CN105304820A - Perovskite solar cell with enhanced graphene and preparation method thereof - Google Patents

Perovskite solar cell with enhanced graphene and preparation method thereof Download PDF

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CN105304820A
CN105304820A CN201510827183.9A CN201510827183A CN105304820A CN 105304820 A CN105304820 A CN 105304820A CN 201510827183 A CN201510827183 A CN 201510827183A CN 105304820 A CN105304820 A CN 105304820A
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杨秋香
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杨秋香
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • H01L51/42Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof specially adapted for sensing infra-red radiation, light, electro-magnetic radiation of shorter wavelength or corpuscular radiation and adapted for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation using organic materials as the active part, or using a combination of organic materials with other material as the active part; Multistep processes for their manufacture
    • H01L51/44Details of devices
    • H01L51/441Electrodes
    • H01L51/442Electrodes transparent electrodes, e.g. ITO, TCO
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • H01L51/0001Processes specially adapted for the manufacture or treatment of devices or of parts thereof
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • H01L51/0032Selection of organic semiconducting materials, e.g. organic light sensitive or organic light emitting materials
    • H01L51/0045Carbon containing materials, e.g. carbon nanotubes, fullerenes
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L2251/00Indexing scheme relating to organic semiconductor devices covered by group H01L51/00
    • H01L2251/10Processes specially adapted for the manufacture or treatment of organic semiconductor devices
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L2251/00Indexing scheme relating to organic semiconductor devices covered by group H01L51/00
    • H01L2251/30Materials
    • H01L2251/301Inorganic materials
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/549Organic PV cells
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a perovskite solar cell with enhanced graphene and a preparation method thereof. The perovskite solar cell comprises a light transmission/transparent electrode layer, an electron transport layer, a light absorption layer, an electron absorption layer, a hole transport layer, and a top electrode which are successively stacked. The light absorption layer is a material provided with perovskite structure. The electron absorption layer is formed by graphene and oxidized graphene. The hole transport layer is formed by a ternary oxide. The top electrode is formed by a material with good conductivity. The perovskite solar cell effectively utilizes the performance of the perovskite material, is increased in the photoelectric converting efficiency by over 17 percent, and is suitable for batch production.

Description

Perovskite solar cell that a kind of Graphene strengthens and preparation method thereof
Technical field
The invention belongs to perovskite area of solar cell, perovskite solar cell of particularly a kind of Graphene enhancing and preparation method thereof.
Background technology
The current solar cell market overwhelming majority is occupied by crystal silicon solar energy battery, but due to crystalline silicon price high, constrain the application development of photovoltaic industry.Perovskite solar cell is the emerging solar cell of a class, its price is much relatively cheap, utilize the photovoltaic material with perovskite structure to realize opto-electronic conversion, have that raw material sources is extensive, structure simple, can be prepared into the advantages such as flexible battery, be with a wide range of applications.But such cell photoelectric transformation efficiency is on the low side at present, the research emphasis of present stage improves its photoelectric conversion efficiency.
Chinese invention patent CN104134711A discloses a kind of perovskite solar cell and solwution method preparation method thereof.This perovskite solar cell comprises the substrate, transparency electrode, electron transfer layer, light-absorption layer, hole transmission layer and the top electrode that stack gradually.Wherein light-absorption layer is the photovoltaic material light-absorption layer with perovskite structure; its electron transfer layer, perovskite material light-absorption layer and hole transmission layer all can realize solwution method preparation under the air ambient of low temperature (200 ° of below C); especially electron transfer layer does not need the nano particle that high temperature (450 ° of more than C) processes or synthesizes; be conducive to simplification of flowsheet; reduce costs; improve the preparation efficiency of battery, be convenient to accomplish scale production.The conversion photoelectric efficiency of this invention battery is lower than lower than 11%.
Chinese invention patent CN104795501A discloses a kind of perovskite solar cell and preparation method thereof, this perovskite solar cell is by FTO transparent conducting glass substrate, electron transfer layer, light-absorption layer, hole transmission layer and metal electrode composition, its light-absorption layer is the perovskite material of two-dimensional layered structure, this invention adopts spin-coating method to prepare Layered Perovskite light-absorption layer, preparation method is simple, filming performance is good, described light-absorption layer material is along with the change of the number of plies, its band gap is adjustable, and there is good chemical stability, this material exposes 30 days without chemical breakdown under higher air humidity (50-80%), and still keep good layer structure, excellent performance and stable, but its transformation efficiency is lower.
