CN104518091A - Preparation method of organic-inorganic perovskite solar battery - Google Patents

Preparation method of organic-inorganic perovskite solar battery Download PDF

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CN104518091A
CN104518091A CN201410831610.6A CN201410831610A CN104518091A CN 104518091 A CN104518091 A CN 104518091A CN 201410831610 A CN201410831610 A CN 201410831610A CN 104518091 A CN104518091 A CN 104518091A
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metal oxide
layer
zinc
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黄素梅
李俊杰
罗玉丹
程锐
张晨曦
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East China Normal University
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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    • C23C14/34—Sputtering
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Abstract

The invention discloses a preparation method of an organic-inorganic hybridization perovskite solar battery in a plane structure. The preparation method comprises the steps of selection and pretreatment of a transparent conduction substrate, magnetron sputtering of an n-type metal oxide layer or pulse laser preparation, preparation of an organic metal perovskite structure light absorption layer by a normal-pressure gas phase assistance solution method, preparation of a hole conduction layer structure, preparation of a metal alloy back electrode and the like. The method overcomes the problems of discontinuity, insufficient density, pinholes and the like of an n-type metal oxide film, an intermediate phase, pinholes, impure phases and the like of hydration organic metal halogen in a perovskite light absorption layer material, metal particle aggregation of the pure metal back electrode, layering of a hole layer and the like. The solar battery prepared by the method is high in efficiency, low in price, simple in technology, good in repeatability and suitable for mass production.

Description

The preparation method of organic and inorganic perovskite solar cell
Technical field
The invention belongs to solar cell and preparing technical field thereof, relate to a kind of preparation method based on planar structure perovskite solar cell, and adopt magnetron sputtering method or pulsed laser deposition prepare n-type metal oxide semiconductor layer method, adopt normal pressure gas phase assisted solution legal system for light absorbing zone method, adopt vapour deposition method to prepare the method for metal alloy electrodes.
Background technology
The mankind are to low cost, and the exploration paces of high electricity conversion photovoltaic device never stop.Especially in this century, energy shortage and environmental pollution more and more govern the sustainable development of society and economy, solar energy power generating, as important clean energy technology, has entered mankind's energy resource structure, and becomes an important supplement part of basic energy resource.Meanwhile, along with the development of whole technology and the maturation of whole photovoltaic industry, expect the middle of this century, photovoltaic generation, by increasing its share in mankind's energy resource structure further, becomes important mankind's energy resource structure.Wherein, solar cell technology of preparing is the foundation stone of whole theCourse of PV Industry.At present, in the solar cell of efficient, low cost, main representative and DSSC and perovskite solar energy solar cell.
Preparation technology is simple, cost is low because it has for perovskite solar cell, and the feature had than DSSC more high-photoelectric transformation efficiency, run into today of high energy consumption, high pollution development bottleneck at silicon solar cell, bring huge hope to whole photovoltaic industry.It is very low that Jie occurred the earliest sees perovskite solar energy blank battery efficiency, but a few years time, namely the photoelectric conversion efficiency of battery brings up to more than 15% by 3.8% the earliest.In this process, along with people are to the electric property of perovskite material, the especially knowable intensification of carrier transport, the perovskite solar cell of planar heterojunction structure arises at the historic moment.Planar structure compares mesoscopic structure, can realize effective collection of charge carrier, can increase the flexibility of device optimization simultaneously, for the solar cell of development high-efficiency tandem structure provides possibility.
Organic and inorganic perovskite light absorbing zone is core prepared by whole planar heterojunction perovskite solar cell, and preparing high-quality hydridization perovskite light absorbing zone is the key that battery obtains high electricity conversion.High-quality organic and inorganic perovskite light absorbing zone has high crystalline, high surface coverage, and the feature such as evenness and density.The organic and inorganic perovskite light absorbing zone possessing these features has large absorptivity and low charge carrier surface coincidence rate.At present, people mainly utilize solwution method to carry out the preparation of organic and inorganic perovskite light absorbing zone.This method can not remove the impact of water or moisture completely, hydration organic metal halide mesophase spherule is there is in preparation-obtained organic and inorganic perovskite light absorbing zone, affect the stable of calcium titanium ore bed, simultaneously because this second-phase presents acicular texture usually, make the surface smoothness of organic and inorganic perovskite light absorbing zone, density, coverage all undesirable, finally have influence on the stability of battery and the photoelectric conversion efficiency of battery.The generation of needle-like secondary phase in organic and inorganic perovskite light absorbing zone, people have attempted the preparation that coevaporation method carries out organic and inorganic perovskite light absorbing zone.This method obtains successfully to a certain extent, avoids the generation of secondary phase, but develops because the uncontrollable of surface topography and high in cost of production factor limit it.
