CN105280822A - Low-cost solar cell suitable for production - Google Patents
Low-cost solar cell suitable for production Download PDFInfo
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- CN105280822A CN105280822A CN201510827180.5A CN201510827180A CN105280822A CN 105280822 A CN105280822 A CN 105280822A CN 201510827180 A CN201510827180 A CN 201510827180A CN 105280822 A CN105280822 A CN 105280822A
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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
- 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
- H10K30/40—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
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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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- 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 solar cell suitable for production and a preparation method thereof. The perovskite solar cell comprises: a light-transmissive/transparent electrode layer, an electron transmission layer, a light absorption layer, an electron absorption layer, a hole transmission layer and a top electrode which are successively laminated, wherein, the electron transmission layer is made of quaternary oxides; the light absorption layer is made of material with a perovskite structure; the electron absorption layer is constituted of fullerene derivatives; the hole transmission layer is constituted of ternary oxides; the top electrode is constituted of materials with excellent conductivity. According to the solar cell, the performance of perovskite material is effectively utilized; the photoelectric conversion efficiency of the perovskite solar cells is increased to 16% and above; the solar cell is suitable for mass production.
Description
Technical field
The invention belongs to perovskite area of solar cell, particularly a kind of low-cost solar battery and preparation method thereof being suitable for producing.
Background technology
At present, because silicon solar cell prevailing on commercial solar cell market still can not meet the requirement of low cost, people are exploring the novel solar battery meeting high efficiency and low cost requirement always.Since two thousand nine, the organic metal halide with perovskite crystal structure is that the solar cell of light-absorption layer (perovskite solar cell) obtains in recent years and develops faster, promises to be high efficiency, the low-cost solar battery with market potential.
In the recent period, perovskite solar cell becomes study hotspot.It take inorganic compound as the perovskite solar cell of hole transmission layer that Chinese invention patent CN103915567A discloses a kind of.Be characterized in that it comprises transparent conductive substrate and stacks gradually the electron transfer layer on this substrate, the light-absorption layer with perovskite crystal structure, inorganic compound hole transmission layer and positive electrode.This invention adopts inorganic compound to be to improve the stability of perovskite solar cell properties as hole transmission layer advantage, extends the useful life of solar cell.
Chinese invention patent CN103746078A discloses a kind of perovskite solar cell and preparation method thereof.This perovskite solar cell comprises the substrate, transparency electrode, electron transfer layer, electric transmission-light-absorption layer, light-absorption layer, hole transport-light-absorption layer, hole transmission layer and the top electrode that stack gradually, wherein: described light-absorption layer is the photovoltaic material light-absorption layer with perovskite structure; Described electric transmission-light-absorption layer is the complex functional layer that electron transport material and perovskite structure photovoltaic material are fitted together to formation; Described hole transport-light-absorption layer is the complex functional layer that hole mobile material and perovskite structure photovoltaic material are fitted together to formation.The both sides of this perovskite solar cell light-absorption layer all have certain micro-nano structure, thus and the mutually chimeric complex functional layer of material between the transport layer outside it, can be formed, significantly improve the contact area of light-absorption layer and transport layer, be conducive to improving exciton dissociation and charge transfer efficiency, thus suppress the compound in light induced electron and hole, improve device performance.The conversion ratio of this battery is below 9%.
Chinese invention patent CN104465994A discloses a kind of preparation method of the perovskite solar cell based on full coating process, relates to solar cell.A kind of preparation method of the perovskite solar cell based on full coating process that can realize low cost, high efficiency, industrialization is provided.1) in electrically conducting transparent substrate, coating process is adopted to prepare electron transfer layer, perovskite active layer, hole transmission layer successively; Described coating process adopts slot-die coating or atomizing coating; 2) on hole transmission layer, be coated with top electrode, described coating adopts silk screen printing and scraper for coating.Solve technique and the Cost Problems of evaporation and printing precious metal electrode, also solve coating pyrocarbon and starch the destruction to calcium titanium ore bed that may cause.Adopt the method for a step annealing, anneal under 70 ~ 150 ° of C after being namely coated with all functional layers.This invention simplifies manufacture craft, but does not mention optoelectronic transformation efficiency.
Perovskite solar cell progressively constantly advances to industrialization by foregoing invention, but, and at present can't large-scale production.As a kind of can the solar battery sheet of volume production, not only require that preparation is simple, cost is low, the more important thing is that the electricity conversion of its output-namely wants high.Also do not report the perovskite sun battery of conversion ratio more than 15% that can produce in batches at present, 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, the invention provides a kind of low-cost solar battery and preparation method thereof being suitable for producing.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) prepare electron transfer layer: the then mixture of the sour acetone nickel of spin coating, lithium acetate, magnesium acetate 4 hydrate, dry (300 DEG C-400 DEG C), prepare electron transfer layer, THICKNESS CONTROL is between 10-100nm;
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.