Chinese invention patent CN103855307A discloses a kind of perovskite solar cell and preparation method thereof.Described perovskite solar cell comprises transparency electrode, hole transmission layer, perovskite light-absorption layer, electron transfer layer and metal electrode, and wherein said hole transmission layer comprises at least one in PEDOT:PSS, P3HT, PTAA, PThTPTI, metal oxide and graphene oxide.The perovskite solar cell of this invention has lower cost; Described preparation method's technique is simple, can carry out large-scale production.Its transformation efficiency is lower than 14%.
Chinese invention patent CN104810479A discloses a kind of solar cell and manufacture method.Avoid existing perovskite cell making process to the needs of high temperature, avoid current perovskite battery simultaneously and will use plumbous shortcoming.The invention provides a kind of tin perovskite structure flexible solar battery, be followed successively by conductive substrates, anode, electron transfer layer, absorbed layer, hole transmission layer, silver from top to bottom, wherein electron transfer layer is nano aluminium oxide film, and absorbed layer is tin perovskite structure absorbed layer.This invention adopts nano aluminium oxide to do electron transfer layer, and do absorbed layer with tin perovskite like structure, its electron transfer layer operates and can complete under 150 ° of C, decreases plumbous use simultaneously.Its transformation efficiency is lower than 14%.
Perovskite solar cell progressively constantly advances to industrialization by foregoing invention, but, and at present can't large-scale production.The transformation efficiency of the perovskite battery that its reason is mainly current is high not enough, generally below 15%.Find the target that more high efficiency solar battery structure is people's concerted effort.
Summary of the invention
Goal of the invention: in order to make full use of the character of perovskite material, preparation can be used for the perovskite solar cell produced, and the invention provides perovskite solar cell of a kind of Graphene enhancing and preparation method thereof.Adopt battery material of the present invention and structure thereof, significantly can improve solar cell to the absorption of photon and transformation efficiency thereof, thus improve the electricity conversion of solar cell, improve device performance.
Technical scheme of the present invention is as follows:
1) adopt electro-conductive glass as printing opacity/transparent electrode layer;
2) electron transfer layer is prepared: adopt the method for evaporation or vapour deposition on electro-conductive glass, prepare manganese sulfide layer; THICKNESS CONTROL is between 10-50nm;
3) light-absorption layer is prepared:
A. prepare PbI2 solution, the concentration of PbI2 is 0.5-3.0Mol/L, and solvent is dimethyl formamide;
B. prepare CH3NH3I solution: concentration 10mg/mL, solvent is isopropyl alcohol;
Adopt solwution method fabricated in situ perovskite material: first spin coating PbI2 solution on the electron transport layer, put into the immersion of CH3NH3I solution after oven dry and grow perovskite material, obtain perovskite light-absorption layer.By the concentration of control PbI2 and CH3NH3I reaction solution, control pattern and the thickness of perovskite, THICKNESS CONTROL is between 50-500nm;
4) Electron absorption layer is prepared:
Being added by graphite powder is equipped with in the container of the concentrated sulfuric acid, container is placed in ice bath, stir, the potassium permanganate powder added again, keep temperature less than 20 DEG C to stir, by the solution warms after stirring to 35 DEG C of Keep agitation 30 minutes, then in solution, add deionized water slowly and concentration is the hydrogen peroxide of 30%, and mixture is warmed up to 98 DEG C of Keep agitation 15 minutes, until mixture color becomes glassy yellow; Then by above-mentioned solution vibrating dispersion in ultrasonic disperse instrument, stable dispersion liquid is obtained.Then hydrazine hydrate is dripped, and this solution is put into after oil bath is heated to 100 DEG C, isothermal reaction 10-20 minute, then filter with pellicle, the product obtained is washed with deionized water, methyl alcohol, ethanol respectively, be spun on perovskite material, finally fully dry under 60 DEG C of conditions, the product obtained is exactly the mixture of Graphene and graphene oxide.The concentration of control reaction time, solution and coating thickness, make the thickness of Electron absorption layer between 30-150nm, the weight percent content of graphene oxide is between 5-30%;
5) hole transmission layer is prepared:
By mixing of titanium isopropoxide (or two (acetylacetone based) diisopropyl titanate precursor solution) and ethanol niobium, stir, be spun on Electron absorption layer;
6) preparation of top electrode:
Adopt the methods such as vacuum thermal evaporation, spraying, deposition, at conductive metal layer or the carbon-coating of device upper surface evaporation 50-300nm.