Summary of the invention
The technical problem to be solved in the present invention relates to n-type metal oxide layer, organic and inorganic perovskite light absorbing zone and the high-performance metal back electrode of preparing high-quality and function admirable, provide a kind of technology of preparing and method of efficient plane structure hybrid inorganic-organic perovskite solar cell, by Optimization Technology, prepare solar cell that is efficient, stable, reproducible and low cost.
In order to solve prior art Problems existing, the present invention proposes a kind of low cost normal pressure gas phase assisted solution method, carries out this organic and inorganic perovskite light absorbing zone and prepare under gas phase and pressure are assisted jointly.The method can avoid hydration organic metal halide CH effectively 3nH 3pbI xz 3-xh 2the generation of O (Z:Cl, Br) secondary phase, assisting simultaneously due to pressure, make film finer and close and smooth, film has the high absorption coefficient of light.And to the preparation growth of the n-type metal-oxide semiconductor (MOS) of solar cell and the preparation of metal alloy back electrode, propose new process for making.By the solar cell that this legal system is standby, there is excellent electricity conversion, stability and long-life, this method has both the advantages such as simple, the reproducible and low cost of technique simultaneously, significant for the development promoting planar heterojunction perovskite solar energy.
The present invention proposes a kind of preparation method of organic and inorganic perovskite solar cell, said method comprising the steps of:
(1) select high-performance transparent conductive substrate, clean and dry;
(2) utilize laser or chemical etching method to etch described electrically conducting transparent substrate, obtain target pattern, clean and dry;
(3) utilize on target pattern described in magnetron sputtering method or pulsed laser deposition and prepare n-type metal oxide layer;
(4) spin-coating method spin coating on described n-type metal oxide layer is utilized to take DMF as the lead iodide precursor liquid of solvent;
(5) normal pressure gas phase assisted solution method is adopted, by evaporating CH in enclosed system 3nH 3y (Y:Cl, Br, I) crystal powder produces gas phase, and in enclosed system, form air pressure promotion CH 3nH 3the PbI on Y gas phase and n-type metal oxide layer surface 2layer reaction generates CH 3nH 3pbI xz 3-x(Z:Cl, Br) perovskite light absorbing zone;
(6) solution containing hole-conducting materials in described perovskite light absorbing zone surface spin coating forms hole transmission layer;
(7) vacuum vapour deposition is utilized to prepare metal alloy back electrode on described Hole transporting layers surface;
Prepare described organic and inorganic perovskite solar cell.
In preparation method of the present invention, in described step (3), the magnetron sputtering condition of described n-type metal oxide layer is: the base vacuum degree of sputtering cavity is for being not more than 3 × 10 -3pa, argon flow amount is 10-20sccm, and oxygen flow is the 1-5% of argon gas, and operating air pressure is 0.2-0.5Pa, and Sputtering power density is 0.5-5W/cm 2, the target of use is the strontium titanates of 99.99% purity, barium stannate, zinc or zinc-oxide ceramic target.
In described step (3), the condition of the pulsed laser deposition of described n-type metal oxide layer is: the base vacuum degree of vacuum cavity is for being not more than 3 × 10 -3pa, argon flow amount is 10-20sccm, and oxygen flow is the 1-5% of argon gas, and operating air pressure during deposition is 0.2-0.5Pa, and optical maser wavelength is 193nm-355nm, and pulsewidth is not more than 30ns, and the energy density on target is 0.2-5J/cm 2, the target of use is the strontium titanates of 99.99% purity, barium stannate, zinc or zinc-oxide ceramic target.
