CN104036963A - Method for preparing all-solid organic-inorganic hybridization perovskite solar battery - Google Patents
Method for preparing all-solid organic-inorganic hybridization perovskite solar battery Download PDFInfo
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- CN104036963A CN104036963A CN201410244599.3A CN201410244599A CN104036963A CN 104036963 A CN104036963 A CN 104036963A CN 201410244599 A CN201410244599 A CN 201410244599A CN 104036963 A CN104036963 A CN 104036963A
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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
- H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a method for preparing an all-solid organic-inorganic hybridization perovskite solar battery. The method comprises the steps of preparation of a transparent conductive substrate, preparation of a metallic oxide compact layer, preparation of a porous structure or plane structure/organic-inorganic perovskite material structural layer, preparation of a hole conduction layer structure and preparation of an electrode. An organic-inorganic perovskite material is utilized to replace photo-sensitive dye in a dye-sensitized solar battery structure and liquid electrolyte, the spectral response range of the battery is increased, preparation and packaging difficulty of the battery is reduced, and the prepared organic-inorganic perovskite solar battery is high in efficiency, good in stability and substrate adaptability, simple in process and good in repeatability and can be applied to mass production.
Description
Technical field
The present invention relates to battery technology field, be specifically related to a kind of preparation method based on all solid state hybrid inorganic-organic perovskite solar cell.
Background technology
Preparation technology is simple, cost is low and photoelectric conversion efficiency is high because it has for dye-sensitized solar cells, is considered to one of novel solar cell promising to be most silicon solar cell substitute.Traditional sensitization solar cell is mainly had the porous TiO of light-sensitive coloring agent molecule by abundant absorption
2the light anode that film and transparent conducting glass form, in transparent conductive glass surface load by thering is catalytic reduction ability Pt material electrode and liquid electrolyte three parts that contain redox couple are formed.From the opto-electronic conversion of photoelectric conversion efficiency to the 2014 year battery in when day 7.1% of dye-sensitized solar cells birth in 1991, change efficiency and break through 13%, in the time of nearly two more than ten years, scientists makes dye-sensitized solar cells obtain significant progress by optimizing the methods such as battery structure and improvement battery material.But one side liquid electrolyte has higher charge carrier rate travel and contributes to obtain high efficiency battery, on the other hand because the liquid electrolyte in battery structure has caused serious obstruction to the encapsulation of battery, the long-term stability that has restricted battery is used.Scientists have been developed the solid-state and solid electrolyte of a series of standard and is being replaced traditional liquid electrolyte in order to address this problem, but it is still lower to be subject to the efficiency of dye-sensitized solar cells of restriction solid electrolyte of carrier mobility in solid electrolyte.
Perovskite sensitization solar cell is the novel sensitization solar cell out of emerging development in recent years, and it utilizes the organic-metallic halide with perovskite structure to substitute the organic dyestuff in conventional dyes sensitization solar cell.Thereby utilize perovskite material to carry out the absorption of sunlight, the process that photovoltaic generation is carried out in utilization as core.Compare with traditional dye-sensitized solar cells, perovskite material has than light-sensitive coloring agent and has the sunlight response range of more widening.And perovskite sensitization solar cell not only can adopt liquid deposition technique, gas-phase deposition and liquid/vapor mixed deposit technique, battery structure is succinct, and preparation technology is simple.Therefore hybrid inorganic-organic perovskite solar cell promises to be solar cell of new generation very much.
Summary of the invention
The object of the invention is to provide a kind of new preparation method based on all solid state hybrid inorganic-organic perovskite material solar cell, overcome the dependence of conventional dyes sensitization solar battery structure to light-sensitive coloring agent and liquid electrolyte, increase the spectral response range of battery, reduced preparation and the encapsulation difficulty of battery.The prepared organic and inorganic perovskite efficiency of solar cell of the present invention is high, and substrate adaptability is good, good stability, and technical process is simple, reproducible, low for equipment requirements, is applicable to industrial large-scale production.
