellent chemical stability and semiconducting behavior simultaneously.Wherein carbon carbon triple bond (s-p) forms linkage unit very important in graphite alkene structure.The graphite alkene monocrystal thin films of this structure has the higher degree of order and lower defect, and film conductivity is 2.516 × 10 -4sm -1.In addition, also there is following characteristics: first, owing to by the variable effect of cis-trans isomerism, therefore can not keep linear structure always; Secondly, less sterically hindered owing to having, be more conducive to the carbon of sp hydridization to be connected to sp 2in the carbon atom of hydridization or sp hydridization in the heart; In addition, define delocalized pi-bond between carbon carbon triple bond and phenyl ring, therefore the organic molecular structure of its height conjugation, carbon enrichment has excellent flexible adjustability.The preparation method of this structure graphite alkynes has been described in detail in patent 201010102048.
Due to the doping of graphite alkene, for in the polymer of hole transport, polymer and graphite alkene produce π-π and act on, and its highest occupied energy level (HOMO) reduces, can mate better with the valence band location of perovskite material, substantially increase the transfer ability of hole transmission layer.Tracing it to its cause, may be because graphite alkene has good charge transmission and two-dimension plane structure, after doping form composite material and prepare hole transmission layer, thus improve the transfer ability of hole transmission layer, and then improve the performance of battery.
In a preferred embodiment of the present utility model, the quality being distributed to the graphite alkene in polymer is 0.1% ~ 5% of polymer quality.If the addition of graphite alkene is too high, graphite alkene particle agglomeration can be caused, and then cause graphite alkene dispersiveness in the polymer not good, not obvious to the performance boost of polymer; If the addition of graphite alkene is too low, DeGrain, the transfer ability of hole transmission layer cannot be improved preferably.Further preferably, the quality of graphite alkene is 3% ~ 5% of polymer quality.
Its accumulation shape of the graphite alkene adopted in the utility model can be nano-sheet, nano strip, Nanoparticulate, nanometer wire or nano tubular structure.When graphite alkene is Nanoparticulate, the particle diameter of the graphite alkene of Nanoparticulate is 30 ~ 300nm, is preferably 30 ~ 100nm.If the nano particle diameter of graphite alkene is too large or too little, easily there is agglomeration, cause bad dispersibility, thus affect the contact of hole transmission layer and metal electrode.
" polymer of hole transport can be carried out " in the utility model and mainly refer in polythiophene class, poly-phenylene vinylene (ppv) class, polysilanes or polyarylamine class one or more.Preferably poly-(3-hexyl) thiophene (P3HT) and/or poly-triphenylamine (PTPAn).If the molecular weight of polymer is too high or too low can reduce cavity transmission ability, affect the lifting of battery efficiency, the molecular weight of preferred polymers is 3000 ~ 200000.
The structure chart of perovskite-based thin film solar cell of the present utility model has been shown in Fig. 2.This perovskite-based thin film solar cell comprises: transparent substrates 10, in transparent substrates 10 formed conductive layer 20, on conductive layer 20 formed semi-conducting material compacted zone 30, on compacted zone 30 formed porous support layer 40, on porous support layer 40 formed hole transmission layer 60 and on hole transmission layer 60 formed to electrode 70.Wherein, in the internal voids of porous support layer 40, be filled with the semiconductor light-absorption layer 41 with perovskite structure.Hole transmission layer 60 is that the composite material formed by the polymeric material being dispersed with graphite alkene is prepared from.
In a preferred embodiment of the present utility model, be also included in the cap layer 50 formed between porous support layer 40 and hole transmission layer 60.Cap layer 50 is same material with the semiconductor light-absorption layer 41 of perovskite structure, can improve the utilization to light, and hole transmission layer 60 and porous support layer 40 can be separated, and reduces Carrier recombination.Preferably, the thickness of cap layer 50 can be 50 ~ 500nm.
Backing material can be generally glass or flexiplast, and the material of transparency electrode is indium tin oxide, fluorine tin-oxide or aluminium zinc oxide.Conductive layer 20 can (electro-conductive glass be the SnO of doped with fluorine for FTO 2, i.e. SnO 2: F, referred to as FTO) or ito thin film.Compacted zone 30 can by TiO 2film is formed.Preferably, the thickness of compacted zone can be 20 ~ 150nm; Further preferably, the thickness of compacted zone can be 50nm.Spin-coating method, knife coating or silk screen print method etc. can be adopted to prepare porous support layer 40.Porous support layer 40 can by TiO 2, Al 2o 3, ZrO 2one or more materials formed, preferably adopt TiO 2the nano material of the forms such as nano particle, nanometer rods or nano wire.Preferably, the thickness of porous support layer 40 can be 50 ~ 500nm.
