CN105070838A - Perovskite type solar cell based on multi-orientation ordered crystallization and preparation method thereof - Google Patents

Perovskite type solar cell based on multi-orientation ordered crystallization and preparation method thereof Download PDF

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CN105070838A
CN105070838A CN201510531478.1A CN201510531478A CN105070838A CN 105070838 A CN105070838 A CN 105070838A CN 201510531478 A CN201510531478 A CN 201510531478A CN 105070838 A CN105070838 A CN 105070838A
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廖良生
王照奎
李萌
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Suzhou University
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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
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • 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 perovskite type solar cell based on multi-orientation ordered crystallization and a preparation method thereof. The preparation method comprises the steps that: step 1, methylammonium iodate, lead chloride, indium chloride or indium iodide dissolves in a N,N-dimethylformamide solution to obtain a perovskite type DMF solution; step 2, an electrode is processed by a poly (3,4-ethylenedioxythiophene) : polystyrene sulfonic acid salline solution to form an anode decoration layer; step 3, annealing is carried out on a thin film to form an anode decoration layer; step 4, the perovskite type thin film is processed and then is treated by annealing to obtain a photosensitive layer; step 5, a methyl [6,6]-phenyl-C61-butyrate (PCBM) thin film is processed to obtain an electron transfer layer; step 6, a 1,10-phenanthronline,4,7-diphenyl (Bphen) thin film is continuously processed to obtain a cathode decoration layer; and step 7, a cathode electrode is processed. With the prepared solar cell, the energy conversion efficiency of the device and the device stability are improved obviously.

Description

Ca-Ti ore type solar cell of a kind of multiple ordered orientation crystallization and preparation method thereof
Technical field
The invention belongs to area of solar cell, relate to a kind of perovskite solar cell and preparation method thereof, particularly relate to Ca-Ti ore type solar cell of a kind of multiple ordered orientation crystallization and preparation method thereof.
Background technology
At present, apply prevailing silica-based solar cell for we providing the product of installed capacity more than 10GW in photovoltaic technology, but because of its preparation cost higher, complex process, can become the main clean energy resource of human future, developing solar cell constantly suffer from query.Ca-Ti ore type solar cell is with low cost with it, advantages of simple structure and simple has attracted the concern of numerous researcher.
Since 2009, the novel solar cell based on organic and inorganic perovskite material gets the attention, in recent years, its energy conversion efficiency from 3% be increased to more than 15% fast, the application prospect of display great potential.
In order to realize the demand of its industrialization further, the perovskite solar cell of efficient stable becomes the target of current World Science man pursuit.In order to better realize this goal, researcher proposes and utilizes iodide (InCl 3, InI 3) preparation technology of adulterated with Ca and Ti ore film, its structure is similar with traditional structure, by doping new material in calcium titanium ore bed membrane-film preparation process, achieve the multiple ordered orientation structure of calcium titanium ore bed internal crystallization, and then the open circuit voltage of battery improved and short circuit current, finally also greatly enhance the energy conversion efficiency of solar cell and the stability of battery device.
Summary of the invention
The technical problem solved: the object of the invention is Ca-Ti ore type solar cell of openly a kind of efficient stable, multiple ordered orientation crystallization and preparation method thereof, improves energy conversion efficiency, the device stability of solar cell device.
Technical scheme: in order to solve the problem, the invention discloses a kind of preparation method of Ca-Ti ore type solar cell of multiple ordered orientation crystallization, described preparation method comprises the following steps:
Step 1: by iodate first ammonium (MAI), lead chloride (PbCl 2), inidum chloride or indium iodide in molar ratio 3:0.85:0.05-0.25 be dissolved in DMF solution, stir 5 hours, obtain the perovskite DMF solution of 30wt%;
Step 2: will 3,4-ethylene dioxythiophene be gathered: poly styrene sulfonate (PEDOT:PSS) solution adopt spin coating, inkjet printing or volume to volume method processing in substrate transparency electrode, form uniform anode modification layer;
Step 3: anneal film at 95 DEG C 10-30 minute in air, forms uniform anode modification layer;
Step 4: at poly-3,4-ethylene dioxythiophene: method processing calcium titanium ore bed film poly styrene sulfonate film adopting spin coating, inkjet printing or volume to volume, anneals at 95-100 DEG C and can obtain uniform curing photosensitive layer in 30-50 minute;
Step 5: continue method processing process [6,6]-phenyl-C61-methyl butyrate (PCBM) film adopting spin coating, inkjet printing or volume to volume on perovskite thin film, uniform electron transfer layer can be obtained;
Step 6: continue method processing process 4,7-diphenyl-1,10-ferrosin (Bphen) film adopting spin coating, inkjet printing or volume to volume on electric transmission layer film, uniform cathodic modification layer can be obtained;
Step 7: adopt evaporation or inkjet printing methods processing cathode electrode on cathodic modification layer.