The invention provides a kind of based on all solid state organic-inorganic perovskite material the preparation method as the solar cell of light absorbing material, go for preparing two kinds of different structures all solid state organic-inorganic perovskite solar cell of (contain porous layer or do not contain porous layer), concrete steps comprise:
(1) utilize magnetically controlled sputter method to prepare transparent conductive film at simple glass or quartz glass surface, make electrically conducting transparent substrate;
(2) utilize chemical etching method that unnecessary transparent conductive film in described electrically conducting transparent substrate is etched away, obtain target pattern;
(3) utilize magnetically controlled sputter method in the region of described target pattern, to prepare metal oxide compacted zone; Wherein, described metal oxide comprises titanium dioxide, zinc oxide; The thickness of described metal oxide compacted zone is 50-100nm;
(4) titanium dioxide electrodes above-mentioned steps being obtained is placed in titanium tetrachloride aqueous solution, 70 ℃ are incubated 30 minutes, use again deionized water and alcohol flushing, oven dry, utilize spin-coating method at described electrode surface spin coating nano titania slurry, in 500 ℃ of Muffle furnaces, heat 20-40 minute, form the titanium dioxide thin layer of loose structure;
(5) the spin coating organic and inorganic perovskite material precursor solution that utilizes spin-coating method on the titanium dioxide porous electrode of above-mentioned steps (4) gained or on the metal oxide compacted zone of above-mentioned steps (3) gained, on 100 ℃ of heating stations, toast 30 minutes, obtain respectively perovskite material/porous material mixed structure or perovskite material-metal oxide structures;
(6) solution that contains hole conduction material in the body structure surface spin coating of above-mentioned steps (5) gained is prepared hole conduction layer;
(7) utilize vacuum evaporation technology in above-mentioned steps (6) the electrode obtained surface preparation layer of metal gold or silver electrode, described in preparing, there is all solid state perovskite battery of loose structure or planar structure.
In one embodiment of the invention, the preparation method of all solid state hybrid inorganic-organic perovskite solar cell of loose structure comprises: the preparation of electrically conducting transparent substrate, the preparation of metal oxide compacted zone, the preparation of the preparation of loose structure (solar cell based on loose structure), organic-inorganic perovskite material structure sheaf, the preparation of hole conduction layer structure and the preparation of metal electrode, and its concrete steps comprise:
(1) utilize magnetically controlled sputter method to prepare transparent conductive film at simple glass or quartz glass surface, prepare electrically conducting transparent substrate;
(2) utilize chemical etching method, unnecessary transparent conductive material in the prepared electrically conducting transparent substrate of step (1) is etched away, to obtain respective objects pattern;
(3) utilize magnetically controlled sputter method, in the respective regions of step (2) gained pattern, prepare the metal oxide compacted zone of one deck densification; Wherein, described metal oxide layer comprises titanium dioxide and zinc oxide; The thickness of described metal oxide compacted zone is 50-100nm;
(4) step (3) gained titanium dioxide electrodes is placed in to titanium tetrachloride aqueous solution, 70 ℃ are incubated 30 minutes, after being incubated, utilize deionized water and ethanol to rinse, dry, utilize spin-coating method at electrode surface spin coating nano titania slurry, in 500 ℃ of Muffle furnaces, heat 20 minutes, form the titanium dioxide thin layer of loose structure;
(5) utilize spin-coating method, at step (4) gained, there is spin coating organic and inorganic perovskite material precursor solution on the electrode of loose structure, on 100 ℃ of heating stations, toast 30 minutes, obtain the electrode with organic and inorganic perovskite material/porous material mixed structure;
(6) solution that contains hole conduction material in the surface spin coating of step (5) the electrode obtained, forms hole conduction layer;
(7) on step (6) the electrode obtained surface, utilize vacuum evaporation technology to prepare layer of metal gold or silver electrode, prepare all solid state hybrid inorganic-organic perovskite solar cell with loose structure.
