CN106803536A - A kind of perovskite solar cell and preparation method thereof - Google Patents
A kind of perovskite solar cell and preparation method thereof Download PDFInfo
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- CN106803536A CN106803536A CN201710019847.8A CN201710019847A CN106803536A CN 106803536 A CN106803536 A CN 106803536A CN 201710019847 A CN201710019847 A CN 201710019847A CN 106803536 A CN106803536 A CN 106803536A
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- H—ELECTRICITY
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- 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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- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- 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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- H—ELECTRICITY
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- 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
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract
The invention discloses a kind of perovskite solar cell and preparation method thereof, belong to solar cell device field.The perovskite solar cell includes negative electrode, electron transfer layer, perovskite active layer, hole transmission layer, anode, the sull of wherein electron transfer layer is prepared by steam induced low temperature, the oxide precursor liquid solution of 30~75nm of spin coating on cell cathode, it is then placed in the closed container containing 1 50mL solvents, closed container is placed in into 8~16h in the batch-type furnace that temperature is 120~180 DEG C is obtained.The preparation method greatly reduces the preparation temperature of sull, can be used for flexible substrates, realizes the low temperature preparation of perovskite solar cell and the method is widely applied to the production field of device;Gained perovskite solar cell open-circuit voltage is larger, the open-circuit voltage of the solar cell made higher than common 500 DEG C of high temperature.
Description
Technical field
The invention belongs to solar cell device field, more specifically to a kind of perovskite solar cell
And preparation method thereof.
Background technology
Energy problem is the major issue of society, in the energy-consuming accounting of China, non-renewable energy resources proportion
Up to 91.27%, and regenerative resource only account for less than 9%, and according to the current earth non-renewable resources (stone explored
Oil, coal, natural gas and nuclear fuel etc.) reserves, it is contemplated that in the near future, the series of problems that energy shortage is brought will
Increasingly highlight.Therefore, it is that China or even whole human society are able to compeling for sustainable development to greatly develop clean reproducible energy
Being essential will.
Perovskite solar cell is high with photoelectric transformation efficiency as emerging solar cell, preparation process is simple, system
Make the low plurality of advantages of cost, in the time of short 6 or seven years, the research of perovskite solar cell achieves major progress,
Its photoelectric transformation efficiency is increased to exceed 22% from initial 3.8%, the progress of perovskite solar cell allow it is seen that
Dawn, imply that it is not used as a kind of efficient regenerative resource device, it would be possible to gather around and have broad application prospects.Borrow
The research progress of mirror polymer organic solar cell, we have reason to speculate:Develop printable perovskite solar cell system
Standby technique simultaneously realizes that flexibility will be imperative.And realize all print and the flexibility of perovskite solar cell, its key element it
One is the low temperature preparation for realizing perovskite battery.
Conventional planar heterojunction perovskite solar cell, it mainly has ITO or FTO electrodes, electron transfer layer (dioxy
Change titanium, tin oxide, zinc oxide), perovskite light-absorption layer, hole transmission layer, metal electrode (gold, silver, aluminium) composition.Perovskite extinction
Layer, hole transmission layer etc. can be prepared at relatively low temperature (being less than 150 DEG C), but electron transfer layer prepare it is general
All over being higher than 300 DEG C, preferable electron transport layer materials titanium dioxide will can just be prepared under the conditions of higher than 500 DEG C, and this does not just have
Method exploitation large area flexible (such as PET wants temperature to be less than 150 DEG C for substrate) perovskite solar cell.Therefore, we have very much must
A kind of cryogenic fluid preparation method towards metal oxide (titanium dioxide, tin oxide, zinc oxide) film is developed, is applied to
In the middle of the device preparation flow of perovskite solar cell.
The content of the invention
For calcium of the existing sull (by taking titanium dioxide as an example) as electron transfer layer present in prior art
Titanium ore solar cell, its electron transfer layer titanium dioxide can only prepare problem under the conditions of higher than 500 DEG C, the invention provides
A kind of perovskite solar cell and preparation method thereof, it can realize that the preparation temperature for reducing sull (can be less than 150
DEG C), realize the low temperature preparation of perovskite solar cell.