As preferred technical scheme, the preparation method of the Ca-Ti ore type solar cell of described a kind of multiple ordered orientation crystallization, in described step 1, iodate first ammonium, lead chloride, inidum chloride or indium iodide mol ratio are 3:0.85:0.15.
As preferred technical scheme, the preparation method of the Ca-Ti ore type solar cell of described a kind of multiple ordered orientation crystallization, anneals film 20 minutes at 95 DEG C in described step 3 in air.
As preferred technical scheme, the preparation method of the Ca-Ti ore type solar cell of described a kind of multiple ordered orientation crystallization, anneals 40 minutes in described step 4 at 98 DEG C.
As preferred technical scheme, the preparation method of the Ca-Ti ore type solar cell of described a kind of multiple ordered orientation crystallization, the inidum chloride chosen, the purity of indium iodide are more than 99.9%.
As preferred technical scheme, the preparation method of the Ca-Ti ore type solar cell of described a kind of multiple ordered orientation crystallization, described substrate is flexible substrates, ito glass, AZO glass or FTO glass.
As preferred technical scheme, the preparation method of the Ca-Ti ore type solar cell of described a kind of multiple ordered orientation crystallization, described cathode electrode is Ag, Al or Au, and thickness of electrode is 60-100nm.
The Ca-Ti ore type solar cell for preparing of the preparation method of the Ca-Ti ore type solar cell of arbitrary described a kind of multiple ordered orientation crystallization above.
beneficial effect:the present invention compared with prior art, has following advantage: (1) adopts doping InCl 3, InI 3decrease the use of Pb poisoning metal element to a certain extent, greatly reduce the pollution to environment in cell fabrication processes, make its preparation process environmental protection;
(2) adulterate InCl 3, InI 3the degree of crystallinity of device calcium titanium ore bed and ordered orientation are improved, there is comparatively perfectly crystal structure, after doping, its film has obvious crystallization behavior along multiple directions, perovskite crystal mask has at most and the multiple order of the most obvious orientation, this is by the passage of the multiple ordered orientation of the crystallization that made calcium titanium ore bed occur, the separation of charge of film can be promoted to a great extent, migration and collection rate, and then effectively can improve the short circuit current of device, fill factor, curve factor and open circuit voltage, make energy conversion efficiency obtain to improve significantly simultaneously, the preparation of Efficient devices is achieved when lower cost, the further instruments industriesization that promoted is produced,
(3) adulterate InCl 3, InI 3perovskite thin film is made to have comparatively stable crystal structure, stable crystal structure effectively can improve the stability of device to a great extent, the stability of device obtains and improves significantly, under same environmental condition, device has longer useful life and the stability of device, also produces for instruments industriesization and provides strong guarantee.
(4) adulterate InCl 3, InI 3while adopt annealing process occur film multiple order be not available for other conventional perovskite thin films, greatly enhance the energy conversion efficiency of device, there is not the crystal structure of this multiple order without perovskite thin film in annealing device, greatly enhance the energy conversion efficiency of device and the stability of device relative to the result without annealing process process yet yet.
Accompanying drawing explanation
Fig. 1 is the Ca-Ti ore type solar cell schematic diagram that preparation method of the present invention prepares;
Fig. 2 is ito glass substrate doping InI prepared by preparation method of the present invention 3the Two dimensional X ray diffraction figure of perovskite thin film.
