CN103943780A - Copper indium sulfide/calcium titanium ore body heterojunction solar cell and manufacturing method thereof - Google Patents

Copper indium sulfide/calcium titanium ore body heterojunction solar cell and manufacturing method thereof Download PDF

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CN103943780A
CN103943780A CN201410162544.8A CN201410162544A CN103943780A CN 103943780 A CN103943780 A CN 103943780A CN 201410162544 A CN201410162544 A CN 201410162544A CN 103943780 A CN103943780 A CN 103943780A
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cuins
perovskite
ito
layer
solar cell
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李洪伟
陈冲
刘振樊
何舟
王敏
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WUHAN XINSHEN OPTOELECTRONICS TECHNOLOGY Co Ltd
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WUHAN XINSHEN OPTOELECTRONICS TECHNOLOGY Co Ltd
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Priority to CN201410315452.9A priority patent/CN104112786B/en
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • 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
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • 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
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • H10K30/35—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains comprising inorganic nanostructures, e.g. CdSe nanoparticles
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    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/60—Forming conductive regions or layers, e.g. electrodes
    • H10K71/611—Forming conductive regions or layers, e.g. electrodes using printing deposition, e.g. ink jet printing
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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    • H—ELECTRICITY
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract

The invention relates to the technical field of solar cells by taking organic-inorganic hybrid calcium titanium ore materials as the base, in particular to a copper indium sulfide/calcium titanium ore body heterojunction solar cell and a manufacturing method of the solar cell. The copper indium sulfide/calcium titanium ore body heterojunction solar cell comprises an ITO substrate layer, a CuInS2 layer on the ITO substrate layer, a nanometer aluminum oxide-copper indium sulfide-calcium titanium ore composite layer arranged on the CuInS2 layer and a silver layer on the nanometer aluminum oxide-copper indium sulfide-calcium titanium ore composite layer. According to the structure, high-temperature sintering is not needed, a flexible ITO substrate is cheap, and the film-forming property of the mixture of the copper indium sulfide and calcium titanium ore is good.

Description

A kind of copper indium sulphur/perovskite bulk heterojunction solar cell and preparation method thereof
Technical field
The perovskite material that the present invention relates to hybrid inorganic-organic is basic technical field of solar batteries, relates in particular to a kind of solar cell with copper indium sulphur/perovskite bulk heterojunction and preparation method thereof.
Background technology
Because fossil energy is a kind of non-renewable resources, consumption day by day along with fossil energy, the development and utilization of new forms of energy always is the focus that science researcher pays close attention to, solar energy has been proved and can have substituted to a certain extent fossil energy as a kind of clean energy resource at present, solar cell is a kind of effective means of utilizing solar energy, at present silica-based inorganic solar cell is comparative maturity, and transformation efficiency can reach 25～30%.But the production cost of silica-based solar cell is high, with and rigidity cannot carry out too greatly the large-scale application that has all limited silica-based solar cell such as crooked.
In the research group of Korea S Cheng Jun shop university in 2009, invented the solar cell that a kind of perovskite material with hybrid inorganic-organic is made, this battery develops into its transformation efficiency now and has reached 15%, and its material easily makes, with low cost, can process by solution process, this large-scale application for its future is laid a good foundation.
According to existing bibliographical information, take at present perovskite material as its structure of basic solar cell be all to adopt following structure mostly: FTO/TiO2/ perovskite/HTM/Au.The battery of this structure first cost of FTO is higher, and need to be on FTO sintering TiO 2, its sintering temperature is more than 450 ℃, and the HTM layer material that secondly this structure adopts is very expensive, moreover pure perovskite filming performance is very poor, and the success rate of element manufacturing is very low, easily has the phenomenon of partial short-circuit to occur.
Summary of the invention
For solving the deficiencies in the prior art, the invention provides a kind of copper indium sulphur/perovskite bulk heterojunction solar cell, its battery structure adopting is: ITO/ copper indium sulphur/aluminium oxide+copper indium sulphur+perovskite/Ag.Adopt this structure need not be again sintering at high temperature, and flexible ITO substrate low price, the mixture filming performance of copper indium sulphur and perovskite is good.