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 quaternary oxide, be made up of, and the mol ratio of Li/Mg is between 1:10 and 1:3 Ni, Mg, Li, O tetra-kinds of elements.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 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 16%.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 mainly adopts the rubbing method of industrial maturation, is applicable to the production of industrialization production large scale, low cost, 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.
embodiment
Below by 1 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) according to the mixed solution of the sour acetone nickel of the proportional arrangement of mol ratio 1:1:10, lithium acetate, magnesium acetate 4 hydrate, be spun on printing opacity/transparent electrode layer, in 350 DEG C of oven dry, prepare electron transfer layer; Thickness 99nm;
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 at 100mW/cm2 solar simulator (Newport) AM1.Carry out under 5G illumination, record optoelectronic transformation efficiency and defend 17%.
embodiment 2
1) adopt aluminium zinc oxide AZO electro-conductive glass as printing opacity/transparent electrode layer;
2) according to the mixed solution of the sour acetone nickel of the proportional arrangement of mol ratio 2:1:3, lithium acetate, magnesium acetate 4 hydrate, be spun on printing opacity/transparent electrode layer, in 360 DEG C of oven dry, prepare electron transfer layer; Thickness 85nm;
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 290nm on hole transmission layer.
Carry out battery performance test, adopt in experimentation at 100mW/cm2 solar simulator (Newport) AM1.Carry out under 5G illumination, record optoelectronic transformation efficiency and defend 16.8%.
embodiment 3
1) ITO(IndiumTinOxides is adopted) electro-conductive glass is as printing opacity/transparent electrode layer;
2) according to the mixed solution of the sour acetone nickel of the proportional arrangement of mol ratio 1:1:5, lithium acetate, magnesium acetate 4 hydrate, be spun on printing opacity/transparent electrode layer, in 300 DEG C of oven dry, prepare electron transfer layer; THICKNESS CONTROL is at 11nm;
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 and carry out under 100mW/cm2 solar simulator (Newport) AM1.5G illumination, record optoelectronic transformation efficiency and defend 18.8%.
embodiment 4
1) adopt aluminium zinc oxide AZO electro-conductive glass as printing opacity/transparent electrode layer;
2) according to the mixed solution of the sour acetone nickel of the proportional arrangement of mol ratio 2:1:6, lithium acetate, magnesium acetate 4 hydrate, be spun on printing opacity/transparent electrode layer, in 350 DEG C of oven dry, prepare electron transfer layer; Thickness 98nm;
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 at 100mW/cm2 solar simulator (Newport) AM1.Carry out under 5G illumination, record optoelectronic transformation efficiency and defend 17.1%.
embodiment 5
1) adopt ITO electro-conductive glass as printing opacity/transparent electrode layer;
2) according to the mixed solution of the sour acetone nickel of the proportional arrangement of mol ratio 1:1:3, lithium acetate, magnesium acetate 4 hydrate, be spun on printing opacity/transparent electrode layer, in 400 DEG C of oven dry, prepare electron transfer layer; Thickness 83nm;
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;
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 at 100mW/cm2 solar simulator (Newport) AM1.Carry out under 5G illumination, record optoelectronic transformation efficiency and defend 16.5%.
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 (7)
1. one kind is suitable for low-cost solar battery produced 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: the quaternary oxide of described electron transfer layer is by forming; 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, the quaternary oxide of described electron transfer layer is made up of Ni, Mg, Li, O tetra-kinds of elements, and the mol ratio of Li/Mg is between 1:10 and 1:3; Described hole transmission layer is made up of Ti, Nb, O tri-kinds of elements, and the mol ratio of Nb/Ti is between 1:30 and 1:10; Described electric transmission layer thickness is between 10-100nm, 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) prepare electron transfer layer: the then mixture of the sour acetone nickel of spin coating, lithium acetate, magnesium acetate 4 hydrate, dry (300 DEG C-400 DEG C), prepare electron transfer layer, THICKNESS CONTROL is between 10-100nm;
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. perovskite 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. perovskite 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. perovskite 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. perovskite solar cell as claimed in claim 1, it is characterized in that, described top electrode is metal electrode or material with carbon element electrode.
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| CN108666435A (en) * | 2018-07-27 | 2018-10-16 | 京东方科技集团股份有限公司 | The manufacturing method of OLED display panel, display device and display panel |
| CN110120454A (en) * | 2019-05-10 | 2019-08-13 | 电子科技大学 | Application, solar battery and the preparation method of organic acid and/or alcohol in preparation solar cell interface adjusting control agent |
| CN110518124A (en) * | 2019-07-26 | 2019-11-29 | 西安电子科技大学 | Using ternary quaternary oxide as the perovskite solar battery and preparation method of electron transfer layer |
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