The material of perovskite solar cell printing opacity/transparent electrode layer of the present invention is transparent and the material that can conduct electricity composition, include but not limited to indium tin oxide (ITO, IndiumTinOxides), fluorine tin-oxide (FTO, fluorinedopedtinoxide) transparent electrode material that, aluminium zinc oxide (AZO, aluminium-dopedzincoxide) etc. are conventional.Electron transfer layer is manganese sulfide; Light-absorption layer is the material with perovskite structure, and the perovskite structure photovoltaic material adopted is the organic inorganic hybridization perovskite of ABX3 type crystal structure.Wherein, B is lead, tin, antimony, and X is halogens.Electron absorption layer is the mixture of Graphene and graphene oxide.Hole transmission layer is made up of ternary oxide, comprise Ti, Nb, O tri-kinds of elements, and the mol ratio of Nb/Ti is between 1:30 and 1:10.Top electrode is metal electrode or conductive carbon material electrode, as silver, gold, copper, graphite, Graphene etc.
Useful effect: adopt material of the present invention and structure, can make full use of the performance of perovskite material, and excavates its potential, and form P-I-N heterojunction, fully absorb solar energy and improve its conversion ratio, its transformation efficiency can reach more than 17%.Present invention employs the electron transfer layer-light-absorption layer-Electron absorption layer of nanoscale uniqueness, P-I-N heterojunction can be promoted catch-the ability of absorb photons.The present invention adopts Containing Sulfur manganese as electron transfer layer, can transmit the electronics that perovskite material produces because of the solar energy absorbed efficiently.But for oxide, its cost is slightly high.Present invention employs Graphene and graphite oxide is rare, make the energy level of adjacent layer more close, be also conducive to improving transformation efficiency.Graphene is more easily prepared relative to fullerene, reduces cost.In general, the present invention mainly adopts the rubbing method of industrial maturation, is applicable to the production of industrialization production large scale, high efficiency solar cell.But, existing perovskite solar cell not yet obtains the sample that large area can be used for producing, the invention solves this problem, the technology of inventing is suitable for preparing large area, high efficiency solar cell, and its cost only has 1/3rd of traditional silicon solar cell.
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Below by describing device of the present invention and preparation method thereof in detail with embodiment by reference to the accompanying drawings, but be not construed as limiting the invention.
Accompanying drawing explanation
Fig. 1 is structural representation of the present invention.1 be printing opacity/transparent electrode layer, 2 be electron transfer layer in figure, 3 be light-absorption layer, 4 be Electron absorption layer, 5 for hole transmission layer and 6 is for top electrode.