Copper indium sulphur/perovskite bulk heterojunction solar cell, comprises the CuInS on ITO basalis, described ITO basalis 2layer, described CuInS 2silver layer on nano oxidized Solder for Al-Cu Joint Welding indium sulphur-perovskite composite bed on layer and described nano oxidized Solder for Al-Cu Joint Welding indium sulphur-perovskite composite bed.
Preferably, described CuInS 2the thickness of layer is 150nm～300nm, and its preparation method is:
By CuInS 2homogeneous solution spin coating on described ITO basalis, rotating speed is 1300～3000rpm,
Be preferably 1500rpm, the time is 10～50 seconds, is preferably 30 seconds, and solvent evaporated under 150～220 ℃ of conditions, is preferably 200 ℃ afterwards, and under 150～180 ℃ of conditions sintering 0.5～1.5 hour, be preferably under 160 ℃ of conditions sintering 1 hour.
Wherein, described CuInS 2homogeneous solution can adopt known method preparation: the indium acetate, thiocarbamide, propionic acid and the butylamine that by the ratio of amount of substance, are 1:5:5:62.5 mix, form the transparent solution without precipitation, then the cuprous iodide equating with indium acetate amount of substance is joined to the described transparent solution without precipitation, carry out ultrasonic dispersion, obtain CuInS 2homogeneous solution.
Spin coating, refers in electronics industry, and substrate rotates perpendicular to the axle on self surface, liquid coating material is coated in to on-chip technique simultaneously.
Ultrasonic dispersion, ultrasonic wave disperses, and can be casually arranged with standby realization by ultrasonic partial waves such as ultrasonic wave separating apparatus, and it utilizes cavitation, can promote the dissolving of solute in solution.
Preferably, the thickness of described nano oxidized Solder for Al-Cu Joint Welding indium sulphur-perovskite composite bed is 400nm～600nm, and its preparation method comprises the following steps:
1) by nano oxidized alfol dispersion liquid at described CuInS 2spin coating is carried out on the surface of layer, and rotating speed is 800～2000rpm, is preferably 1000rpm, and the time is 10～40 seconds, is preferably 20 seconds, then at 120～200 ℃, toasts 10～30 minutes, is preferably and at 150 ℃, toasts 20 minutes, obtains nano oxidized aluminium coating.
2) mixed solution of copper indium sulphur and perovskite is dripped to painting on the surface of described alumina coated layer, then sintering 20～60 minutes at 80～120 ℃, be preferably at 100 ℃ sintering 30 minutes, copper indium sulphur and perovskite are infiltrated through in described nano oxidized aluminium coating, wherein, the compound method of the mixed solution of described copper indium sulphur and perovskite is:
By the In of every 0.085～0.34mmol (OAc) 3be dissolved in the DMF solution of perovskite of 0.4～1.6mL with the CuI of 0.09～0.36mmol, the thiocarbamide of 0.043～0.17mmol, in the DMF solution of described perovskite, the mass percent of perovskite is 20～40%.
Nano oxidized alfol dispersion liquid refers to adopt advanced dispersing technology, by nano alumina powder jointed, is dispersed in organic solvent, and height of formation is decentralized, the nano oxidized alfol dispersion liquid of homogenizing and stabilisation.Nano oxidized alfol dispersion liquid has outside the characteristic of nano-powder material, and nano oxidized alfol dispersion liquid has higher activity, easily the characteristic such as adds.Its method that can buy by market obtains.
Preferably, by the In of every 0.17mmol (OAc) 3be dissolved in the DMF solution of perovskite of 0.8mL with the CuI of 0.1mmol, the thiocarbamide of 0.085mmol, in the DMF solution of described perovskite, the mass percent of perovskite is 40%.
Preferred, described alumina coated layer consists of γ type nano aluminium oxide, and particle diameter is 10nm～30nm.
Preferably, the thickness of described silver layer is 500nm～1000nm.