Porous support layer 40 is formed semiconductor light-absorption layer 41, and this light-absorption layer 41 is formed by the organic metal semiconductor light absorbent with perovskite structure.Preferably, light-absorption layer 41 material can be (CH for being selected from chemical general formula 3nH 3) PbX my nin one or more materials, wherein X, Y=Cl, Br, I; M=1,2,3; N=3-m.Be specifically as follows CH 3nH 3pbCl 3, CH 3nH 3pbBr 3, CH 3nH 3pbI 3, CH 3nH 3pbClBr 2, CH 3nH 3pbCl 2br, CH 3nH 3pbBrI 2, CH 3nH 3pbBr 2i, CH 3nH 3pbClI 2and CH 3nH 3pbCl 2one in I, or in above-mentioned perovskite material any two or more with any mol ratio compound.
In a preferred embodiment of the present utility model, semiconductor light-absorption layer 41 is Organic leadP iodine methylamine semi-conducting material.When hole transmission layer 60 is for being dispersed with the polymeric material of graphite alkene, Organic leadP iodine methylamine semi-conducting material is adopted to have better level-density parameter as light-absorption layer 41.
In the process forming light-absorption layer 41, part or all of organic metal semiconductor light absorbent can be permeated downwards from the upper surface of porous support layer 40, and then be filled in the hole of porous support layer 40 inside, and then on organic metal semiconductor light-absorption layer 41, form hole transmission layer 60 prepared by polymer-graphite alkynes composite material, thus on hole transmission layer 60 shape paired electrode 60.
Polymeric material for hole transmission layer 60 of the present utility model can comprise polythiophene class, poly-phenylene vinylene (ppv) class, polysilanes, polyarylamine class etc.The hole transmission layer that the composite material formed by polymeric material doped graphite alkynes makes, its thickness can be 10 ~ 500nm.If the thickness of hole transmission layer is excessive, the internal resistance of battery can be caused excessive; Thickness is less, and hole transmission layer 60 can be caused to cover not exclusively, and both of these case all can reduce battery efficiency.Therefore, the THICKNESS CONTROL of hole transmission layer is contributed to separation and the transmission of photohole by the utility model in above-mentioned scope, can realize high efficiency.Preferably, the thickness of hole transmission layer 60 can be 50 ~ 300nm.
Can be formed by materials such as gold or silver electrode 70, it can pass through the method preparations such as vacuum evaporation, magnetron sputtering or molecular beam epitaxy, and thickness can be 50 ~ 200nm.
According to another aspect of the present utility model, additionally provide a kind of preparation method of perovskite-based thin film solar cell, comprise the step forming hole transmission layer 60.Wherein, the step forming hole transmission layer 60 comprises: polymer and the graphite alkene that can carry out hole transport are distributed in organic solvent equably, form mixed slurry, then this mixed slurry is arranged in preformed porous support layer 40 or its cap layer 50; Drying is carried out to mixed slurry, to form hole transmission layer 60.
In practical operation, generally first graphite alkene is distributed in organic solvent, after stirring, then adds polymeric material.After forming mixed slurry, by the mode of coating or silk screen printing, mixed slurry is deposited on porous support layer 40, then dry slurry, thus defines hole transmission layer 60 on porous support layer 40.Organic solvent be selected from benzene, toluene, chlorobenzene, dichloro-benzenes, trichloro-benzenes and ethyl acetate one or more, be preferably chlorobenzene.The utility model preferably but be not limited to above-mentioned organic solvent.
In a preferred embodiment of the present utility model, the mass percent concentration of polymer in mixed slurry is 0.5 ~ 5%.If the mass percent concentration of polymer is too high, the thickness of hole transmission layer can be caused excessive; On the contrary, if the mass percent concentration of polymer is too low, hole transmission layer 60 can be caused to cover not exclusively.Preferably, the mass percent concentration of polymer in mixed slurry is 1%.