embodiment 1
1) adopt aluminium zinc oxide AZO electro-conductive glass as printing opacity/transparent electrode layer;
2) adopt the method for hot evaporation, ITO is prepared manganese sulfide film, thickness 38 nanometer;
3) light-absorption layer is prepared:
A. prepare PbI2 solution, concentration is 2.0Mol/L, and solvent is dimethyl formamide;
B. prepare CH3NH3I solution: concentration 8mg/mL, solvent is isopropyl alcohol;
Adopt solwution method fabricated in situ perovskite material: first spin coating PbI2 solution on the electron transport layer, put into the immersion of CH3NH3I solution after oven dry and grow perovskite material, obtain perovskite light-absorption layer; Thickness 312nm;
4) Electron absorption layer is prepared
Being added by graphite powder is equipped with in the container of the concentrated sulfuric acid, container is placed in ice bath, stir, the potassium permanganate powder added again, keep temperature 15 DEG C to stir, by the solution warms after stirring to 35 DEG C of Keep agitation 30 minutes, then in solution, add deionized water slowly and concentration is the hydrogen peroxide of 30%, and mixture is warmed up to 98 DEG C of Keep agitation 15 minutes, until mixture color becomes glassy yellow; Then by above-mentioned solution vibrating dispersion in ultrasonic disperse instrument, stable dispersion liquid is obtained; Then hydrazine hydrate is dripped, and this solution is put into after oil bath is heated to 100 DEG C, isothermal reaction 20 minutes, then filter with pellicle, the product obtained is washed with deionized water, methyl alcohol, ethanol respectively, is spun on perovskite material, last fully dry under 60 DEG C of conditions, the product obtained is exactly the mixture of Graphene and graphene oxide, and thickness is 34nm, and the weight percent content of graphene oxide is 6.2%;
5) hole transmission layer is prepared:
By titanium isopropoxide and ethanol niobium the mixing of ratio in 30:1, stir, be spun on Electron absorption layer, obtain hole transmission layer;
6) preparation of top electrode:
Adopt the carbon-coating of method evaporation 125nm on hole transmission layer of chemical deposition.
Carry out battery performance test, adopt in experimentation and carry out under 100mW/cm2 solar simulator (Newport) AM1.5G illumination, record optoelectronic transformation efficiency and defend 18.4%.
embodiment 2
1) ITO(IndiumTinOxides is adopted) electro-conductive glass is as printing opacity/transparent electrode layer;
2) adopt the method for vacuum evaporation, AZO is prepared manganese sulfide film, thickness 45 nanometer;
3) light-absorption layer is prepared:
A. prepare PbI2 solution, concentration is 2.3Mol/L, and solvent is dimethyl formamide;
B. prepare CH3NH3I solution: concentration 7.5mg/mL, solvent is isopropyl alcohol;
Adopt solwution method fabricated in situ perovskite material: first spin coating PbI2 solution on the electron transport layer, put into the immersion of CH3NH3I solution after oven dry and grow perovskite material, obtain perovskite light-absorption layer; Thickness 441nm;
4) Electron absorption layer is prepared
Being added by graphite powder is equipped with in the container of the concentrated sulfuric acid, container is placed in ice bath, stir, the potassium permanganate powder added again, keep temperature 15 DEG C to stir, by the solution warms after stirring to 35 DEG C of Keep agitation 30 minutes, then in solution, add deionized water slowly and concentration is the hydrogen peroxide of 30%, and mixture is warmed up to 98 DEG C of Keep agitation 15 minutes, until mixture color becomes glassy yellow; Then by above-mentioned solution vibrating dispersion in ultrasonic disperse instrument, stable dispersion liquid is obtained; Then hydrazine hydrate is dripped, and this solution is put into after oil bath is heated to 100 DEG C, isothermal reaction 10 minutes, then filter with pellicle, the product obtained is washed with deionized water, methyl alcohol, ethanol respectively, is spun on perovskite material, last fully dry under 60 DEG C of conditions, the product obtained is exactly the mixture of Graphene and graphene oxide, and thickness is at 55nm, and the weight percent content measuring graphene oxide is 29%;
5) hole transmission layer is prepared:
By titanium isopropoxide and ethanol niobium the mixing of ratio in 25:1, stir, be spun on Electron absorption layer, obtain hole transmission layer;
6) preparation of top electrode:
Adopt the silver layer of method evaporation 52nm on hole transmission layer of vacuum thermal evaporation.
Carry out battery performance test, adopt in experimentation and carry out under 100mW/cm2 solar simulator (Newport) AM1.5G illumination, record optoelectronic transformation efficiency and defend 18.1%.