Preferably, the thickness of described ITO basalis is 30nm～100nm.
The present invention also provides a kind of preparation method of copper indium sulphur/perovskite bulk heterojunction solar cell, comprises the following steps:
1) ITO substrate is carried out to ultrasonic cleaning with deionized water, absolute ethyl alcohol, acetone successively, then ITO substrate is dried up with nitrogen, obtain ITO basalis.
2) by CuInS 2precursor solution spin coating on described ITO basalis, rotating speed is 1000～3000rpm, the time is 10～50 seconds, by sample on hot platform with 150～220 ℃ by solvent evaporate to dryness, and then sample is placed among baking oven, sintering is 0.5～1.5 hour at 150～180 ℃, obtains ITO/CuInS 2layer, wherein, spin coating frequency n=1,2 or 3.
Described CuInS 2prepared by the known method that adopts of precursor solution:
The indium acetate, thiocarbamide, propionic acid and the butylamine that by the ratio of amount of substance, are 1:5:5:62.5 mix, and form the transparent solution without precipitation, then add the cuprous iodide equating with indium acetate amount of substance, carry out ultrasonic dispersion, obtain described CuInS 2precursor solution.
Ultrasonic cleaning, i.e. Ultrasonic Cleaning, be utilize cavitation, acceleration effect and the direct flow effect of ultrasonic wave in liquid to liquid and dirt directly, indirectly effect, make that crud layer is dispersed, emulsification, peel off and reach cleaning object.
3) will be oxidized alfol dispersion liquid through described step 2) the described ITO/CuInS that obtains 2spin coating is carried out on the surface of layer, and rotating speed is 800～2000rpm, and the time is 10～40 seconds, then at 120～200 ℃, toasts 10～30 minutes, obtains ITO/CuInS 2/ Al 2o 3layer.
Wherein, Al 2o 3layer forms the mesoporous layer of one deck, and the copper indium sulphur in step and perovskite can infiltrate wherein afterwards, form composite bed.
4) by the mixed solution of copper indium sulphur and perovskite at described ITO/CuInS 2/ Al 2o 3painting is dripped on the surface of layer, sintering 20～60 minutes at 80～120 ℃ then, and wherein, the compound method of the mixed solution of described copper indium sulphur and perovskite is:
By the In of every 0.085～0.34mmol (OAc) 3be dissolved in the DMF solution of perovskite of 0.4～1.6mL with the CuI of 0.09～0.36mmol, the thiocarbamide of 0.043～0.17mmol, in the DMF solution of described perovskite, the mass percent of perovskite is 20～40%.Obtain ITO/CuInS 2/ Al 2o 3+ CuInS 2+ CaTiO 3layer.
5) at described ITO/CuInS 2/ Al 2o 3+ CuInS 2+ CaTiO 3one deck silver slurry is brushed by the method for silk screen printing in layer surface, and at 80～120 ℃, makes it solidify, and obtains ITO/CuInS 2/ Al 2o 3+ CuInS 2+ CaTiO 3/ Ag solar cell.
During silk screen printing finger mark brush, by the extruding of scraper plate, ink is transferred on stock by the mesh of picture and text part, formed the picture and text the same with original copy.Screen printing apparatus is simple, easy to operate, prints, makes a plate and be simple and easy and with low cost, strong adaptability.The common printed matter of silk screen printing applied range has: colored oil painting, pictorial poster, business card, binding and layout front cover, product tag and dyeing textile product etc.