In described step (3), described metal oxide comprises strontium titanates SrTiO 3, barium stannate Ba 2snO4, zinc Zn 2snO 4, zinc oxide ZnO.The thickness of described n-type metal oxide layer is 20-100nm.
In described step (4), the rotating speed of spin coating is 2000-4000 rev/min, and the time is 30-50 second.Then in 70-110 DEG C of heating 15-20 minute.Wherein, in spin coating take DMF as the concentration of the lead iodide precursor liquid of solvent is 400-500mg/ml.
In described step (7), described metal alloy back electrode comprises aerdentalloy electrode.In described aerdentalloy electrode, Al content is 10-20wt%.
In the present invention, being different from prior art, adopting normal pressure gas phase assisted solution legal system to have machine-inorganic calcium titanium ore light absorbing zone, that is, based on the interfacial reaction of gas-solid phase, by evaporating CH in enclosed system 3nH 3y (Y:Cl, Br, I) crystal powder produces gas phase, and in enclosed system, form air pressure promotion CH 3nH 3the PbI on Y gas phase and n-type metal oxide layer surface 2layer reaction generates CH 3nH 3pbI xz 3-x(Z:Cl, Br) perovskite light absorbing zone.Adopt normal pressure gas phase assisted solution legal system to have machine-inorganic calcium titanium ore light absorbing zone and can avoid CH 3nH 3pbI xz 3-xthe generation of the moisture secondary phase of hydridization perovskite.
The present invention innovatively proposes the method adopting magnetron sputtering method or pulsed laser deposition to prepare n-type metal oxide semiconductor layer, prepares high fine and close, smooth, crystallization and transparent n-type metal oxide semiconductor layer.Wherein, metal oxide comprises strontium titanates SrTiO 3, barium stannate Ba 2snO4, zinc Zn 2snO 4, zinc oxide ZnO.The thickness of described n-type metal oxide layer is 20-100nm.The method of the invention is different from the solwution method of prior art.
The present invention's innovation proposes a kind of method adopting vapour deposition method to prepare metal alloy electrodes, prepares low resistance and is combined firmly metal alloy electrodes with cavitation layer.The present invention is different from the elemental metals that prior art adopts, and avoids traditional elemental metals back electrode and prepares the reunion in growth course and the problem with cavitation layer layering.
The present invention innovates the method proposing and adopt brand-new normal pressure gas phase assisted solution legal system to have machine-inorganic calcium titanium ore light absorbing zone first, and described method is, based on the interfacial reaction of gas-solid phase, by evaporating CH in enclosed system 3nH 3y (Y:Cl, Br, I) crystal powder produces gas phase, and in enclosed system, form air pressure promotion CH 3nH 3the PbI on Y gas phase and n-type metal oxide layer surface 2layer reaction generates CH 3nH 3pbI xz 3-x(Z:Cl, Br) perovskite light absorbing zone.The present invention adopts normal pressure gas phase assisted solution legal system to have machine-inorganic calcium titanium ore light absorbing zone, avoids CH 3nH 3pbI xz 3-xthe generation of the moisture secondary phase of hydridization perovskite.
The present invention also proposes a kind of high efficiency organic-inorganic perovskite solar cell, is made up of successively transparency carrier, conductive layer, n-type metal oxide semiconductor layer, organic and inorganic calcium titanium ore bed, hole transmission layer and metal alloy back electrode.
In organic and inorganic perovskite solar cell of the present invention, described metal oxide layer comprises the metal oxide semiconductor films such as strontium titanates, barium stannate, zinc, zinc oxide.Described metal alloy back electrode comprises aerdentalloy electrode.In described aerdentalloy electrode, Al content is 10-20wt%.
In organic and inorganic perovskite solar cell of the present invention, described n-type metal oxide semiconductor layer is prepared by magnetron sputtering method or pulsed laser deposition.Described organic and inorganic perovskite light absorbing zone is prepared, that is, by evaporating CH in enclosed system by normal pressure gas phase assisted solution method 3nH 3y (Y:Cl, Br, I) crystal powder produces gas phase, and in enclosed system, form air pressure promotion CH 3nH 3the PbI on Y gas phase and n-type metal oxide layer surface 2layer reaction generates CH 3nH 3pbI xz 3-x(Z:Cl, Br) perovskite light absorbing zone.