embodiment 3
1) adopt fluorine tin-oxide (FTO, fluorinedopedtinoxide) electro-conductive glass as printing opacity/transparent electrode layer;
2) adopt the method for physical vapour deposition (PVD), ITO is prepared manganese sulfide film, thickness 10 nanometer;
3) light-absorption layer is prepared:
A. prepare PbI2 solution, concentration is 3.0Mol/L, and solvent is dimethyl formamide;
B. prepare CH3NH3I solution: concentration 5mg/mL, solvent is isopropyl alcohol;
Adopt solwution method fabricated in situ perovskite material: first spin coating PbI2 solution on the electron transport layer, put into the immersion of CH3NH3I solution after oven dry and grow perovskite material, obtain perovskite light-absorption layer; Thickness 55nm;
4) Electron absorption layer is prepared
Being added by graphite powder is equipped with in the container of the concentrated sulfuric acid, container is placed in ice bath, stir, the potassium permanganate powder added again, keep temperature 15 DEG C to stir, by the solution warms after stirring to 35 DEG C of Keep agitation 30 minutes, then in solution, add deionized water slowly and concentration is the hydrogen peroxide of 30%, and mixture is warmed up to 98 DEG C of Keep agitation 15 minutes, until mixture color becomes glassy yellow; Then by above-mentioned solution vibrating dispersion in ultrasonic disperse instrument, stable dispersion liquid is obtained; Then hydrazine hydrate is dripped, and this solution is put into after oil bath is heated to 100 DEG C, isothermal reaction 15 minutes, then filter with pellicle, the product obtained is washed with deionized water, methyl alcohol, ethanol respectively, is spun on perovskite material, last fully dry under 60 DEG C of conditions, the product obtained is exactly the mixture of Graphene and graphene oxide, and thickness is 36nm, and the weight percent content of graphene oxide is 17%;
5) hole transmission layer is prepared:
By two (acetylacetone based) diisopropyl titanate precursor solution and the mixing mixing the ratio in 10:1 of ethanol niobium, stir, be spun on Electron absorption layer, obtain hole transmission layer;
6) preparation of top electrode:
Adopt the silver layer of method evaporation 277nm on hole transmission layer of vacuum thermal evaporation.
Carry out battery performance test, adopt in experimentation and carry out under 100mW/cm2 solar simulator (Newport) AM1.5G illumination, record optoelectronic transformation efficiency and defend 18.7%.
embodiment 4
1) adopt ITO electro-conductive glass as printing opacity/transparent electrode layer;
2) adopt the method for physical vapour deposition (PVD), FTO is prepared manganese sulfide film, thickness 15 nanometer;
3) light-absorption layer is prepared:
A. prepare PbI2 solution, concentration is 1.5Mol/L, and solvent is dimethyl formamide;
B. prepare CH3NH3I solution: concentration 8.5mg/mL, solvent is isopropyl alcohol;
Adopt solwution method fabricated in situ perovskite material: first spin coating PbI2 solution on the electron transport layer, put into the immersion of CH3NH3I solution after oven dry and grow perovskite material, obtain perovskite light-absorption layer; Thickness 488nm;
A. prepare PbI2 solution, concentration is 1.5Mol/L, and solvent is dimethyl formamide;
B. prepare CH3NH3I solution: concentration 8.5mg/mL, solvent is isopropyl alcohol;
Adopt solwution method fabricated in situ perovskite material: first spin coating PbI2 solution on the electron transport layer, put into the immersion of CH3NH3I solution after oven dry and grow perovskite material, obtain perovskite light-absorption layer; Thickness 493nm;
4) Electron absorption layer is prepared
Being added by graphite powder is equipped with in the container of the concentrated sulfuric acid, container is placed in ice bath, stir, the potassium permanganate powder added again, keep temperature 15 DEG C to stir, by the solution warms after stirring to 35 DEG C of Keep agitation 30 minutes, then in solution, add deionized water slowly and concentration is the hydrogen peroxide of 30%, and mixture is warmed up to 98 DEG C of Keep agitation 15 minutes, until mixture color becomes glassy yellow; Then by above-mentioned solution vibrating dispersion in ultrasonic disperse instrument, stable dispersion liquid is obtained; Then hydrazine hydrate is dripped, and this solution is put into after oil bath is heated to 100 DEG C, isothermal reaction 10 minutes, then filter with pellicle, the product obtained is washed with deionized water, methyl alcohol, ethanol respectively, is spun on perovskite material, last fully dry under 60 DEG C of conditions, the product obtained is exactly the mixture of Graphene and graphene oxide, and thickness is 144nm, and the weight percent content of graphene oxide is 28%;
5) hole transmission layer is prepared:
By titanium isopropoxide and ethanol niobium the mixing of ratio in 20:1, stir, be spun on Electron absorption layer, obtain hole transmission layer;
6) preparation of top electrode:
Adopt the silver layer of method evaporation 161nm on hole transmission layer of vacuum thermal evaporation.