The purpose of the present invention is achieved through the following technical solutions.
Perovskite solar cell, including negative electrode, electron transfer layer, perovskite active layer, hole transmission layer, anode are cloudy
Pole connects electron transfer layer in perovskite solar cell bottom, and electron transfer layer connection perovskite active layer, perovskite is lived
Property layer connection hole transmission layer, hole transmission layer connection galvanic anode, it is characterised in that the oxide of the electron transfer layer is thin
Film is prepared by steam induced low temperature.
Further, the sull of the electron transfer layer is titanium dioxide, zinc oxide, tin oxide and titanium dioxide
One kind of silicon.
Further, the perovskite solar battery structure is planar heterojunction structure or laminated construction.
The method for preparing the perovskite solar cell, it is characterised in that step is as follows:
The preparation of step one, cathode electrode:Electrode basement is carried out patterning etching by electrode basement as cathode layer, and
Electrode substrate is cleaned up;
The preparation of step 2, electron transfer layer:In atmosphere, the oxide precursor of 30~75nm of spin coating is molten above negative electrode
Liquid, is then placed in the closed container containing 1-50mL solvents, and closed container is placed in into the case that temperature is 120~180 DEG C
8~16h in formula stove;
The preparation of step 3, perovskite active layer:In the glove box that nitrogen removes water, on the electron transport layer by methyl iodide
Change the active layer that amine and lead chloride solution film forming form 250~400nm, after perovskite active layer is made annealing treatment;
It is prepared by step 4, hole transmission layer:In the glove box that nitrogen removes water, 150~200nm of spin coating on active layer
2,2', 7,7'- tetra- [N, N- bis- (4- methoxyphenyls) amino] fluorenes solution of -9,9'- spiral shells two;
The preparation of step 5, anode electrode:On hole transmission layer using gaseous phase deposition instrument evaporation thickness be 80~
The gold of 150nm is less than 4 × 10 as negative electrode, the air pressure environment of evaporation-4Pa。
Further, electrode basement is the SnO of fluorine doped in the step one2Transparent conducting glass FTO or tin indium oxide
Electro-conductive glass ITO.
Further, oxide precursor liquid solution is ethanol acid solution, two water of isopropyl titanate in the step 2
The volume ratio of one kind of the diethanol methyl ether ethanol solution of zinc acetate or the ethanol acid solution of stannous oxalate, solute and solvent is
1:10~1:20.
Further, solvent is one kind of deionized water, ethanol or isopropanol in the step 2.
Further, the film build method of electron transfer layer is spin-coating method, spraying process or print process in the step 3
It is a kind of.
Further, it is 100 DEG C that temperature is made annealing treatment in the step 3.
Compared to prior art, the advantage of the invention is that:
(1) perovskite solar cell open-circuit voltage of the invention is 0.99~1.04v, is done higher than common 500 DEG C of high temperature
The open-circuit voltage of the solar cell for going out:0.84~8.89v.
(2) present invention greatly reduces the preparation temperature (can be less than 150 DEG C) of sull with solvent vapo(u)r revulsion,
The low temperature preparation of perovskite solar cell is realized, can be used for flexible substrates, such as the flexible device based on PET base;
(3) present invention process is simple, low cost, it is adaptable to flexible device, and is easily achieved large-scale production, is expected to popularization
It is applied to the production field of device.
Brief description of the drawings
Fig. 1 is the main working process figure that the present invention prepares perovskite solar cell.
Fig. 2 is the device architecture schematic diagram of perovskite solar cell of the present invention.
Fig. 3 is the 120 DEG C of device photoelectric made conversions of steam treatment perovskite solar cell electron transfer layer 8h
Efficiency and device performance figure.
Fig. 4 is the 120 DEG C of device photoelectric made conversions of steam treatment perovskite solar cell electron transfer layer 16h
Efficiency and device performance figure.
Fig. 5 is the 180 DEG C of device photoelectric made conversions of steam treatment perovskite solar cell electron transfer layer 8h
Efficiency and device performance figure.
Fig. 6 is the 180 DEG C of device photoelectric made conversions of steam treatment perovskite solar cell electron transfer layer 16h
Efficiency and device performance figure.