In a specific embodiments of the present invention, the preparation method who does not contain all solid state hybrid inorganic-organic perovskite solar cell of porous layer of plane formula structure comprises: the preparation of the preparation of the preparation of electrically conducting transparent substrate, metal oxide compacted zone, organic-inorganic perovskite material structure sheaf, the preparation of hole conduction layer structure and the preparation of metal electrode; Specifically comprise the following steps:
(1) utilize magnetically controlled sputter method to prepare transparent conductive film at simple glass or quartz glass surface, prepare electrically conducting transparent substrate;
(2) utilize chemical etching method that unnecessary transparent conductive material in the prepared electrically conducting transparent substrate of above-mentioned steps is etched away, to obtain respective objects pattern;
(3) utilize magnetically controlled sputter method in the respective regions of above-mentioned steps gained pattern, to prepare the metal oxide compacted zone of one deck densification, wherein, metal oxide layer comprises titanium dioxide and zinc oxide, and described metal oxide dense layer thickness is 50-100nm;
(5) utilize spin-coating method spin coating organic and inorganic perovskite material precursor solution on the metal oxide compacted zone of above-mentioned steps (3) gained, on 100 ℃ of heating stations, toast 30 minutes, obtain perovskite material-metal oxide structures;
(6) solution that contains hole conduction material in the surface spin coating of above-mentioned steps the electrode obtained, forms hole conduction layer;
(7) on above-mentioned steps the electrode obtained surface, utilize vacuum evaporation technology to prepare layer of metal gold or silver electrode, prepare plane formula structure not containing all solid state hybrid inorganic-organic perovskite solar cell of porous layer.
Preparation method's comparison of all solid state hybrid inorganic-organic perovskite solar cell that contains loose structure with the present invention, that prepares plane formula structure has not omitted step (4) in the process containing all solid state hybrid inorganic-organic perovskite solar cell of porous layer, and other Step By Conditions are all identical.
In preparation method of the present invention, in step (1), described transparent conductive film comprises the broad stopband sull of the doping such as tin-doped indium oxide, fluorine-doped tin oxide, aluminium-doped zinc oxide.Preferably, described transparent conductive film is preparing aluminum-doped zinc oxide transparent conducting films.
In step (1), the described concrete technology of preparing the magnetically controlled sputter method of transparent conductive film is: the base vacuum degree of sputter cavity is 3 * 10
-3pa, argon flow amount is 15sccm, and sputtering chamber underlayer temperature is 250 ℃, and operating air pressure during sputter is 0.3Pa, and Sputtering power density is 1W/cm
-2, the target of use is the zinc-oxide ceramic target of 1wt% aluminium doping.
In step (2), described chemical etching method is to utilize the watery hydrochloric acid reaction of zinc powder and 0.2M to carry out etching.
In step (3), the described titanium dioxide (TiO for preparing
2) the magnetically controlled sputter method concrete technology of compacted zone is: the base vacuum degree of sputter cavity is 2 * 10
-3pa, argon flow amount is 15sccm, and operating air pressure during sputter is 0.4Pa, and radio frequency sputtering power is 4W/cm
2, the target of use is the titanium dioxide ceramic target of 99.99% purity.
In step (3), the described magnetically controlled sputter method concrete technology of preparing zinc oxide (ZnO) compacted zone is: the base vacuum degree of sputter cavity is for being not more than 3 * 10
-3pa, argon flow amount is 15-25sccm, and operating air pressure during sputter is 0.2-0.4Pa, and radio frequency sputtering power is 0.8-1.2W/cm
2, the target of use is the zinc-oxide ceramic target of 99.99% purity.
In step (4), the concentration of described titanium tetrachloride aqueous solution is 40mM.
In step (4), porous layer titanium dioxide (TiO
2) the pulp bales composition and the ratio that contain be: by the P25TiO of acetic acid acidifying
2powder, the ethanolic solution that contains ethyl cellulose 10% mass ratio and terpinol are to carry out at 0.06: 3: 2 evenly mixing and disperseing according to mass ratio.Finally add the ethanol of three times of quality to dilute.
In step (4), described spin coating rotating speed is 2000 revs/min.
In step (5), composition and the ratio of described organic and inorganic perovskite material precursor solution are: CH
3nH
3i and PbCl
2according to mol ratio, be to be dissolved in the solution that forms 40wt% in nitrogen-nitrogen dimethyl formamide solution at 3: 1.