Carry out battery performance test, adopt in experimentation and carry out under 100mW/cm2 solar simulator (Newport) AM1.5G illumination, record optoelectronic transformation efficiency and defend 19.7%.
embodiment 5
1) adopt aluminium zinc oxide AZO electro-conductive glass as printing opacity/transparent electrode layer;
2) adopt the method for physical vapour deposition (PVD), AZO is prepared manganese sulfide film, thickness 50 nanometer;
3) light-absorption layer is prepared:
A. prepare PbI2 solution, concentration is 0.5Mol/L, and solvent is dimethyl formamide;
B. prepare CH3NH3I solution: concentration 10mg/mL, solvent is isopropyl alcohol;
Adopt solwution method fabricated in situ perovskite material: first spin coating PbI2 solution on the electron transport layer, put into the immersion of CH3NH3I solution after oven dry and grow perovskite material, obtain perovskite light-absorption layer; Thickness 493nm;
4) Electron absorption layer is prepared
Being added by graphite powder is equipped with in the container of the concentrated sulfuric acid, container is placed in ice bath, stir, the potassium permanganate powder added again, keep temperature 15 DEG C to stir, by the solution warms after stirring to 35 DEG C of Keep agitation 30 minutes, then in solution, add deionized water slowly and concentration is the hydrogen peroxide of 30%, and mixture is warmed up to 98 DEG C of Keep agitation 15 minutes, until mixture color becomes glassy yellow; Then by above-mentioned solution vibrating dispersion in ultrasonic disperse instrument, stable dispersion liquid is obtained; Then hydrazine hydrate is dripped, and this solution is put into after oil bath is heated to 100 DEG C, isothermal reaction 20 minutes, then filter with pellicle, the product obtained is washed with deionized water, methyl alcohol, ethanol respectively, is spun on perovskite material, last fully dry under 60 DEG C of conditions, the product obtained is exactly the mixture of Graphene and graphene oxide, and thickness is 79nm, and the weight percent content of graphene oxide is 5.8%;
5) hole transmission layer is prepared:
By titanium isopropoxide and ethanol niobium the mixing of ratio in 10:1, stir, be spun on Electron absorption layer, obtain hole transmission layer;
6) preparation of top electrode:
Adopt the silver layer of the method for hot evaporation evaporation 322nm on hole transmission layer.
Carry out battery performance test, adopt in experimentation and carry out under 100mW/cm2 solar simulator (Newport) AM1.5G illumination, record optoelectronic transformation efficiency and defend 17.6%.
The above is only some examples of embodiment of the present invention; be noted that for those skilled in the art; under the premise without departing from the principles of the invention; some improvements and modifications can also be made; such as; protected at the external transparent material adding last layer category of glass of printing opacity/transparent electrode layer, these improvements and modifications also should be considered as protection scope of the present invention.

Claims (6)

1. perovskite solar cell of strengthening of a Graphene and preparation method thereof, printing opacity/transparent electrode layer that this battery stacks gradually, electron transfer layer, light-absorption layer, Electron absorption layer, hole transmission layer and top electrode, wherein: described electron transfer layer is made up of manganese sulfide; Described light-absorption layer is the material with perovskite structure; Described Electron absorption layer is made up of Graphene and graphene oxide; Described hole transmission layer is made up of ternary oxide, and described top electrode is made up of the material that electric conductivity is good.
2. a solar cell as claimed in claim 1, is characterized in that, described hole transmission layer is ternary oxide, be made up of, and the mol ratio of Nb/Ti is between 1:30 and 1:10 Ti, Nb, O tri-kinds of elements; Described electric transmission layer thickness is between 10-50nm, and described light-absorption layer thickness is between 50-500nm, and described Electron absorption layer thickness is between 30-150nm, and described top electrode thickness is between 50-300nm.