Description of symbols in accompanying drawing
1. the spin coating electron transfer layer on negative electrode;2. steam treatment is carried out to electron transfer layer in closed container;3. calcium
Titanium ore active layer preparation process;4. the preparation process of hole transmission layer;5. anodic process is deposited with;6. cell cathode;7. electronics is passed
Defeated layer;8. active layer;9. hole transmission layer;10. galvanic anode.
Specific embodiment
With reference to Figure of description and specific embodiment, the present invention is described in detail.
Embodiment 1
Fig. 1 is the main working process figure that the present invention prepares perovskite solar cell, wherein 1 is the spin coating electricity on negative electrode
Sub- transport layer, 2 is to carry out steam treatment to electron transfer layer in closed container, and 3 is perovskite active layer preparation process, and 4 are
The preparation process of hole transmission layer, 5 is evaporation anodic process.
Fig. 2 is the device architecture schematic diagram of perovskite solar cell of the present invention, wherein 6 is cell cathode, 7 pass for electronics
Defeated layer, 8 is active layer, and 9 is hole transmission layer, and 10 is galvanic anode.
Embodiment 2
It is as follows using standard perovskite preparation method of solar battery, including step:
1st, selection is coated with the clear glass of FTO electrodes as anode layer 6, FTO is etched, and FTO glass substrates are cleaned
Totally.
2nd, prepared by electron transfer layer:In atmosphere, on negative electrode 6 spin coating 40nm TiO 2 precursor solution (isopropyl
The ethanol acid solution of alcohol titanium), then it is placed in the closed container containing 5mL deionized waters, 8h is processed at 120 DEG C,
Form electron transfer layer 7.Can be learnt by Fig. 3 and the perovskite solar cell that electron transfer layer is made is processed under this technique
Photoelectric transformation efficiency and device performance.
3rd, prepared by active layer:In glove box (nitrogen, except water environment), the methyl of spin coating 350nm on electron transfer layer 7
Iodate amine (CH3NH3) and lead chloride (PbCl I2) solution, form active layer 8.In the glove box of nitrogen water removal, to active layer 8
Annealing, temperature is 100 DEG C, and the time is 90min;
4th, prepared by hole transmission layer:In the glove box of nitrogen water removal, the 2,2' of spin coating 160nm, 7,7'- on active layer
Four [N, N- bis- (4- methoxyphenyls) amino] -9,9'- spiral shells two fluorenes (Spiro-OMeTAD) solution form hole transmission layer 9;
5th, the preparation of anode electrode:The gold that meteorological precipitation instrument evaporation thickness is 100nm is used on hole transmission layer 9
(Au) as negative electrode 10, the air pressure environment of its evaporation is less than 4 × 10-4Pa。
Embodiment 3
Preparation method is in addition to step 2 difference, and its preparation process of its each layer is same as Example 2.Electricity in embodiment 2
The preparation of sub- transport layer:In atmosphere, on negative electrode 6 spin coating 40nm TiO 2 precursor solution (the two of zinc acetate dihydrate
The volume ratio of ethanol methyl ether ethanol solution, solute and solvent is 1:10), then it is placed on and contains the closed of 5mL deionized waters
Container in, 120 DEG C process 16h, formed electron transfer layer 7.Can be learnt by Fig. 4 and process electron transfer layer under this technique
The photoelectric transformation efficiency and device performance of the perovskite solar cell made.
Embodiment 4
Preparation method is in addition to step 2 difference, and its preparation process of its each layer is same as Example 2.Electricity in embodiment 2
The preparation of sub- transport layer:In atmosphere, on negative electrode 6 spin coating 40nm the TiO 2 precursor solution (ethanol of stannous oxalate
The volume ratio of acid solution, solute and solvent is 1:15), then it is placed in the closed container containing 10mL ethanol,
180 DEG C for the treatment of 8h, form electron transfer layer 7.Can be learnt by Fig. 5 and the perovskite that electron transfer layer is made is processed under this technique
The photoelectric transformation efficiency and device performance of solar cell.