In step (5), described spin coating rotating speed is 3000 revs/min.
In step (6), the concrete composition of the described solution (being cavitation layer spin coating solution) containing hole conduction material and consisting of: 2 of 0.17M, 2 ', 7,7 '-tetra-[N, N-bis-(4-methoxyphenyl) amino]-9,9 '-spiral shell two fluorenes, the 4-tert .-butylpyridine of 0.198M, the sulfimide lithium of two fluoroform 0.064M is dissolved in the solution of the middle 40wt% of formation of mixed solvent (volume ratio is 10: 1) of chlorobenzene and acetonitrile.
In step (6), the rotating speed of described cavitation layer spin coating is 3000 revs/min.
In step (7), the vacuum degree of vacuum evaporation is 7 * 10
-4pa, the evaporation thickness of gold is 100nm.
Wherein, " magnetron sputtering technique " adopting is to utilize gas glow discharge under vacuum to form plasma, and plasma realizes by accelerating bombing target target the method that target material deposits in target substrate.Magnetron sputtering technique is widely used in the preparation field of thin-film material.
Wherein, " spin coating method " that adopt refers to the centrifugal action that utilizes High Rotation Speed, and solution or colloid be even film forming method for manufacturing thin film in substrate.Spin-coating method is widely used in the chemical preparation field of thin-film material.
Wherein, " vacuum evaporation technology " adopting refers under high vacuum degree, and solid raw material is heated and reaches and surpass its boiling point, and solid material forms gas and in target base plate, deposits the method that forms solid film.Vacuum evaporation technology is widely used in the preparation field of thin-film material.
In the present invention, organic and inorganic perovskite material mainly contains organic metal halide, comprises CH
3nH
3pbBr
3, CH
3nH
3pbI
3and CH
3nH
3pbI
2cl.Due to CH
3nH
3pbI
2cl has better stability to glassware for drinking water under atmospheric environment, and therefore preferably organic and inorganic perovskite material is CH
3nH
3pbI
2cl.
In the present invention, hole conduction material (being hole-conductive material) mainly comprises poly--3 hexyl thiophenes (P3HT), 4-(diethylamino) benzaldehyde diphenyl hydrazone (DEH) and 2,2 ', 7,7 '-tetra-[N, N-bis-(4-methoxyphenyl) amino]-9,9 '-spiral shell, two fluorenes (spiro-OMeTAD) etc., wherein, owing to having the longest carrier lifetime in spiro-OMeTAD, therefore preferably hole-conductive material is spiro-OMeTAD.
The invention allows for all solid state hybrid inorganic-organic perovskite solar cell that contains loose structure preparing as stated above, its structure comprises glass substrate, transparent conductive film material, metal compaction layer, loose structure/organic and inorganic perovskite structure layer, hole-conductive layer and metal electrode layer.The invention allows for the planar structure for preparing as stated above not containing all solid state hybrid inorganic-organic perovskite solar cell of porous layer; it comprises organic and inorganic perovskite structure layer, hole-conductive layer and the metal electrode layer of glass substrate, transparent conductive film material, metal compaction layer, plane; it has the p--n structure of traditional inorganic silicon or CIGS thin-film solar cell; relevant technology of preparing controllability is good, easily realizes large-scale preparation.
Preparation method's technique of the present invention is simple, related is simple for structure, overcome in the conventional dyes sensitization solar cell based on loose structure the use to organic photosensitive dyestuff and the liquid electrolyte that contains redox couple, reduce the difficulty of cell package, and can realize very high battery efficiency.Utilize the cell photoelectric conversion efficiency with loose structure prepared by the inventive method to reach 12.1%, the efficiency that does not contain the plane formula battery of loose structure has reached 11.6%.Full solid thin film solar cell technique prepared by the inventive method is simple, photoelectric conversion efficiency is high, and can break through and solve the long-term stability problem using of liquid dye sensitization solar cell.
Accompanying drawing explanation
Fig. 1 is the structural representation of the organic and inorganic perovskite solar cell that contains loose structure prepared of the inventive method.