Embodiment
Embodiment 1
Step 1: an ito glass substrate is provided, column criterionization of going forward side by side is cleaned; By iodate first ammonium, lead chloride, inidum chloride in molar ratio 3:0.85:0.05 be dissolved in DMF solution, stir 5 hours, obtain the perovskite DMF solution of 30wt%;
Step 2: will 3,4-ethylene dioxythiophene be gathered: poly styrene sulfonate solution adopts spin coating method processing in substrate transparency electrode, rotates 40 seconds, form uniform anode modification layer under accelerating to the rotating speed of 4500rpm;
Step 3: film is annealed 30 minutes at 95 DEG C in air, forms uniform anode modification layer;
Step 4: at poly-3,4-ethylene dioxythiophene: poly styrene sulfonate film adopts spin coating method process calcium titanium ore bed film, at 100 DEG C, annealing can obtain uniform curing photosensitive layer in 30 minutes;
Step 5: continue to adopt spin coating method processing process [6,6]-phenyl-C61-methyl butyrate film on perovskite thin film, rotate 40 seconds under accelerating to the rotating speed of 2000rpm, uniform electron transfer layer can be obtained;
Step 6: continue to adopt spin coating method processing process 4,7-diphenyl-1,10-ferrosin film on electric transmission layer film, rotate 40 seconds under accelerating to the rotating speed of 4000rpm, uniform cathodic modification layer can be obtained;
Step 7: adopt evaporation coating method to process cathode electrode Ag on cathodic modification layer.
Embodiment 2
Step 1: an ito glass substrate is provided, column criterionization of going forward side by side is cleaned; By iodate first ammonium, lead chloride, inidum chloride in molar ratio 3:0.85:0.25 be dissolved in DMF solution, stir 5 hours, obtain the perovskite DMF solution of 30wt%;
Step 2: will 3,4-ethylene dioxythiophene be gathered: poly styrene sulfonate solution adopts spin coating method processing in substrate transparency electrode, rotates 40 seconds, form uniform anode modification layer under accelerating to the rotating speed of 4500rpm;
Step 3: film is annealed 10 minutes at 95 DEG C in air, forms uniform anode modification layer;
Step 4: at poly-3,4-ethylene dioxythiophene: poly styrene sulfonate film adopts spin coating method process calcium titanium ore bed film, at 95 DEG C, annealing can obtain uniform curing photosensitive layer in 50 minutes;
Step 5: continue to adopt spin coating method processing process [6,6]-phenyl-C61-methyl butyrate film on perovskite thin film, rotate 40 seconds under accelerating to the rotating speed of 2000rpm, uniform electron transfer layer can be obtained;
Step 6: continue to adopt spin coating method processing process 4,7-diphenyl-1,10-ferrosin film on electric transmission layer film, rotate 40 seconds under accelerating to the rotating speed of 4000rpm, uniform cathodic modification layer can be obtained;
Step 7: adopt evaporation coating method to process cathode electrode Au on cathodic modification layer.
Embodiment 3
Step 1: an ito glass substrate is provided, column criterionization of going forward side by side is cleaned; By iodate first ammonium, lead chloride, inidum chloride in molar ratio 3:0.85:0.15 be dissolved in DMF solution, stir 5 hours, obtain the perovskite DMF solution of 30wt%;
Step 2: will 3,4-ethylene dioxythiophene be gathered: poly styrene sulfonate solution adopts spin coating method processing in substrate transparency electrode, rotates 40 seconds, form uniform anode modification layer under accelerating to the rotating speed of 4500rpm;
Step 3: film is annealed 20 minutes at 95 DEG C in air, forms uniform anode modification layer;
Step 4: at poly-3,4-ethylene dioxythiophene: poly styrene sulfonate film adopts spin coating method process calcium titanium ore bed film, at 98 DEG C, annealing can obtain uniform curing photosensitive layer in 40 minutes;
Step 5: continue to adopt spin coating method processing process [6,6]-phenyl-C61-methyl butyrate film on perovskite thin film, rotate 40 seconds under accelerating to the rotating speed of 2000rpm, uniform electron transfer layer can be obtained;
Step 6: continue to adopt spin coating method processing process 4,7-diphenyl-1,10-ferrosin film on electric transmission layer film, rotate 40 seconds under accelerating to the rotating speed of 4000rpm, uniform cathodic modification layer can be obtained;
Step 7: adopt evaporation coating method to process cathode electrode Au on cathodic modification layer.