In the present invention, described conductive layer comprises the broad stopband sull of the doping such as indium doping tin oxide (ITO), fluorine-doped tin oxide (FTO) and aluminium-doped zinc oxide (AZO).
The invention provides a kind of method that brand-new employing magnetron sputtering method or pulsed laser deposition prepare n-type metal oxide semiconductor layer; Additionally provide the method for a kind of brand-new normal pressure gas phase assisted solution legal system for hybrid inorganic-organic calcium titanium ore bed; Additionally provide a kind of preparation method adopting vapour deposition method to prepare metal alloy electrodes.Conventional solution technology of preparing is when depositing n-type metal oxide semiconductor films, and the n-type semiconductor film environmental microbes obtained is uneven, have pin hole and crystallinity is bad; Conventional solution method is attended by CH when preparing hybrid inorganic-organic calcium titanium ore bed 3nH 3pbI xz 3-xh 2the formation of O secondary phase, pin hole, instant invention overcomes the predicament that conventional solution method faces.Tradition elemental metals back electrode easily formed in preparation process metallic particles assemble and with the problem of cavitation layer layering, instant invention overcomes the reunion of traditional elemental metals back electrode, problem with cavitation layer layering.Present invention process process is simple, reproducible, low for equipment requirements, and battery efficiency is high, is applicable to industrialization large-scale production.
The present invention proposes a kind of preparation method based on hybrid inorganic-organic perovskite solar cell completely newly in conjunction with aforementioned preparation process.Present approach provides the physical deposition method of high-quality n-type metal oxide semiconductor films; Provide the normal pressure gas phase assisted solution preparation method of hybrid inorganic-organic perovskite thin film, carry out the preparation of organic and inorganic perovskite light absorbing zone; Provide low resistance and be combined the preparation method of firmly metal alloy back electrode with cavitation layer, and then carrying out the preparation method of planar structure perovskite solar cell.The method of the invention comprises step: the selection of transparency electrode, the preparation of n-metal oxide, PbI 2the preparation of film, n-metal oxide/p-type methylamine metal halide CH 3nH 3pbI xz 3-xthe preparation of the preparation of heterojunction structure, the preparation of hole transport Rotating fields and metal alloy back electrode.
In a particular embodiment, the preparation method of hybrid inorganic-organic perovskite solar cell of the present invention, namely carries out planar structure perovskite solar cell based on the process of normal pressure gas phase assisted solution and prepares manufacture craft, comprise the steps:
(1) select high-performance transparent conductive substrate, and ozone, ultraviolet, ultrasonic wave combined type cleaning drying are carried out to electrically-conductive backing plate; Described transparent conductive film comprises tin-doped indium oxide, fluorine-doped tin oxide, aluminum-doped zinc oxide films; Substrate comprises glass, poly terephthalic acid class plastics PET, polyethylene naphthalate (PEN);
(2) method of laser or chemical etching is utilized to etch away, unnecessary transparent conductive material in aforementioned obtained electrically conducting transparent substrate to obtain respective objects pattern;
(3) utilize magnetron sputtering method or pulsed laser deposition on the target pattern of aforementioned gained, prepare n-type metal oxide layer; Wherein said metal oxide comprises barium stannate strontium titanates, barium stannate, zinc, zinc oxide ZnO; The thickness of described n-type metal oxide layer is 20-100nm;
The magnetron sputtering technique condition of described n-type metal oxide semiconductor layer is: the base vacuum degree of sputtering cavity is for being not more than 3 × 10 -3pa, argon flow amount is 10-20sccm, and oxygen flow is the 1-5% of argon gas, and operating air pressure is 0.2-0.5Pa, and Sputtering power density is 0.5-5W/cm 2, the target of use is the strontium titanates of 99.99% purity, barium stannate, zinc or zinc-oxide ceramic target;