Fig. 2 is the structural representation of the organic and inorganic perovskite solar cell of the planar structure prepared of the inventive method.
Fig. 3 is the plumbous iodine chlorine of methylamine (CH prepared by the inventive method
3nH
3pbI
2cl) the XRD test result of perovskite light absorbing material.
Fig. 4 is the outer quantum effect spectrum that all solid state hybrid inorganic-organic perovskite of loose structure battery prepared by the inventive method is solar cell, and battery has good spectral effects characteristic within the scope of 400-700nm.
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.Do not deviating under the spirit and scope of inventive concept, variation and advantage that those skilled in the art can expect are all included in the present invention, and take appending claims as protection range.Implement process of the present invention, condition, reagent, experimental technique etc., except the content of mentioning specially below, be universal knowledege and the common practise of this area, the present invention is not particularly limited content.
The preparation method of all solid state organic and inorganic perovskite of the present invention solar cell, comprises following concrete steps:
1. the cleaning of substrate of glass.
Simple glass or quartz glass substrate are cleaned, adopt mixed solvent (volume ratio 1: 3) and the deionized water of acetone and absolute ethyl alcohol respectively substrate base to be carried out to ultrasonic cleaning, for example, clean 15 minutes, with nitrogen, dry up substrate.
2. at the glass basic surface cleaning, prepare transparent conductive film; Preferably, be preparing aluminum-doped zinc oxide transparent conducting films.
3. the transparent conducting glass substrate preparing is carried out to chemical etching, obtain corresponding construction figure.Cleaning obtains electrically conducting transparent substrate.
4. preparation can be for the TiO of spin coating
2porous slurry.
5. etching has also been cleaned to electrically conducting transparent substrate and used titanium tetrachloride aqueous solution at 70 ℃, to carry out preliminary treatment, with deionized water and ethanol, repeatedly rinsed oven dry
6. use in the electrically conducting transparent substrate of magnetron sputtering technique after titanium tetrachloride preliminary treatment completes and prepare TiO
2compacted zone.
7. utilize spin-coating method spin-on porous TiO in the electrically conducting transparent substrate that is prepared with compacted zone
2slurry sintering, obtain porous TiO
2layer.
8. the TiO complete to sintering
2porous layer working concentration is to be incubated reprocessing 30 minutes at 70 ℃ of the titanium tetrachloride aqueous solutions of 40mM, then with deionized water and ethanol, repeatedly rinses oven dry.
9. at porous TiO
2the organic and inorganic perovskite material solution that on layer, spin coating prepares, dries at 100 ℃ and within 30 minutes, obtains loose structure/perovskite material mixed structure.
10. spin coating spiro-OMeTAD hole-conductive material layer on loose structure/perovskite material mixed structure.
utilize vacuum evaporation to prepare metallic gold electrode at hole-conductive material surface evaporation, complete the preparation of whole all solid state organic and inorganic perovskite solar cell.
In above-mentioned preparation method, can also substitute TiO with ZnO
2.
As shown in Figure 1, 2,1-substrate of glass, 2-transparent conductive film, 3-metal oxide compacted zone, 41-porous TiO
2structure/hybrid inorganic-organic perovskite mixed structure layer, the hybrid inorganic-organic perovskite material bed of material of 42-planar structure, 5-hole-conductive layer, 6-metal electrode.