Embodiment 5
Preparation method is in addition to step 2 difference, and its preparation process of its each layer is same as Example 2.Electricity in embodiment 2
The preparation of sub- transport layer:In atmosphere, on negative electrode 6 spin coating 40nm the TiO 2 precursor solution (ethanol of isopropyl titanate
The volume ratio of acid solution, solute and solvent is 1:20), then it is placed in the closed container containing 25mL isopropanols,
1h is processed at 180 DEG C, electron transfer layer 7 is formed.Can be learnt by Fig. 6 and the calcium titanium that electron transfer layer is made is processed under this technique
The photoelectric transformation efficiency and device performance of ore deposit solar cell.
Fig. 3 is that embodiment 2 is made of 120 DEG C of steam treatment perovskite solar cell electron transfer layer titanium dioxide 8h
The device photoelectric conversion efficiency and device performance figure for going out.
Fig. 4 is the device that embodiment 3 is made with 120 DEG C of steam treatment perovskite solar cell electron transfer layer 16h
Part photoelectric transformation efficiency and device performance figure.
Fig. 5 is the device that embodiment 4 is made with 180 DEG C of steam treatment perovskite solar cell electron transfer layer 8h
Photoelectric transformation efficiency and device performance figure.
Fig. 6 is the device that embodiment 5 is made with 180 DEG C of steam treatment perovskite solar cell electron transfer layer 16h
Part photoelectric transformation efficiency and device performance figure.
The energy conversion efficiency of the perovskite solar cell prepared by embodiment 2 and embodiment 3 as shown in Figure 3 and Figure 4,
120 DEG C for the treatment of for carrying out 8h and 16h to electron transfer layer with vapor, the perovskite solar cell prepared in this way
Device performance approach, the process time device more long performance shorter than process time is somewhat better, the He of embodiment 4
The energy conversion efficiency of the perovskite solar cell prepared by embodiment 5 as shown in Figure 3 and Figure 4, at 180 DEG C, uses vapor
The treatment of 8h and 16h is carried out to electron transfer layer, the device performance of the perovskite solar cell prepared in this way connects
Closely, process time device more long is that time shorter performance is somewhat better than treatment, but with embodiment 2 and embodiment
3 compare, and device performance is enhanced.
Four embodiments of the above all make efficient perovskite solar cell in the case of less than 180 DEG C, and this is than common report
500 DEG C of road high-temperature process electron transfer layer and the perovskite solar cell for preparing will more energy savings, it is important that water steams
Vapour treatment electron transfer layer can be greatly lowered the treatment temperature (reducing 320~380 DEG C) of electron transfer layer, not only have so
Effect reduces the difficulty of experiment, also for the device later with metal oxides such as titanium dioxide as electron transfer layer moves towards flexibility
Large-scale commercial applications road is cleared away the obstacles, to the field industrial development significance.
Below schematically the invention and embodiments thereof are described, the description does not have restricted, accompanying drawing
Shown in be also the invention one of implementation method, actual structure is not limited thereto.So, if this area
Those of ordinary skill enlightened by it, in the case where this creation objective is not departed from, designed and the technology without creative
The similar frame mode of scheme and embodiment, all should belong to the protection domain of this patent.
Claims (9)
1. a kind of perovskite solar cell, including negative electrode, electron transfer layer, perovskite active layer, hole transmission layer, anode,
Cell cathode connects electron transfer layer, electron transfer layer connection perovskite active layer, calcium in perovskite solar cell bottom
Titanium ore active layer is connected with hole transmission layer, hole transmission layer connection galvanic anode, it is characterised in that the electron transfer layer
Sull be to be prepared by steam induced low temperature.
2. a kind of perovskite solar cell according to claim 1, it is characterised in that the oxidation of the electron transfer layer
Thing film is one kind of titanium dioxide, zinc oxide, tin oxide and silica.
3. a kind of perovskite solar cell according to claim 1, it is characterised in that the perovskite solar cell
Structure is planar heterojunction structure or laminated construction.