The pulse laser deposition process condition of described n-type metal oxide semiconductor layer is: the base vacuum degree of vacuum cavity is for being not more than 3 × 10 -3pa, argon flow amount is 10-20sccm, and oxygen flow is the 1-5% of argon gas, and operating air pressure during deposition is 0.2-0.5Pa, and optical maser wavelength is 193nm-355nm, and pulsewidth is not more than 30ns, and the energy density on target is 0.2-5J/cm 2, the target of use is the strontium titanates of 99.99% purity, barium stannate, zinc or zinc-oxide ceramic target;
(4) utilize spin-coating method on aforementioned gained n-type metal oxide layer spin coating with N, the lead iodide precursor liquid (400-500mg/ml) that dinethylformamide (DMF) is solvent, rotating speed 2000-4000 rev/min, time is 30-50 second, then in 70-110 DEG C of heating 15-20 minute;
(5) in an airtight container, first in the some apertures of container bottom, a certain amount of methylamine halogen CH is placed 3nH 3y (Y:Cl, Br, I) crystal powder, places filtering net film above aperture, then by the PbI in abovementioned steps prepared by spin-coating method 2film sample is placed in top or two walls of this closed container, airtight container, and evaporated by methylamine halogen crystal powder in 120-150 DEG C of heating, the reaction time continues 2 hours, obtains smooth, fine and close, high crystalline methylamine metal halide CH 3nH 3pbI xz 3-x/ metal oxide p-n heterojunction structure;
(6) solution that the perovskite light absorbing zone surface spin coating obtained in abovementioned steps contains hole-conducting materials forms hole transmission layer;
(7) utilize vacuum evaporation technology to prepare silver-colored aluminium (Al:10-20wt%) alloy electrode on abovementioned steps gained Hole transporting layers surface, complete the preparation of planar heterojunction structure perovskite battery.
In the present invention, the preparation of n-type metal oxide semiconductor layer adopts magnetron sputtering method or pulsed laser deposition, improves the uniformity of n-type metal oxide semiconductor layer film, compactness and crystallinity; The preparation of calcium titanium ore bed adopts normal pressure gas phase assisted solution method, CH 3nH 3y (Y:Cl, Br, I) gas phase and solution spin coating, anneal the PbI prepared 2the plumbous halide CH of methylamine is carried out in solid phase interface reaction 3nH 3pbI xz 3-xthe preparation of calcium titanium ore bed, improve the crystallinity of calcium titanium ore bed film on the one hand, homogeneity, evenness and compactness, greatly reduce the surface recombination rate of charge carrier; Improve the interracial contact of p-perovskite/n-metal oxide heterojunction on the other hand, reduce the compound of photo-generated carrier; Meanwhile, effectively improve the preparation of calcium titanium ore bed, avoid the generation that pure solwution method prepares moisture secondary phase in calcium titanium ore bed, improve the quality of p-perovskite/n-metal oxide heterojunction, improve the photoelectric conversion efficiency of battery and the rate of finished products of product.
The present invention adopts magnetron sputtering method or pulsed laser deposition to prepare strontium titanates, barium stannate, zinc, zinc-oxide film as high-performance n-type metal oxide layer, and the n-type metal-oxide film avoiding the prepared growth of conventional soln method is discontinuous, fine and close not, have the problems such as pin hole, in an enclosed system, normal pressure gas phase assisted solution method is utilized to carry out the preparation of organic and inorganic perovskite light absorbing zone crucial in planar heterojunction perovskite solar cell, this method avoids hydration organic metal halide mesophase spherule in conventional solution legal system standby growth organic and inorganic perovskite light absorption layer material process, pin hole, the formation of dephasign etc., prepared perovskite light absorbing zone has excellent surface coverage, evenness, density and degree of crystallinity, and the perovskite single crystal grain size of growth can reach micron level, the surface recombination rate reducing charge carrier in solar cell greatly, adopt aerdentalloy vapour deposition method to prepare high-test metal back electrode, overcome traditional law system assemble for the metallic particles of elemental metals back electrode and with the problem of cavitation layer layering.The solar battery efficiency standby by this legal system is high, and cheap, technique is simple, and reproducible, is applicable to large-scale production.
Accompanying drawing explanation
Fig. 1 is the structural representation of planar structure organic and inorganic perovskite solar cell of the present invention.
Fig. 2 is ZnO semiconductive thin film (100nm the is thick) transmission spectrum in visible-range prepared by the inventive method.