The organic and inorganic perovskite solar cell that embodiment 1 preparation contains loose structure
(a) glass substrate 1 is cleaned: use acetone, alcohol, deionized water are distinguished ultrasonic cleaning 15 minutes, then dried up with purity nitrogen successively;
(b) use the zinc-oxide ceramic target of 1wt% aluminium doping, utilizing magnetically controlled DC sputtering technology is 3 * 10 at chamber vacuum degree
-3pa, argon flow amount is 15sccm, and underlayer temperature is 250 ℃, and operating air pressure during sputter is 0.3P
a, Sputtering power density is 1W/cm
2condition under at cleaned glass basic surface, prepare preparing aluminum-doped zinc oxide transparent conducting films 2;
(c) utilize the watery hydrochloric acid of 0.1M and zinc powder to carry out etching to the preparing aluminum-doped zinc oxide transparent conducting films 2 preparing, then with glass substrate washing method, clean and dry up;
(d) the complete aluminium-doped zinc oxide electro-conductive glass of etching is inserted in magnetron sputtering vacuum chamber, the base vacuum degree of sputter cavity is 2 * 10
-3pa, argon flow amount is 15sccm, and operating air pressure during sputter is 0.4Pa, and radio frequency sputtering power is 4W/cm
2, the target of use is the titanium dioxide ceramic target of 99.99% purity, adopts RF sputtering method to prepare fine and close TiO
2film 3, its thickness is 100nm;
(e) working concentration is TiO prepared by 40mM titanium tetrachloride aqueous solution film by RF magnetron sputtering
2film 3 is incubated processing at 70 ℃, uses subsequently deionized water and alcohol flushing clean;
(f) with the ethanol of 3 times of quality to TiO
2the porous TiO of powder, ethyl cellulose and terpinol configuration
2slurry dilutes, and the method for then utilizing spin coating is at the spin-on porous layer of speed of 2000 revs/min, through the sintering of 30 minutes at 500 ℃, has obtained the TiO that thickness is about 500nm
2porous layer.
(g) porous membrane sintering being completed utilizes the titanium tetrachloride aqueous solution that concentration is 40mM at 70 ℃, to carry out the insulation reprocessing of 30 minutes, uses subsequently deionized water and alcohol flushing clean, repeats 500 ℃ of sintering 20 minutes, and cooling taking-up is stand-by;
(h) use CH
3nH
3i and PbCl
2according to mol ratio, be to be dissolved in the CH that forms 40wt% in nitrogen-nitrogen dimethyl formamide solution at 3: 1
3nH
3pbCl
2i organic and inorganic perovskite material spin coating solution, utilizes the method for spin coating under the rotating speed of 3000 revs/min, to prepare porous TiO
2/ organic and inorganic perovskite mixed structure.After spin coating completes, electrode is placed on the heating plate of 100 ℃ and toasts 30 minutes, when porous mixed structure color becomes dark-brown from white, represent that organic and inorganic perovskite material is at porous TiO
2formation in structure;
(i) after cooling, under the rotating speed of 3000 revs/min at porous TiO
2/ organic and inorganic perovskite mixed structure surface preparation spiro-OMeTAD hole-conductive layer 5;
(i) use vacuum evaporation in hole-conductive layer, to prepare metallic gold or silver electrode 6, complete the preparation of all solid state hybrid inorganic-organic perovskite battery that contains loose structure.
The structure of all solid state hybrid inorganic-organic perovskite battery that this contains loose structure, as shown in Figure 1, comprise glass substrate 1, transparent conductive film material 2, metal compaction layer 3, loose structure/organic and inorganic perovskite structure layer 41, hole-conductive layer 5 and metallic gold or silver electrode layer 6.Described metal compaction layer 3 is TiO
2compacted zone.Described metal compaction layer 3 can also be ZnO compacted zone.The plumbous iodine chlorine of methylamine (CH prepared by the present invention as shown in Figure 3
3nH
3pbI
2cl) the XRD test result of perovskite light absorbing material.The outer quantum effect spectrum that all solid state hybrid inorganic-organic perovskite of loose structure battery prepared by the present invention is as shown in Figure 4 solar cell, battery has good spectral effects characteristic within the scope of 400-700nm.
Embodiment 2 preparations do not contain the plane organic and inorganic perovskite solar cell of loose structure
With TiO
2during for compacted zone, its preparation process, in omitting loose structure technique, the preparation process of titanium tetrachloride aqueous solution pre-process and post-process and poriferous titanium dioxide structure, all the other Step By Conditions are all identical with embodiment 1.Prepare not containing the plane organic and inorganic perovskite solar cell of loose structure, its structure as shown in Figure 2, comprises organic and inorganic perovskite structure 42, hole-conductive layer 5 and the metallic gold electrode layer 6 of glass substrate 1, transparent conductive film material 2, metal compaction layer 3, plane.