Embodiment 4
Step 1: an ito glass substrate is provided, column criterionization of going forward side by side is cleaned; By iodate first ammonium, lead chloride, indium iodide in molar ratio 3:0.85:0.15 be dissolved in DMF solution, stir 5 hours, obtain the perovskite DMF solution of 30wt%;
Step 2: will 3,4-ethylene dioxythiophene be gathered: poly styrene sulfonate solution adopts spin coating method processing in substrate transparency electrode, rotates 40 seconds, form uniform anode modification layer under accelerating to the rotating speed of 4500rpm;
Step 3: film is annealed 20 minutes at 95 DEG C in air, forms uniform anode modification layer;
Step 4: at poly-3,4-ethylene dioxythiophene: poly styrene sulfonate film adopts spin coating method process calcium titanium ore bed film, at 98 DEG C, annealing can obtain uniform curing photosensitive layer in 40 minutes;
Step 5: continue to adopt spin coating method processing process [6,6]-phenyl-C61-methyl butyrate film on perovskite thin film, rotate 40 seconds under accelerating to the rotating speed of 2000rpm, uniform electron transfer layer can be obtained;
Step 6: continue to adopt spin coating method processing process 4,7-diphenyl-1,10-ferrosin film on electric transmission layer film, rotate 40 seconds under accelerating to the rotating speed of 4000rpm, uniform cathodic modification layer can be obtained;
Step 7: adopt evaporation coating method to process cathode electrode Au on cathodic modification layer.
Comparative example 1
Step 1: an ito glass substrate is provided, column criterionization of going forward side by side is cleaned; By iodate first ammonium, lead chloride in molar ratio 3:1 be dissolved in DMF solution, stir 5 hours, obtain the perovskite DMF solution of 30wt%;
Step 2: will 3,4-ethylene dioxythiophene be gathered: poly styrene sulfonate solution adopts spin coating method processing in substrate transparency electrode, rotates 40 seconds, form uniform anode modification layer under accelerating to the rotating speed of 4500rpm;
Step 3: film is annealed 30 minutes at 95 DEG C in air, forms uniform anode modification layer;
Step 4: at poly-3,4-ethylene dioxythiophene: poly styrene sulfonate film adopts spin coating method process calcium titanium ore bed film, at 100 DEG C, annealing can obtain uniform curing photosensitive layer in 30 minutes;
Step 5: continue to adopt spin coating method processing process [6,6]-phenyl-C61-methyl butyrate film on perovskite thin film, rotate 40 seconds under accelerating to the rotating speed of 2000rpm, uniform electron transfer layer can be obtained;
Step 6: continue to adopt spin coating method processing process 4,7-diphenyl-1,10-ferrosin film on electric transmission layer film, rotate 40 seconds under accelerating to the rotating speed of 4000rpm, uniform cathodic modification layer can be obtained;
Step 7: adopt evaporation coating method to process cathode electrode Ag on cathodic modification layer.
Comparative example 2
(1) provide an ITO flexible substrates, column criterionization of going forward side by side is cleaned;
(2) by iodate first ammonium and lead chloride and inidum chloride in molar ratio 3:0.85:0.05 be dissolved in DMF solution, stir 5 hours, obtain the perovskite DMF solution of 30wt%;
(3) adopted by PEDOT:PSS solution spin coating method processing in substrate transparency electrode, rotate 40 seconds under accelerating to the rotating speed of 4500rpm, form uniform anode modification layer, anneal 20 minutes for 100 DEG C;
(4) on PEDOT:PSS film, adopt spin coating method to process calcium titanium ore bed film, rotate 40 seconds under accelerating to the rotating speed of 4000rpm, the good photosensitive layer of homogeneously crystallized property can be obtained without the need to annealing in process;
(5) spin coating method processing electron transfer layer PCBM on perovskite thin film, rotates 40 seconds under accelerating to the rotating speed of 2000rpm, obtains uniform electric transmission layer film;
(6) adopt the method for evaporation to prepare cathode electrode Ag, its thickness is 100nm.