Fig. 3 is the I-V curve of planar structure hybrid inorganic-organic perovskite battery solar cell prepared by the inventive method.
Embodiment
In conjunction with following specific embodiments and the drawings, the present invention is described in further detail, and protection content of the present invention is not limited to following examples.Under the spirit and scope not deviating from inventive concept, the change that those skilled in the art can expect and advantage are all included in the present invention, and are protection range with appending claims.Implement process of the present invention, condition, reagent, experimental technique etc., except the following content mentioned specially, be universal knowledege and the common practise of this area, the present invention is not particularly limited content.
As shown in Figure 1,1-transparent substrates; 2-transparency conducting layer; 3-n-type metal oxide semiconductor layer; The 4-hybrid inorganic-organic perovskite material bed of material; 5-hole transmission layer; 6-metal alloy back electrode.
The organic and inorganic perovskite solar cell of the inventive method planar structure, from bottom to top, it comprises transparent substrates 1; Transparency conducting layer 2; N-type metal oxide semiconductor layer 3; The hybrid inorganic-organic perovskite material bed of material 4; Hole transmission layer 5 and metal alloy back electrode 6 form, as shown in Figure 1.
The method that following specific embodiment the inventive method comprises the physical deposition preparation method of n-type metal oxide semiconductor films, the normal pressure gas phase assisted solution preparation method of hybrid inorganic-organic perovskite thin film, the vacuum evaporation preparation method of metal alloy back electrode and prepares perovskite solar cell in conjunction with aforementioned preparation process is described.
Embodiment 1 prepares planar structure organic and inorganic perovskite solar cell
(1) processing cleaning AZO glass substrate: glass substrate is cut into suitable size, then glass substrate is placed in successively acetone, alcohol, deionized water for ultrasonic clean 15 minutes, dry up with pure nitrogen again, and utilize UV ozone surface treatment immediately 12 minutes; (2) etching of AZO transparent conductive oxide: the AZO transparent conductive film utilizing pulse laser good to preliminary treatment etches, and then be placed in acetone successively, alcohol, deionized water for ultrasonic clean 15 minutes, and dry up with pure nitrogen; (3) preparation of n-type ZnO semiconductor layer: utilize magnetron sputtering method making ZnO film on the AZO conductive layer etched, magnetron sputtering preparation process is: adopt purity to be the zinc-oxide ceramic target of 99.99%, the vacuum degree of vacuum cavity is 1 × 10 -4pa, argon flow amount is 15sccm, and oxygen flow is the 1-2% of argon gas, and operating air pressure is 0.3Pa, RF radio frequency sputtering power is 3W/cm 2, ZnO thickness is 50nm.Be illustrated in figure 2 the transmission spectrum of ZnO semiconductive thin film in visible-range prepared by the present invention, ZnO visible ray near infrared transmissivity more than 85%.(4) PbI 2film preparation: the precursor liquid (460mg/ml) utilizing spin-coating method spin coating lead iodide on step (3) gained ZnO semiconductive thin film, rotating speed 2500 revs/min, the time is 30 seconds, toasts 15 minutes afterwards on 110 DEG C of heating stations; (5) normal pressure gas phase assisted solution method perovskite light absorbing zone (CH 3nH 3pbI 3) preparation, i.e. n-ZnO/p-CH 3nH 3pbI 3the preparation of heterojunction structure: in an airtight graphite container, the bottom part of graphite is furnished with the some apertures placing dusty material, by the PbI of 1 square centimeter 2film, places 21mg methylamine iodine CH altogether in aperture 3nH 3i 3crystal powder, and above aperture, place filtering net film, then by the PbI prepared by spin-coating method in step () 2film sample is placed in top or two walls of this closed container, airtight container, and evaporated by methylamine iodine crystal powder in 120-150 DEG C of heating, the reaction time continues 2 hours, obtains smooth, fine and close, high crystalline n-ZnO/p-CH 3nH 3pbI 3heterojunction structure; (6) preparation of Hole transporting layers: utilize spin-coating method CH after the cooling period under the rotating speed of 3000 revs/min 3nH 3pbI 3/ n-TiO 2body structure surface prepares one deck spiro-OMeTAD hole-conductive layer; (7) preparation of silver-colored aluminum back electrode: adopt the method for hot evaporation evaporation one deck AgAl (Al:20wt%) film in spiro-OMeTAD hole-conductive layer as electrode, so far, to complete the preparation of battery.