Preferably, the preparation method of described copper indium sulphur/perovskite bulk heterojunction solar cell, comprises the following steps:
1) ITO substrate is carried out to ultrasonic cleaning with deionized water, absolute ethyl alcohol, acetone successively, then ITO substrate is dried up with nitrogen, obtain ITO basalis;
2) by CuInS 2precursor solution spin coating on described ITO basalis, rotating speed is 1500rpm, the time is 30 seconds, by sample on hot platform with 200 ℃ by solvent evaporate to dryness, and then sample is placed among baking oven, sintering is 1 hour at 160 ℃, obtains ITO/CuInS 2layer, wherein, spin coating frequency n=1,2 or 3, described CuInS 2the preparation method of precursor solution is:
The indium acetate, thiocarbamide, propionic acid and the butylamine that by the ratio of amount of substance, are 1:5:5:62.5 mix, and form the transparent solution without precipitation, then add the cuprous iodide equating with indium acetate amount of substance, carry out ultrasonic dispersion, obtain described CuInS 2precursor solution;
3) will be oxidized alfol dispersion liquid through described step 2) the described ITO/CuInS that obtains 2spin coating is carried out on the surface of layer, and rotating speed is 1000rpm, and the time is 20 seconds, then at 150 ℃, toasts 20 minutes, obtains ITO/CuInS 2/ Al 2o 3layer;
4) by the mixed solution of copper indium sulphur and perovskite at described ITO/CuInS 2/ Al 2o 3painting is dripped on the surface of layer, sintering 30 minutes at 100 ℃ then, and wherein, the compound method of the mixed solution of described copper indium sulphur and perovskite is:
By the In of every 0.17mmol (OAc) 3be dissolved in the DMF solution of perovskite of 0.8mL with the CuI of 0.18mmol, the thiocarbamide of 0.085mmol, in the DMF solution of described perovskite, the mass percent of perovskite is 40%, obtains ITO/CuInS 2/ Al 2o 3+ CuInS 2+ CaTiO 3layer;
5) at described ITO/CuInS 2/ Al 2o 3+ CuInS 2+ CaTiO 3one deck silver slurry is brushed by the method for silk screen printing in layer surface, and at 100 ℃, makes it solidify, and obtains ITO/CuInS 2/ Al 2o 3+ CuInS 2+ CaTiO 3/ Ag solar cell.
Preferably, described oxidation alfol dispersion liquid is the dispersion liquid of the isopropyl alcohol of γ type nano aluminium oxide, and wherein, the solid content of aluminium oxide is 20%～25%, and the particle diameter of nano alumina particles is 10～30 nanometers.
Accompanying drawing explanation
Fig. 1 is the i-v curve that the prepared sample of embodiment 1 records.
Fig. 2 is the i-v curve that the prepared sample of embodiment 2 records.
Fig. 3 is the i-v curve that the prepared sample of embodiment 3 records.
Embodiment
Below principle of the present invention and feature are described, example, only for explaining the present invention, is not intended to limit scope of the present invention.
Embodiment 1
A. prepare CuInS 2precursor solution, is dissolved in 0.1mmol indium acetate, 0.5mmol thiocarbamide and 40 μ L acetic acid in 0.6mL butylamine, and carries out ultrasonic dispersion and make it form homogeneous solution, 0.1mmol cuprous iodide is joined in above-mentioned solution subsequently again.
B. ITO substrate is carried out to ultrasonic cleaning with deionized water, absolute ethyl alcohol and acetone successively, each 15 minutes, finally with nitrogen, ITO substrate is dried up.
C. by CuInS 2precursor solution carries out spin coating in ITO substrate, and rotating speed is 1500rpm, and the time is 30 seconds, and spin coating once.By sample on hot platform with 200 ℃ by solvent evaporate to dryness, and then sample is placed among baking oven, sintering is 1 hour at 160 ℃.
D. will be oxidized alfol dispersion liquid at ITO/CuInS 2spin coating is carried out on surface, and rotating speed is 1000rpm, and the time is 20 seconds, then sample is placed on hot platform and at 150 ℃, toasts 20 minutes.
E. by the In of 0.17mmol (OAc) 3, to be dissolved into 0.8mL mass fraction be (solvent is DMF) in 40% perovskite precursor solution for the CuI of 0.18mmol and the thiocarbamide of 0.085mmol.The mixed solution of copper indium sulphur presoma and perovskite presoma is dripped to painting at sample surfaces, then the mixed solution of 5uL is dropped in to sample surfaces, and make its sufficient drawout, then sample is placed on hot platform and at 100 ℃, carries out sintering 30 minutes.