The Ca-Ti ore type solar cell properties of the above embodiments and comparative example is as follows:
Short circuit current (V) Open circuit voltage (mA/cm 2) Fill factor, curve factor (%) Energy conversion efficiency (%)
Embodiment 1 0.99 22.64 68 15.31
Embodiment 2 0.96 21.69 75 15.65
Embodiment 3 1.01 21.82 75 16.80
Embodiment 4 1.03 21.30 75 17.05
Comparative example 1 1.07 12.30 64 8.50
Comparative example 2 1.09 13.80 66 9.90
As can be seen from the above table, the energy conversion efficiency that the employing indium iodide of embodiment 4 obtains as the solar cell of perovskite component is the highest, and inidum chloride takes second place.And the energy conversion efficiency having lacked the perovskite solar cell of inidum chloride and indium iodide declines greatly.

Claims (8)

1. a preparation method for the Ca-Ti ore type solar cell of multiple ordered orientation crystallization, is characterized in that, described preparation method comprises the following steps:
Step 1: by iodate first ammonium, lead chloride, inidum chloride or indium iodide in molar ratio 3:0.85:0.05-0.25 be dissolved in DMF solution, stir 5 hours, obtain the perovskite DMF solution of 30wt%;
Step 2: will 3,4-ethylene dioxythiophene be gathered: poly styrene sulfonate solution adopt spin coating, inkjet printing or volume to volume method processing in substrate transparency electrode, form uniform anode modification layer;
Step 3: anneal film at 95 DEG C 10-30 minute in air, forms uniform anode modification layer;
Step 4: at poly-3,4-ethylene dioxythiophene: method processing calcium titanium ore bed film poly styrene sulfonate film adopting spin coating, inkjet printing or volume to volume, anneals at 95-100 DEG C and can obtain uniform curing photosensitive layer in 30-50 minute;
Step 5: continue method processing process [6, the 6]-phenyl-C61-methyl butyrate film adopting spin coating, inkjet printing or volume to volume on perovskite thin film, uniform electron transfer layer can be obtained;
Step 6: continue method processing process 4,7-diphenyl-1, the 10-ferrosin film adopting spin coating, inkjet printing or volume to volume on electric transmission layer film, uniform cathodic modification layer can be obtained;
Step 7: adopt evaporation or inkjet printing methods processing cathode electrode on cathodic modification layer.
2. the preparation method of the Ca-Ti ore type solar cell of a kind of multiple ordered orientation crystallization according to claim 1, it is characterized in that, in described step 1, iodate first ammonium, lead chloride, inidum chloride or indium iodide mol ratio are 3:0.85:0.15.
3. the preparation method of the Ca-Ti ore type solar cell of a kind of multiple ordered orientation crystallization according to claim 1, is characterized in that, is annealed 20 minutes by film in described step 3 at 95 DEG C in air.
4. the preparation method of the Ca-Ti ore type solar cell of a kind of multiple ordered orientation crystallization according to claim 1, is characterized in that, anneals 40 minutes in described step 4 at 98 DEG C.
5. the preparation method of the Ca-Ti ore type solar cell of a kind of multiple ordered orientation crystallization according to claim 1, it is characterized in that, the inidum chloride chosen, the purity of indium iodide are more than 99.9%.
6. the preparation method of the Ca-Ti ore type solar cell of a kind of multiple ordered orientation crystallization according to claim 1, is characterized in that, described substrate is flexible substrates, ito glass, AZO glass or FTO glass.
7. the preparation method of the Ca-Ti ore type solar cell of a kind of multiple ordered orientation crystallization according to claim 1, it is characterized in that, described cathode electrode is Ag, Al or Au, and thickness of electrode is 60-100nm.
8. according to the Ca-Ti ore type solar cell that the preparation method of the Ca-Ti ore type solar cell of the arbitrary described a kind of multiple ordered orientation crystallization of claim 1 to 7 prepares.
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CN111341916A (en) * 2020-03-05 2020-06-26 苏州大学 Indium compound doped perovskite film, preparation method and application thereof
CN111613727A (en) * 2020-07-02 2020-09-01 中国科学技术大学 Negative electrode buffer layer-containing inverse perovskite solar cell and preparation method thereof

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