Embodiment 2 prepares planar structure organic and inorganic perovskite solar cell
(1) processing cleaning FTO glass substrate: glass substrate is cut into suitable size, then glass substrate is placed in successively acetone, alcohol, deionized water for ultrasonic clean 15 minutes, dry up with pure nitrogen again, and utilize UV ozone surface treatment immediately 12 minutes; (2) etching of transparent conductive oxide: utilize the watery hydrochloric acid of 0.1M and the zinc powder FTO transparent conductive film good to preliminary treatment to etch, and then be placed in acetone successively, alcohol, deionized water for ultrasonic clean 15 minutes, and dry up with pure nitrogen; (3) pulse laser deposition in preliminary treatment with the FTO etched is utilized to prepare strontium titanates for n-type metal oxide semiconductor layer.The preparation technology of its strontium titanates n-type layer is: use 99.99% strontium titanate ceramics target, utilizes pulsed laser deposition technique to be 1 × 10 at the base vacuum degree of vacuum cavity -4pa, argon flow amount is 10sccm, and oxygen flow is 2% of argon gas, and operating air pressure during deposition is 0.3Pa, and optical maser wavelength is 248nm, and pulsewidth is 10ns, and the energy density on target is 0.5J/cm 2, the thickness of strontium titanates n-type layer is 30nm; (4) normal pressure gas phase assisted solution legal system is identical with embodiment 1 for the preparation of perovskite light absorbing zone, cavitation layer; (5) preparation of Ag/Al alloy back electrode: adopt the method for hot evaporation in spiro-OMeTAD hole-conductive layer evaporation one deck Ag/Al (Al:15wt%) alloy firm as electrode.
The planar structure organic and inorganic perovskite solar cell prepared in above embodiment, its structure as shown in Figure 1, comprises glass substrate 1, transparent conductive film material 2, n-type metal oxide semiconductor layer 3, the hybrid inorganic-organic perovskite material bed of material 4, hole transmission layer 5, metal alloy back electrode 6.Be the I-V curve take strontium titanates as the planar structure hybrid inorganic-organic perovskite battery of n-type layer being solar cell prepared by the present invention as shown in Figure 3, the photoelectric conversion efficiency of solar cell is 12%.
Metal oxide semiconductor layer prepared by the present invention, comprises strontium titanates, barium stannate, zinc or zinc-oxide film, and titanium deoxid film compactness, crystallinity and the transparency more standby than conventional solution legal system are better.The planar structure perovskite solar battery process adopting normal pressure gas phase assisted solution legal system standby is simple, photoelectric conversion efficiency is high, and the existence such as hydration organic metal halide mesophase spherule, pin hole, dephasign avoided in conventional solution method preparation process, improves stability and the useful life of battery.

Claims (10)

1. a preparation method for organic and inorganic perovskite solar cell, is characterized in that, comprises the following steps:
(1) select high-performance transparent conductive substrate, clean and dry;
(2) utilize laser or chemical etching method to etch described electrically conducting transparent substrate, obtain target pattern, clean and dry;
(3) magnetron sputtering method or pulsed laser deposition is utilized to prepare n-type metal oxide layer on described target pattern;
(4) spin-coating method spin coating on described n-type metal oxide layer is utilized to take DMF as the lead iodide precursor liquid of solvent;
(5) normal pressure gas phase assisted solution method is adopted, by evaporating CH in enclosed system 3nH 3y crystal powder produces gas phase, and in enclosed system, form air pressure promotion CH 3nH 3the PbI on Y gas phase and n-type metal oxide layer surface 2layer reaction generates CH 3nH 3pbI xz 3-xperovskite light absorbing zone; Wherein, Y is Cl, Br or I, and Z is Cl or Br;
(6) solution containing hole-conducting materials in described perovskite light absorbing zone surface spin coating forms hole transmission layer;
(7) vacuum vapour deposition is utilized to prepare metal alloy back electrode on described Hole transporting layers surface;
Prepare described organic and inorganic perovskite solar cell; Wherein, described organic and inorganic perovskite solar cell is made up of transparency carrier, conductive layer, n-type metal oxide semiconductor layer, organic and inorganic calcium titanium ore bed, hole transmission layer and metal alloy back electrode successively.