Embodiment 3 preparations do not contain the plane organic and inorganic perovskite solar cell of loose structure
Take ZnO during as compacted zone, and the preparation technology of ZnO compacted zone is: use 99.99% zinc-oxide ceramic target, utilizing radiofrequency magnetron sputtering technology is 3 * 10 at chamber vacuum degree
-3pa, argon flow amount is 20sccm, and operating air pressure during sputter is 0.3Pa, and Sputtering power density is 1W/cm
2condition under, at cleaned glass basic surface, prepare the zinc oxide compacted zone that thickness is 100nm.Concrete preparation technology is identical with embodiment 1 for other layers.Prepare not containing the plane organic and inorganic perovskite solar cell of loose structure, its structure as shown in Figure 2, comprises organic and inorganic perovskite structure layer 42, hole-conductive layer 5 and metallic gold or the silver electrode layer 6 of glass substrate 1, transparent conductive film material 2, metal compaction layer 3, plane.
Claims (7)
1. a preparation method for all solid state hybrid inorganic-organic perovskite solar cell, is characterized in that, comprises step:
(1) utilize magnetically controlled sputter method to prepare transparent conductive film at simple glass or quartz glass surface, make electrically conducting transparent substrate;
(2) utilize chemical etching method that unnecessary transparent conductive film in described electrically conducting transparent substrate is etched away, obtain target pattern;
(3) utilize magnetically controlled sputter method in the region of described target pattern, to prepare metal oxide compacted zone; Wherein, described metal oxide comprises titanium dioxide, zinc oxide; The thickness of described metal oxide compacted zone is 50-100nm;
(4) titanium dioxide electrodes above-mentioned steps being obtained is placed in titanium tetrachloride aqueous solution, 70 ℃ are incubated 30 minutes, use again deionized water and alcohol flushing, oven dry, utilize spin-coating method at described electrode surface spin coating nano titania slurry, in 500 ℃ of Muffle furnaces, heat 20-40 minute, form the titanium dioxide thin layer of loose structure;
(5) the spin coating organic and inorganic perovskite material precursor solution that utilizes spin-coating method on the titanium dioxide porous electrode of above-mentioned steps (4) gained or on the metal oxide compacted zone of above-mentioned steps (3) gained, on 100 ℃ of heating stations, toast 30 minutes, obtain respectively perovskite material/porous material mixed structure or perovskite material/metal oxide structures;
(6) solution that contains hole conduction material in the body structure surface spin coating of above-mentioned steps (5) gained is prepared hole conduction layer;
(7) utilize vacuum evaporation technology in above-mentioned steps (6) the electrode obtained surface preparation layer of metal gold or silver electrode, described in preparing, there is all solid state perovskite battery of loose structure or planar structure.
2. preparation method as claimed in claim 1, is characterized in that, described transparent conductive film comprises the broad stopband sull of tin-doped indium oxide, fluorine-doped tin oxide, aluminium-doped zinc oxide doping.
3. preparation method as claimed in claim 1, is characterized in that, in described step (1), the condition of magnetron sputtering is: the base vacuum degree of sputter cavity is for being not more than 3 * 10
-3pa, argon flow amount is 10-20sccm, and sputtering chamber underlayer temperature is 200-300 ℃, and operating air pressure during sputter is 0.2-0.5Pa, and Sputtering power density is 0.5-2W/cm
2, the target of use is the zinc-oxide ceramic target of 1wt% aluminium doping.
4. preparation method as claimed in claim 1, is characterized in that, in described step (3),
The condition of the magnetron sputtering of titanium dioxide dense layer is: the base vacuum degree of sputter cavity is for being not more than 3 * 10
-3pa, argon flow amount is 10-20sccm, and operating air pressure during sputter is 0.2-0.5Pa, and radio frequency sputtering power is 3-5W/cm
2, the target of use is the titanium dioxide ceramic target of 99.99% purity;
The magnetron sputtering preparation process of zinc oxide compacted zone is: the base vacuum degree of sputter cavity is for being not more than 3 * 10
-3pa, argon flow amount is 15-25sccm, and operating air pressure during sputter is 0.2-0.4Pa, and radio frequency sputtering power is 0.5-1.2W/cm
2, the target of use is the zinc-oxide ceramic target of 99.99% purity.