Preparation method provided by the utility model just prepares on the basis of hole transmission layer existing, additionally mix graphite alkene, do not need additionally to increase other special solvent and special instruments and equipment because of the doping of graphite alkene, also high-temperature process can not be needed because of adding of graphite alkene, only need drying at room temperature, the composite hole transporting layer that qualified thickness is adjustable can be obtained.This manufacturing process is simple, and be easy to operation, graphite alkene can mix in multiple polymers hole mobile material, and matching is wide, has expanded the range of application of the hole mobile material of perovskite thin film solar cell.
The beneficial effects of the utility model are further illustrated below in conjunction with embodiment more specifically.
Embodiment 1
First silk screen printing one deck TiO on FTO glass 2thin layer, 450 DEG C of heating, after 30 minutes, obtain the compacted zone that thickness is the semi-conducting material of 50nm.Method for printing screen printing disclosed in preferred employing document (Chin.Phys.Lett., 2006,23 (9), 2606-2608) forms compacted zone.Spin-coating method is adopted to apply TiO on compacted zone 2nano-particle material, at room temperature dry rear 500 DEG C of sintering can obtain porous support Rotating fields, and thickness is 100nm.
Two-step method-first spin coating is adopted to flood again: by PbI 2be dissolved in DMF and make the spin coating liquid that mass percent concentration is 32%, be spin-coated on porous support layer with the rotating speed of 3000rpm, spin-coating time is 30 seconds.The PbI by spin coating again 2porous support layer film be immersed in the CH that concentration is 10mg/mL 3nH 3in I solution, formed simultaneously and be filled in organic metal semiconductor light absorbent light-absorption layer and the cap layer that porous support layer is interior, have perovskite structure.The cap layer thickness formed on the surface of porous support layer is 200nm.
Get the graphite alkene that particle diameter is 100nm, be distributed in toluene, after stirring, add the polymer P 3HT of molecular weight 30000 again, stir afterwards and obtain mixed slurry.It is 1wt% that the graphite alkene added accounts for 3% of polymer P 3HT weight, the polymer P 3HT concentration in mixed slurry.Be spun in cap layer by mixed slurry with 3000rpm, the time is 20 seconds, and the thickness of hole transmission layer is 100nm.(vacuum degree is less than 10 to adopt vacuum vapour deposition -6pa) on hole transmission layer, form silver to electrode, thickness is 80nm.So namely, complete the making of whole perovskite thin film solar cell.
Embodiment 2
First silk screen printing one deck TiO on FTO glass 2thin layer, 450 DEG C of heating, after 30 minutes, obtain the compacted zone that thickness is the semi-conducting material of 50nm.Method for printing screen printing disclosed in preferred employing document (Chin.Phys.Lett., 2006,23 (9), 2606-2608) forms compacted zone.Spin-coating method is adopted to apply TiO on compacted zone 2nano-particle material, at room temperature dry rear 500 DEG C of sintering can obtain porous support Rotating fields, and thickness is 100nm.
One-step method is adopted to be deposited on porous support layer by the organic metal semiconductor light absorbent with perovskite structure.This process comprises: by the PbI of equimolar amounts 3with organic iodate amine CH 3nH 3i is dissolved in DMF jointly, is mixed with the spin coating liquid that concentration is 40wt%, is filled to the space of porous support layer inside by organic metal semiconductor light absorbent by spin-coating method from the surface of porous support layer.
Get the graphite alkene that particle diameter is 100nm, be distributed in toluene, after stirring, add the polymer P 3HT that molecular weight is 30000 again, stir, obtain mixed slurry.Wherein added graphite alkene accounts for 3% of polymer weight, and the concentration of polymer P 3HT in mixed slurry is 1wt%.Be spun in shelf layer by mixed slurry with 3000rpm, the time is 20 seconds, and the thickness of hole transmission layer is 100nm.(vacuum degree is less than 10 to adopt vacuum vapour deposition -6pa) formed on hole transmission layer ag material to electrode, thickness is 80nm.So namely, complete the making of whole perovskite thin film solar cell.
Embodiment 3-14
Its preparation method is identical with embodiment 1, and difference is the mixed proportion of graphite alkene and polymer, and the molecular weight, graphite alkene particle diameter etc. of polymeric material, polymer are different simultaneously, specifically refer to table 1.