F. at sample surfaces, use the method for silk screen printing to brush one deck silver slurry, and at 100 ℃, make it solidify.
Gained solar cell process is measured, at AM1.5, and 100mW/cm 2under the irradiation of etalon optical power, the open circuit voltage 0.79V of solar cell sample, short circuit current 5.2mA, fill factor, curve factor 0.25, efficiency is 1.02%.As shown in Figure 1, be its i-v curve figure recording.
Embodiment 2
A. prepare CuInS 2precursor solution, is dissolved in 0.1mmol indium acetate, 0.5mmol thiocarbamide and 40 μ L acetic acid in 0.6mL butylamine, and carries out ultrasonic dispersion and make it form homogeneous solution, 0.1mmol cuprous iodide is joined in above-mentioned solution subsequently again.
B. ITO substrate is carried out to ultrasonic cleaning with deionized water, absolute ethyl alcohol and acetone successively, each 15 minutes, finally with nitrogen, ITO substrate is dried up.
C. by CuInS 2precursor solution carries out spin coating in ITO substrate, and rotating speed is 1500rpm, and the time is 30 seconds, spin coating secondary.By sample on hot platform with 200 ℃ by solvent evaporate to dryness, and then sample is placed among baking oven, sintering is 1 hour at 160 ℃.
D. will be oxidized alfol dispersion liquid at ITO/CuInS 2spin coating is carried out on surface, and rotating speed is 1000rpm, and the time is 20 seconds, then sample is placed on hot platform and at 150 ℃, toasts 20 minutes.
E. by the In of 0.17mmol (OAc) 3, to be dissolved into 0.8mL mass fraction be (solvent is DMF) in 40% perovskite precursor solution for the CuI of 0.18mmol and the thiocarbamide of 0.085mmol.The mixed solution of copper indium sulphur presoma and perovskite presoma is dripped to painting at sample surfaces, then the mixed solution of 5uL is dropped in to sample surfaces, and make its sufficient drawout, then sample is placed on hot platform and at 100 ℃, carries out sintering 30 minutes.
F. at sample surfaces, use the method for silk screen printing to brush one deck silver slurry, and at 100 ℃, make it solidify
Spin coating number of times in step c becomes twice above, and other step is identical with embodiment 1.
Gained solar cell process is measured, at AM1.5, and 100mW/cm 2under the irradiation of etalon optical power, the open circuit voltage 0.8V of solar cell sample, short circuit current 7.8mA, fill factor, curve factor 0.3, efficiency is 1.8%.As shown in Figure 2, be its i-v curve figure recording.
Embodiment 3
A. prepare CuInS 2precursor solution, is dissolved in 0.1mmol indium acetate, 0.5mmol thiocarbamide and 40 μ L acetic acid in 0.6mL butylamine, and carries out ultrasonic dispersion and make it form homogeneous solution, 0.1mmol cuprous iodide is joined in above-mentioned solution subsequently again.
B. ITO substrate is carried out to ultrasonic cleaning with deionized water, absolute ethyl alcohol and acetone successively, each 15 minutes, finally with nitrogen, ITO substrate is dried up.
C. by CuInS 2precursor solution carries out spin coating in ITO substrate, and rotating speed is 1500rpm, and the time is 30 seconds, spin coating three times.By sample on hot platform with 200 ℃ by solvent evaporate to dryness, and then sample is placed among baking oven, sintering is 1 hour at 160 ℃.
D. will be oxidized alfol dispersion liquid at ITO/CuInS 2spin coating is carried out on surface, and rotating speed is 1000rpm, and the time is 20 seconds, then sample is placed on hot platform and at 150 ℃, toasts 20 minutes.
E. by the In of 0.17mmol (OAc) 3, to be dissolved into 0.8mL mass fraction be (solvent is DMF) in 40% perovskite precursor solution for the CuI of 0.18mmol and the thiocarbamide of 0.085mmol.The mixed solution of copper indium sulphur presoma and perovskite presoma is dripped to painting at sample surfaces, then the mixed solution of 5uL is dropped in to sample surfaces, and make its sufficient drawout, then sample is placed on hot platform and at 100 ℃, carries out sintering 30 minutes.