3. a solar cell as claimed in claim 1, is characterized in that, its preparation method comprises following steps:
1) adopt electro-conductive glass as printing opacity/transparent electrode layer;
2) electron transfer layer is prepared: adopt the method for evaporation or vapour deposition to prepare manganese sulfide on electro-conductive glass; THICKNESS CONTROL is between 10-50nm;
3) light-absorption layer is prepared:
A. prepare PbI2 solution, the concentration of PbI2 is 0.5-3.0Mol/L, and solvent is dimethyl formamide;
B. prepare CH3NH3I solution: concentration 5-10mg/mL, solvent is isopropyl alcohol;
Adopt solwution method fabricated in situ perovskite material: first spin coating PbI2 solution on the electron transport layer, put into the immersion of CH3NH3I solution after oven dry and grow perovskite material, obtain perovskite light-absorption layer; By the concentration of control PbI2 and CH3NH3I reaction solution, control pattern and the thickness of perovskite, THICKNESS CONTROL is between 50-500nm;
4) Electron absorption layer is prepared:
Being added by graphite powder is equipped with in the container of the concentrated sulfuric acid, container is placed in ice bath, stir, the potassium permanganate powder added again, keep temperature less than 20 DEG C to stir, by the solution warms after stirring to 35 DEG C of Keep agitation 30 minutes, then in solution, add deionized water slowly and concentration is the hydrogen peroxide of 30%, and mixture is warmed up to 98 DEG C of Keep agitation 15 minutes, until mixture color becomes glassy yellow; Then by above-mentioned solution vibrating dispersion in ultrasonic disperse instrument, stable dispersion liquid is obtained; Then hydrazine hydrate is dripped, and this solution is put into after oil bath is heated to 100 DEG C, isothermal reaction 10-20 minute, then filter with pellicle, the product obtained is washed with deionized water, methyl alcohol, ethanol respectively, be spun on perovskite material, finally fully dry under 60 DEG C of conditions, the product obtained is exactly the mixture of Graphene and graphene oxide; The concentration of control reaction time, solution and coating thickness, make the thickness of Electron absorption layer between 30-150nm, the weight percent content of graphene oxide is between 5-30%;
5) hole transmission layer is prepared:
By mixing of titanium isopropoxide (or two (acetylacetone based) diisopropyl titanate precursor solution) and ethanol niobium, stir, be spun on Electron absorption layer;
6) preparation of top electrode:
Adopt the methods such as vacuum thermal evaporation, spraying, deposition, at conductive metal layer or the carbon-coating of device upper surface evaporation 50-300nm.
4. solar cell as claimed in claim 1, it is characterized in that, the material of transparency electrode is transparent and the material that can conduct electricity composition, include but not limited to indium tin oxide (ITO, IndiumTinOxides), fluorine tin-oxide (FTO, fluorinedopedtinoxide), the transparent electrode material such as aluminium zinc oxide (AZO, aluminium-dopedzincoxide).
5. solar cell as claimed in claim 1, it is characterized in that, described perovskite structure photovoltaic material is the organic inorganic hybridization perovskite of ABX3 type crystal structure; Wherein, B is lead, tin, antimony, and X is halogen.
6. solar cell as claimed in claim 1, it is characterized in that, described top electrode is metal electrode or material with carbon element electrode.
CN201510827183.9A 2015-11-24 2015-11-24 Perovskite solar cell with enhanced graphene and preparation method thereof Pending CN105304820A (en)

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CN105977386A (en) * 2016-07-04 2016-09-28 陕西煤业化工技术研究院有限责任公司 Perovskite solar cell of nano metal oxide hole transport layer and preparation method thereof
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CN108722019A (en) * 2018-05-05 2018-11-02 安徽乐金环境科技有限公司 A kind of composite Nano purification strainer and preparation method thereof
CN108744727A (en) * 2018-05-05 2018-11-06 安徽乐金环境科技有限公司 A kind of Household ceramic filter core and preparation method thereof
CN109078390A (en) * 2018-05-05 2018-12-25 安徽乐金环境科技有限公司 A kind of active carbon base strainer and preparation method thereof purifying benzene

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