Embodiment 15-16
Its preparation method is identical with embodiment 1, and difference is that the mass ratio of the graphite alkene be doped in polymer is not in the scope of 0.1% ~ 5%, specifically refers to table 1.
Battery efficiency method of measurement in embodiment 1-16 and comparative example 1 is as follows: constant potential/galvanostat (Princeton Applied Research, Model 263A) that the photoelectric properties of battery are computerizedd control.By light anode and the photocathode of the solar cell device of preparation respectively with the work electrode of constant potential/galvanostat be connected electrode tip.Light source uses 500W xenon lamp, and incident intensity is 100mW/cm 2, illuminating area is 0.1cm 2.Except as otherwise noted, the photoelectric properties in each embodiment of the present utility model are measured and are all at room temperature carried out.
Table 1. perovskite thin film solar cell
Data from table 1 are known, and the photoelectric conversion efficiency of the perovskite-based thin film solar cell in embodiment 1-14 obtains lifting by a relatively large margin relative to comparative example 1, even reaches as high as 14.0%.This is owing to adopting the polymeric material being dispersed with graphite alkene as the hole transmission layer of perovskite-based thin film solar cell, due to the doping of graphite alkene, make polymeric material and graphite alkene produce π-π to act on, its the highest occupied energy level (HOMO) reduces, can mate better with the valence band location of perovskite material, therefore substantially increase the transfer ability of hole transmission layer, and then improve the performance of battery.And there is no dispersed graphite alkynes in hole transmission layer in comparative example 1, can find out that its battery efficiency is very low, be less than the half in embodiment 4.
As can be seen from table 1 simultaneously, the conversion efficiency of solar cell all can be affected for the kind of the polymeric material of hole transport, the grain size of graphite alkene, the concentration etc. of polymer.The utility model by carrying out creationary selection to the numerical value of above-mentioned performance parameter, thus obtains the solar cell of high conversion efficiency.
So far, those skilled in the art will recognize that, although multiple exemplary embodiment of the present utility model is illustrate and described herein detailed, but, when not departing from the utility model spirit and scope, still can directly determine or derive other modification many or amendment of meeting the utility model principle according to content disclosed in the utility model.Therefore, scope of the present utility model should be understood and regard as and cover all these other modification or amendments.

Claims (9)

1. a perovskite-based thin film solar cell, is characterized in that, comprising:
Transparent substrates (10);
At the upper conductive layer (20) formed of described transparent substrates (10);
At the compacted zone (30) of the upper semi-conducting material formed of described conductive layer (20);
At the upper porous support layer (40) formed of described compacted zone (30);
The semiconductor light-absorption layer (41) with perovskite structure of filling in the internal voids of described porous support layer (40);
At the upper hole transmission layer (60) formed of described porous support layer (40), wherein, described hole transmission layer (60) is the graphite alkene-polymer composites that can carry out hole transport; And
Described hole transmission layer (60) upper formed to electrode (70).
2. perovskite-based thin film solar cell according to claim 1, is characterized in that, also comprises the cap layer (70) be formed between described porous support layer (40) and described hole transmission layer (60).
3. perovskite-based thin film solar cell according to claim 1, is characterized in that, described graphite alkene has large pi-conjugated structure.
4. perovskite-based thin film solar cell according to claim 3, is characterized in that, described graphite alkene be 1,3-bis-acetylene bond phenyl ring is linked together composition structure.
5. perovskite-based thin film solar cell according to claim 1, is characterized in that, described graphite alkene is nano-sheet, nano strip, Nanoparticulate, nanometer wire or nano tubular structure.
6. perovskite-based thin film solar cell according to claim 5, is characterized in that, when described graphite alkene is Nanoparticulate, the particle diameter of the graphite alkene of described Nanoparticulate is 30 ~ 300nm.
7. perovskite-based thin film solar cell according to claim 6, is characterized in that, the particle diameter of the graphite alkene of described Nanoparticulate is 30 ~ 100nm.
8. perovskite-based thin film solar cell according to claim 1, is characterized in that, the thickness of described hole transmission layer (60) is 10 ~ 500nm.
9. perovskite-based thin film solar cell according to claim 8, is characterized in that, the thickness of described hole transmission layer (60) is 50 ~ 300nm.
CN201420649588.9U 2014-09-12 2014-11-03 Perovskite-based thin film solar cell Active CN204243085U (en)

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