F. at sample surfaces, use the method for silk screen printing to brush one deck silver slurry, and at 100 ℃, make it solidify.
Spin coating number of times in step c becomes three times above, and other step is identical with embodiment 1.Gained solar cell process is measured, at AM1.5, and 100mW/cm 2under the irradiation of etalon optical power, the open circuit voltage 0.78V of solar cell sample, short circuit current 6.1mA, fill factor, curve factor 0.28, efficiency is 1.3%.As shown in Figure 3, be its i-v curve figure recording.
In above three embodiment, the effective area of gained battery is all less than 1 square centimeter.
The foregoing is only better embodiment of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.

Claims (9)

1. copper indium sulphur/perovskite bulk heterojunction solar cell, is characterized in that: comprise the CuInS on ITO basalis, described ITO basalis 2layer, described CuInS 2silver layer on nano oxidized Solder for Al-Cu Joint Welding indium sulphur-perovskite composite bed on layer and described nano oxidized Solder for Al-Cu Joint Welding indium sulphur-perovskite composite bed.
2. solar cell according to claim 1, is characterized in that: described CuInS 2the thickness of layer is 150nm～300nm, and its preparation method is:
By CuInS 2homogeneous solution spin coating on described ITO basalis, rotating speed is 1300～3000rpm, the time is 10～50 seconds, solvent evaporated under 150～220 ℃ of conditions afterwards, and under 150～180 ℃ of conditions sintering 0.5～1.5 hour.
3. solar cell according to claim 1, is characterized in that: the thickness of described nano oxidized Solder for Al-Cu Joint Welding indium sulphur-perovskite composite bed is 400nm～600nm, and its preparation method comprises the following steps:
1) by nano oxidized alfol dispersion liquid at described CuInS 2spin coating is carried out on the surface of layer, and rotating speed is 800～2000rpm, and the time is 10～40 seconds, then at 120～200 ℃, toasts 10～30 minutes, obtains nano oxidized aluminium coating;
2) mixed solution of copper indium sulphur and perovskite is dripped to painting on the surface of described alumina coated layer, then sintering 20～60 minutes at 80～120 ℃, copper indium sulphur and perovskite are infiltrated through in described nano oxidized aluminium coating, wherein, the compound method of the mixed solution of described copper indium sulphur and perovskite is:
By the In of every 0.085～0.34mmol (OAc) 3be dissolved in the DMF solution of perovskite of 0.4～1.6mL with the CuI of 0.09～0.36mmol, the thiocarbamide of 0.043～0.17mmol, in the DMF solution of described perovskite, the mass percent of perovskite is 20～40%.
4. solar cell according to claim 3, is characterized in that: described nano oxidized aluminium coating consists of γ type nano aluminium oxide, and particle diameter is 10nm～30nm.
5. according to the arbitrary described solar cell of claim 1 to 4, it is characterized in that: the thickness of described silver layer is 500nm～1000nm.
6. according to the arbitrary described solar cell of claim 1 to 4, it is characterized in that: the thickness of described ITO basalis is 30nm～100nm.