2. the method for claim 1, is characterized in that, in described step (3), the magnetron sputtering condition of described n-type metal oxide layer is: the base vacuum degree of sputtering cavity is for being not more than 3 × 10 -3pa, argon flow amount is 10-20sccm, and oxygen flow is the 1-5% of argon gas, and operating air pressure is 0.2-0.5Pa, and Sputtering power density is 0.5-5W/cm 2, the target of use is the strontium titanates of 99.99% purity, barium stannate, zinc or zinc-oxide ceramic target.
3. the method for claim 1, is characterized in that, in described step (3), the condition of the pulsed laser deposition of described n-type metal oxide layer is: the base vacuum degree of vacuum cavity is for being not more than 3 × 10 -3pa, argon flow amount is 10-20sccm, and oxygen flow is the 1-5% of argon gas, and operating air pressure during deposition is 0.2-0.5Pa, and optical maser wavelength is 193nm-355nm, and pulsewidth is not more than 30ns, and the energy density on target is 0.2-5J/cm 2, the target of use is the strontium titanates of 99.99% purity, barium stannate, zinc or zinc-oxide ceramic target.
4. the method for claim 1, is characterized in that, in described step (3), described metal oxide comprises strontium titanates SrTiO 3, barium stannate Ba 2snO4, zinc Zn 2snO 4, zinc oxide ZnO; The thickness of described n-type metal oxide layer is 20-100nm.
5. the method for claim 1, is characterized in that, in described step (4), described lead iodide Concentration of precursor solution is 400-500mg/ml, and the condition of spin coating comprises: rotating speed 2000-4000 rev/min, and the time is 30-50 second.
6. the method for claim 1, is characterized in that, in described step (7), described metal alloy back electrode comprises aerdentalloy electrode; Wherein, Al content is 10-20wt%.
7. an organic and inorganic perovskite solar cell, is characterized in that, is made up of successively transparency carrier, conductive layer, n-type metal oxide semiconductor layer, organic and inorganic calcium titanium ore bed, hole transmission layer and metal alloy back electrode; Wherein, described metal oxide comprises strontium titanates, barium stannate, zinc, zinc oxide.
8. prepare a method for n-type metal oxide semiconductor layer with magnetron sputtering method or pulsed laser deposition, it is characterized in that, wherein, described magnetron sputtering condition is: the base vacuum degree of sputtering cavity is for being not more than 3 × 10 -3pa, argon flow amount is 10-20sccm, and oxygen flow is the 1-5% of argon gas, and operating air pressure is 0.2-0.5Pa, and Sputtering power density is 0.5-5W/cm 2, the target of use is the strontium titanates of 99.99% purity, barium stannate, zinc or zinc-oxide ceramic target;
Wherein, the condition of described pulsed laser deposition is: the base vacuum degree of vacuum cavity is for being not more than 3 × 10 -3pa, argon flow amount is 10-20sccm, and oxygen flow is the 1-5% of argon gas, and operating air pressure during deposition is 0.2-0.5Pa, and optical maser wavelength is 193nm-355nm, and pulsewidth is not more than 30ns, and the energy density on target is 0.2-5J/cm 2, the target of use is the strontium titanates of 99.99% purity, barium stannate, zinc or zinc-oxide ceramic target.
9. prepare a method for metal alloy electrodes with vapour deposition method, it is characterized in that, wherein, described metal alloy electrodes comprises aerdentalloy electrode.
10. having a method for machine-inorganic calcium titanium ore light absorbing zone by normal pressure gas phase assisted solution legal system, it is characterized in that, based on the interfacial reaction of gas-solid phase, by evaporating CH in enclosed system 3nH 3y crystal powder produces gas phase, and in enclosed system, form air pressure promotion CH 3nH 3the PbI on Y gas phase and n-type metal oxide layer surface 2layer reaction generates CH 3nH 3pbI xz 3-xperovskite light absorbing zone; Wherein, Y is Cl, Br or I, and Z is Cl or Br.
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