CN105355790A - Low cost perovskite solar cell being suitable for production - Google Patents
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/40—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising a p-i-n structure, e.g. having a perovskite absorber between p-type and n-type charge transport layers
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- 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
- H10K30/80—Constructional details
- H10K30/81—Electrodes
- H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
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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
- H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
- H10K85/211—Fullerenes, e.g. C60
- H10K85/215—Fullerenes, e.g. C60 comprising substituents, e.g. PCBM
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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
- Y02E10/549—Organic PV cells
Abstract
The invention discloses a low cost perovskite solar cell being suitable for production, and a preparation method thereof. The solar cell comprises a light transmission/transparent electrode layer, an electronic transmission layer, a light-absorption layer, an electronic absorbing layer, a cavity transmission layer and a top electrode, wherein the light transmission/transparent electrode layer, the electronic transmission layer, the light-absorption layer, the electronic absorbing layer, the cavity transmission layer and the top electrode are stacked successively; the light-absorption layer is provided with a material with a perovskite structure; the electronic absorbing layer is formed by fullerene derivatives; the cavity transmission layer is formed by ternary oxides; and the top electrode is formed by materials with good conductivity. The low cost perovskite solar cell effectively utilizes the performance of perovskite materials, and improves the photoelectric conversion efficiency of a perovskite solar cell by more than 17%, and is suitable for volume production.
Description
Technical field
The invention belongs to perovskite area of solar cell, particularly a kind of low cost perovskite solar cell and preparation method thereof being suitable for producing.
Background technology
Along with the fast development of economy, the demand of the mankind to the energy grows with each passing day, and the problem of energy and environment has become the focal issue of the world today.Political economy relation and this two problems in the world are in close relations.Current, sustainable, the environmentally friendly energy receives much concern, and wherein theCourse of PV Industry is swift and violent.But current photovoltaic industry, mainly based on crystal silicon material, also exists the shortcoming that cost is high, various countries' photovoltaic industry all mainly relies on government subsidy to promote.If the solar cell of low cost can be produced, then greatly can accelerate the development of photovoltaic industry.
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 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 a kind of low cost perovskite solar cell and preparation method thereof being suitable for producing.Adopt battery material of the present invention and structure thereof, not only cost is low, and significantly can improve solar cell to the absorption of photon and transformation efficiency thereof, thus improves the electricity conversion of solar cell, improves 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 to prepare sulfurized layer 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 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:
Adopt the chlorobenzene solution of fullerene derivate to be spun on light-absorption layer, dry, obtain Electron absorption layer, control concentration and the coating thickness of solution, make the thickness of Electron absorption layer between 30-150nm;
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 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 derivative of fullerene, including but not limited to PCBM, PC71BM.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 excavate its potential, 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 and contains nanometer sulfide film 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.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.
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 illustrates:accompanying drawing 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 fluorine tin-oxide (FTO, fluorinedopedtinoxide) electro-conductive glass as printing opacity/transparent electrode layer;
2) adopt the method for physical vapour deposition (PVD), FTO is prepared chromic sulfide film, thickness 15 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 53nm;
4) Electron absorption layer is prepared
Adopt the chlorobenzene solution of PCBM to be spun on light-absorption layer, dry, obtain the Electron absorption layer of thickness 145nm;
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 276nm 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%.
embodiment 2
1) ITO(IndiumTinOxides is adopted) electro-conductive glass is 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 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 430nm;
4) Electron absorption layer is prepared
Adopt the chlorobenzene solution of PCBM to be spun on light-absorption layer, dry, obtain thickness 83nm and obtain Electron absorption layer;
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 18.6%.
embodiment 3
1) adopt ITO 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 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 491nm;
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 491nm;
4) Electron absorption layer is prepared
Adopt the chlorobenzene solution of PCBM to be spun on light-absorption layer, dry, obtain the Electron absorption layer of thickness 68nm;
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 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 19.3%.
embodiment 4
1) adopt aluminium zinc oxide AZO electro-conductive glass 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 2.0Mol/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 310nm;
4) Electron absorption layer is prepared
Adopt the chlorobenzene solution of PCBM to be spun on light-absorption layer, dry, obtain thickness 95nm and obtain Electron absorption layer;
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 carbon-coating of method evaporation 126nm 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 17.1%.
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 490nm;
4) Electron absorption layer is prepared
Adopt the chlorobenzene solution of PC71BM to be spun on light-absorption layer, dry, obtain the Electron absorption layer of thickness 32nm;
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 the method for hot evaporation evaporation 283nm 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 18.9%.
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 (8)
1. perovskite solar cell 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 sulfide; Described light-absorption layer is the material with perovskite structure; Described Electron absorption layer is made up of fullerene derivate; 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 perovskite 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 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:
Adopt the chlorobenzene solution of fullerene derivate to be spun on light-absorption layer, dry, obtain Electron absorption layer, control concentration and the coating thickness of solution, make the thickness of Electron absorption layer between 30-150nm;
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, Electron absorption layer is the derivative of fullerene, including but not limited to PCBM, PC71BM.
7. solar cell as claimed in claim 1, it is characterized in that, described top electrode is metal electrode or material with carbon element electrode.
8. solar cell as claimed in claim 1, is characterized in that, described sulfide is violent including but not limited to sulfuration, chromic sulfide.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106410048A (en) * | 2016-10-14 | 2017-02-15 | 宁波大学 | Method for preparing secondary perovskite solar cell |
| CN106601833A (en) * | 2017-02-17 | 2017-04-26 | 镇江皮埃纳米科技有限公司 | Low-cost and high-stability solar cell applicable to production and preparation method thereof |
| CN106711334A (en) * | 2017-02-17 | 2017-05-24 | 镇江皮埃纳米科技有限公司 | Solar battery containing perovskite material and preparation method of solar battery |
| CN106848067A (en) * | 2017-02-17 | 2017-06-13 | 镇江皮埃纳米科技有限公司 | A kind of perovskite solar cell of excellent performance |
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| CN105070834A (en) * | 2015-07-28 | 2015-11-18 | 华中科技大学 | Perovskite solar cell based on doped NiO hole transport layer and preparation method thereof |
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2015
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| CN105070834A (en) * | 2015-07-28 | 2015-11-18 | 华中科技大学 | Perovskite solar cell based on doped NiO hole transport layer and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106410048A (en) * | 2016-10-14 | 2017-02-15 | 宁波大学 | Method for preparing secondary perovskite solar cell |
| CN106410048B (en) * | 2016-10-14 | 2019-05-03 | 宁波大学 | A method of preparing secondary perovskite solar battery |
| CN106601833A (en) * | 2017-02-17 | 2017-04-26 | 镇江皮埃纳米科技有限公司 | Low-cost and high-stability solar cell applicable to production and preparation method thereof |
| CN106711334A (en) * | 2017-02-17 | 2017-05-24 | 镇江皮埃纳米科技有限公司 | Solar battery containing perovskite material and preparation method of solar battery |
| CN106848067A (en) * | 2017-02-17 | 2017-06-13 | 镇江皮埃纳米科技有限公司 | A kind of perovskite solar cell of excellent performance |
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Application publication date: 20160224 |