7. a preparation method for copper indium sulphur/perovskite bulk heterojunction solar cell, comprises the following steps:
1) ITO substrate is carried out to ultrasonic cleaning with deionized water, absolute ethyl alcohol, acetone successively, then ITO substrate is dried up with nitrogen, obtain ITO basalis;
2) by CuInS 2precursor solution spin coating n time on described ITO basalis, the rotating speed of each spin coating is 1000～3000rpm, time is 10～50 seconds, by the sample after spin coating on hot platform with 150～220 ℃ by solvent evaporate to dryness, and then sample is placed among baking oven, at 150～180 ℃, sintering is 0.5～1.5 hour, obtains ITO/CuInS 2layer, wherein, spin coating frequency n=1,2 or 3;
3) by nano oxidized alfol dispersion liquid through described step 2) the described ITO/CuInS that obtains 2spin coating spin coating is carried out on the surface of layer, and rotating speed is 800～2000rpm, and the time is 10～40 seconds, then at 120～200 ℃, toasts 10～30 minutes, obtains ITO/CuInS 2/ Al 2o 3layer;
4) by the mixed solution of copper indium sulphur and perovskite at described ITO/CuInS 2/ Al 2o 3painting is dripped on the surface of layer, sintering 20～60 minutes at 80～120 ℃ then, and wherein, the compound method of the mixed solution of described copper indium sulphur and perovskite is:
By the In of every 0.085～0.34mmol (OAc) 3, the CuI of 0.09～0.36mmol is, the thiocarbamide of 0.043～0.17mmol is dissolved in the DMF solution of perovskite of 0.4～1.6mL, in the DMF solution of described perovskite, the mass percent of perovskite is 20～40%.Obtain ITO/CuInS 2/ Al 2o 3+ CuInS 2+ CaTiO 3layer;
5) at described ITO/CuInS 2/ Al 2o 3+ CuInS 2+ CaTiO 3one deck silver slurry is brushed by the method for silk screen printing in layer surface, and at 80～120 ℃, makes it solidify, and obtains ITO/CuInS 2/ Al 2o 3+ CuInS 2+ CaTiO 3/ Ag solar cell.
8. the preparation method of copper indium sulphur/perovskite bulk heterojunction solar cell according to claim 7, comprises the following steps:
1) ITO substrate is carried out to ultrasonic cleaning with deionized water, absolute ethyl alcohol, acetone successively, then ITO substrate is dried up with nitrogen, obtain ITO basalis;
2) by CuInS 2precursor solution spin coating n time on described ITO basalis, the rotating speed of each spin coating is 1500rpm, the time is 30 seconds, by the sample after spin coating on hot platform with 200 ℃ by solvent evaporate to dryness, and then sample is placed among baking oven, sintering is 1 hour at 160 ℃, obtains ITO/CuInS 2layer, wherein, spin coating frequency n=1,2 or 3, described CuInS 2the preparation method of precursor solution is:
The indium acetate, thiocarbamide, propionic acid and the butylamine that by the ratio of amount of substance, are 1:5:5:62.5 mix, and form the transparent solution without precipitation, then add the cuprous iodide equating with indium acetate amount of substance, carry out ultrasonic dispersion, obtain described CuInS 2precursor solution;
3) by nano oxidized alfol dispersion liquid through described step 2) the described ITO/CuInS that obtains 2spin coating is carried out on the surface of layer, and rotating speed is 1000rpm, and the time is 20 seconds, then at 150 ℃, toasts 20 minutes, obtains ITO/CuInS 2/ Al 2o 3layer;
4) by the mixed solution of copper indium sulphur and perovskite at described ITO/CuInS 2/ Al 2o 3painting is dripped on the surface of layer, sintering 30 minutes at 100 ℃ then, and wherein, the compound method of the mixed solution of described copper indium sulphur and perovskite is:
By the In of every 0.17mmol (OAc) 3be dissolved in the DMF solution of perovskite of 0.8mL with the CuI of 0.18mmol, the thiocarbamide of 0.085mmol, in the DMF solution of described perovskite, the mass percent of perovskite is 40%, obtains ITO/CuInS 2/ Al 2o 3+ CuInS 2+ CaTiO 3layer;
5) at described ITO/CuInS 2/ Al 2o 3+ CuInS 2+ CaTiO 3one deck silver slurry is brushed by the method for silk screen printing in layer surface, and at 100 ℃, makes it solidify, and obtains ITO/CuInS 2/ Al 2o 3+ CuInS 2+ CaTiO 3/ Ag solar cell.
9. according to the preparation method of the copper indium sulphur/perovskite bulk heterojunction solar cell described in claim 7 or 8, described nano oxidized alfol dispersion liquid is the dispersion liquid of the isopropyl alcohol of γ type nano aluminium oxide, wherein, the solid content of aluminium oxide is 20%～25%, and the particle diameter of nano alumina particles is 10～30 nanometers.
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