5. preparation method as claimed in claim 1, is characterized in that, in described step (4), described titania slurry is: by the P25TiO of acetic acid acidifying
2powder, containing ethanolic solution and the terpinol of ethyl cellulose 10% mass ratio, according to mass ratio, be 0.06
:3
:2 carry out evenly mixing and disperseing; Then add the ethanol of three times of quality to dilute.
6. all solid state hybrid inorganic-organic perovskite solar cell with loose structure preparing by claim 1 method, it is characterized in that, it comprises glass substrate, transparent conductive film material, metal compaction layer, loose structure/organic and inorganic perovskite structure layer, hole-conductive layer and metal electrode layer.
7. all solid state hybrid inorganic-organic perovskite solar cell with planar structure preparing by claim 1 method, it is characterized in that, it comprises organic and inorganic perovskite structure layer, hole-conductive layer and the metal electrode layer of glass substrate, transparent conductive film material, metal compaction layer, plane.
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| CN104576929A (en) * | 2014-11-26 | 2015-04-29 | 华北电力大学 | Perovskite-lead sulfide quantum dot stacked solar cell and preparation method thereof |
| CN104810478A (en) * | 2014-12-27 | 2015-07-29 | 镇江市双利光电科技有限公司 | Solar cell with tin perovskite structure and manufacturing method thereof |
| CN105140401A (en) * | 2015-07-24 | 2015-12-09 | 北京大学 | Preparation method of organic or organic-inorganic hybrid framework-based perovskite solar cell |
| CN105428537A (en) * | 2015-12-10 | 2016-03-23 | 华北电力大学 | Perovskite solar cell based on titanium dioxide/perovskite novel composite nano structure, and preparation method thereof |
| CN105957966A (en) * | 2016-05-31 | 2016-09-21 | 华东师范大学 | REO (rare earth oxide) down-conversion material perovskite solar cell and preparation method |
| CN107565031A (en) * | 2016-07-01 | 2018-01-09 | 中国科学院上海硅酸盐研究所 | A kind of method that high surface coverage perovskite light-absorption layer is prepared on ZnO compacted zones |
| CN109536990A (en) * | 2018-10-15 | 2019-03-29 | 华南理工大学 | A kind of flat thin-film electro catalyst operation electrode and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104576929A (en) * | 2014-11-26 | 2015-04-29 | 华北电力大学 | Perovskite-lead sulfide quantum dot stacked solar cell and preparation method thereof |
| CN104810478A (en) * | 2014-12-27 | 2015-07-29 | 镇江市双利光电科技有限公司 | Solar cell with tin perovskite structure and manufacturing method thereof |
| CN105140401A (en) * | 2015-07-24 | 2015-12-09 | 北京大学 | Preparation method of organic or organic-inorganic hybrid framework-based perovskite solar cell |
| CN105428537A (en) * | 2015-12-10 | 2016-03-23 | 华北电力大学 | Perovskite solar cell based on titanium dioxide/perovskite novel composite nano structure, and preparation method thereof |
| CN105428537B (en) * | 2015-12-10 | 2018-04-24 | 华北电力大学 | Perovskite solar cell based on titanium dioxide/perovskite embedded type composite nanostructure and preparation method thereof |
| CN105957966A (en) * | 2016-05-31 | 2016-09-21 | 华东师范大学 | REO (rare earth oxide) down-conversion material perovskite solar cell and preparation method |
| CN107565031A (en) * | 2016-07-01 | 2018-01-09 | 中国科学院上海硅酸盐研究所 | A kind of method that high surface coverage perovskite light-absorption layer is prepared on ZnO compacted zones |
| CN109536990A (en) * | 2018-10-15 | 2019-03-29 | 华南理工大学 | A kind of flat thin-film electro catalyst operation electrode and its preparation method and application |
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