4. a kind of method of the perovskite solar cell prepared described in claim 1, it is characterised in that step is as follows:
The preparation of step one, cathode electrode:Electrode basement is carried out patterning etching as cathode layer by electrode basement, and by electricity
Pole substrate is cleaned up;
The preparation of step 2, electron transfer layer:In atmosphere, above negative electrode 30~75nm of spin coating oxide precursor liquid solution,
It is then placed in the closed container containing 1-50mL solvents, closed container is placed in the batch-type furnace that temperature is 120~180 DEG C
In 8~16h;
The preparation of step 3, perovskite active layer:In the glove box that nitrogen removes water, on the electron transport layer by methylpyridinium iodide amine
With lead chloride solution film forming formed 250~400nm perovskite active layer, after to perovskite active layer make annealing treatment;
It is prepared by step 4, hole transmission layer:In the glove box that nitrogen removes water, the 2 of 150~200nm of spin coating on active layer,
2', 7,7'- tetra- [N, N- bis- (4- methoxyphenyls) amino] fluorenes solution of -9,9'- spiral shells two;
The preparation of step 5, anode electrode:The use of gaseous phase deposition instrument evaporation thickness is 80~150nm's on hole transmission layer
Gold is less than 4 × 10 as negative electrode, the air pressure environment of evaporation-4Pa。
5. a kind of preparation method of perovskite solar cell according to claim 4, it is characterised in that the step one
Middle electrode basement is the SnO of fluorine doped2Transparent conducting glass FTO or indium tin oxide-coated glass ITO.
6. a kind of preparation method of perovskite solar cell according to claim 4, it is characterised in that the step 2
Middle oxide precursor liquid solution is ethanol acid solution, the diethanol methyl ether ethanol solution or grass of zinc acetate dihydrate of isopropyl titanate
The volume ratio of one kind of the ethanol acid solution of sour stannous, solute and solvent is 1:10~1:20.
7. a kind of preparation method of perovskite solar cell according to claim 4, it is characterised in that the step 2
Middle solvent is one kind of deionized water, ethanol or isopropanol.
8. a kind of preparation method of perovskite solar cell according to claim 4, it is characterised in that the step 3
The film build method of middle electron transfer layer is one kind of spin-coating method, spraying process or print process.
9. a kind of preparation method of perovskite solar cell according to claim 4, it is characterised in that the step 3
Middle annealing temperature is 100 DEG C.
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CN109037457A (en) * | 2018-06-25 | 2018-12-18 | 南京邮电大学 | The preparation method and applications of sull as electron transfer layer |
CN110021679A (en) * | 2018-01-10 | 2019-07-16 | 中国科学院大学 | With the electron transfer layer of solwution method preparation and including its crystal silicon solar battery |
WO2019148326A1 (en) * | 2018-01-30 | 2019-08-08 | 南方科技大学 | Method for preparing perovskite thin film and application thereof |
CN110718595A (en) * | 2018-11-07 | 2020-01-21 | 中国科学院大学 | Oxide-metal composite electron transport layer prepared based on solution method and crystalline silicon solar cell comprising same |
CN112750733A (en) * | 2020-12-31 | 2021-05-04 | 阳光中科(福建)能源股份有限公司 | Perovskite solar cell titanium dioxide compact layer apparatus for producing |
CN112993168A (en) * | 2021-02-07 | 2021-06-18 | 广东技术师范大学 | Tin dioxide porous structure perovskite photovoltaic cell without annealing effect and preparation method thereof |
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Cited By (7)
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CN110021679A (en) * | 2018-01-10 | 2019-07-16 | 中国科学院大学 | With the electron transfer layer of solwution method preparation and including its crystal silicon solar battery |
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CN110718595A (en) * | 2018-11-07 | 2020-01-21 | 中国科学院大学 | Oxide-metal composite electron transport layer prepared based on solution method and crystalline silicon solar cell comprising same |
CN112750733A (en) * | 2020-12-31 | 2021-05-04 | 阳光中科(福建)能源股份有限公司 | Perovskite solar cell titanium dioxide compact layer apparatus for producing |
CN112750733B (en) * | 2020-12-31 | 2024-03-08 | 阳光中科(福建)能源股份有限公司 | Perovskite solar cell titanium dioxide compact layer apparatus for producing |
CN112993168A (en) * | 2021-02-07 | 2021-06-18 | 广东技术师范大学 | Tin dioxide porous structure perovskite photovoltaic cell without annealing effect and preparation method thereof |
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