CN112599681A - Perovskite solar cell with improved metal electrode and preparation method thereof - Google Patents
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- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
- H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
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Abstract
The invention discloses a perovskite solar cell with an improved metal electrode and a preparation method thereof, and belongs to the technical field of solar cell devices. Firstly, preparing a transparent electrode layer on a high-transparency glass layer, preparing and forming an electron transport layer on the transparent electrode layer, preparing a perovskite active layer on the electron transport layer, and preparing a hole transport layer on the perovskite active layer to obtain a perovskite battery main body; carrying out patternable batch preparation on a backboard substrate by adopting physical deposition, cutting according to the shape and the circuit of a main body part of the perovskite battery after deposition to obtain a metal electrode layer, and preparing a barrier layer on the metal electrode layer to obtain an electrode main body; and aligning and superposing the perovskite cell main body and the electrode main body, and slowly cooling to room temperature after heat treatment to obtain the perovskite solar cell with the improved metal electrode. On the premise of obtaining the high-performance solar cell, the production efficiency is improved.
Description
Technical Field
The invention belongs to the technical field of solar cell devices, and relates to a perovskite solar cell with an improved metal electrode and a preparation method thereof.
Background
Perovskite solar cells (perovskite solar cells) are solar cells using perovskite type organic metal halide semiconductors as light absorbing materials, and belong to the third generation solar cells, which are also called new concept solar cells. Upon exposure to sunlight, the perovskite layer first absorbs photons to generate electron-hole pairs. These carriers either become free carriers or form excitons due to differences in exciton binding energy of the perovskite material. Furthermore, because these perovskite materials tend to have a lower probability of carrier recombination and higher carrier mobility, the diffusion distance and lifetime of carriers are longer. Then, the non-recombined electrons and holes are respectively collected by an electron transport layer and a hole transport layer, namely the electrons are transported to the equal electron transport layer from the perovskite layer and are finally collected by the ITO; the holes are transported from the perovskite layer to the hole transport layer and finally collected by the metal electrode, and of course, the processes are not always accompanied by some losses of carriers, such as reversible recombination of electrons of the electron transport layer with holes of the perovskite layer, recombination of electrons of the electron transport layer with holes of the hole transport layer (in the case of a non-dense perovskite layer), and recombination of electrons of the perovskite layer with holes of the hole transport layer. These carrier losses should be minimized to improve the overall performance of the cell. Finally, the photocurrent is generated through the electrical circuit connecting the FTO and the metal electrode.
The metal back electrode in the traditional perovskite battery is usually prepared by independently depositing each battery, and the metal back electrode is deposited by using evaporation/sputtering and other methods at the final stage of perovskite battery preparation, so that the production efficiency is low.
Disclosure of Invention
In order to solve the above problems, an object of the present invention is to provide a perovskite solar cell having an improved metal electrode and a method for manufacturing the same, which can improve the production efficiency on the premise of obtaining a high-performance solar cell.
The invention is realized by the following technical scheme:
the invention discloses a preparation method of a perovskite solar cell with an improved metal electrode, which comprises the following steps:
preparing a transparent electrode layer on the high-transparency glass layer, preparing and forming an electron transport layer on the transparent electrode layer, preparing a perovskite active layer on the electron transport layer, and preparing a hole transport layer on the perovskite active layer to obtain a perovskite battery main body;
carrying out patternable batch preparation on a backboard substrate by adopting physical deposition, cutting according to the shape and the circuit of a main body part of the perovskite battery after deposition to obtain a metal electrode layer, and preparing a barrier layer on the metal electrode layer to obtain an electrode main body;
and aligning and superposing the perovskite cell main body and the electrode main body, carrying out heat treatment at 100-150 ℃ for 10-30min, and slowly cooling to room temperature to obtain the perovskite solar cell with the improved metal electrode.
Preferably, the transparent electrode layer is FTO, ITO or AZO.
Preferably, before the electron transport layer is formed on the transparent electrode layer, the surface of the flexible transparent electrode substrate is sequentially subjected to ultrasonic treatment for 15min by using deionized water, acetone and isopropanol, then is cleaned for 10min by using ultraviolet light, and is dried by using nitrogen flow.
Preferably, the electron transport layer is prepared by atomic deposition, vapor deposition, magnetron sputtering or spin coating; the electron transport layer comprises tin oxide or titanium oxide nanoparticles, the diameter of the tin oxide or titanium oxide nanoparticles is 2-10nm, and the thickness of the electron transport layer is 10-40 nm.
Preferably, the perovskite active layer is FAPbI3The thickness of the perovskite active layer is 300-600 nm.
Preferably, the material of the hole transport layer is Spiro-OMeTAD, PTAA, nickel oxide, cuprous iodide, PEDOT: PSS, polytereylenes, polythiophenes, polysilanes, triphenylmethanes, triarylamines, hydrazones, pyrazolines, carbazoles, or butadienes; the thickness of the hole transport layer was 100 nm.
Preferably, the backplane substrate of the metal electrode layer is non-conductive glass or polymer plastic, and the metal electrode is gold, silver, copper or aluminum; the thickness of the metal electrode layer is 60-120 nm.
Preferably, the barrier layer is a reduced graphene oxide layer, and the thickness of the barrier layer is 10-20 nm.
Further preferably, the barrier layer is prepared by a solution spin coating method, specifically: adopting chlorobenzene solvent, preparing reduced graphene oxide with the diameter of 0.2-1.0 mu m and the thickness of less than 5nm into slurry with the concentration of 0.5-2mg/mL, and spin-coating the slurry on a substrate for 40-60s at the rotating speed of 1000-4000 rpm.
The perovskite solar cell with the improved metal electrode prepared by the preparation method disclosed by the invention comprises a high-transmittance glass layer, a transparent electrode layer, an electron transport layer, a perovskite active layer, a hole transport layer, a barrier layer and a metal electrode layer which are sequentially connected to form the whole solar cell.
Compared with the prior art, the invention has the following beneficial technical effects:
according to the preparation method of the perovskite solar cell with the improved metal electrode, disclosed by the invention, the metal back electrode can be prepared in a large area at one time and cut as required to obtain the electrode main body suitable for a single solar cell, the electrode main body and the main part of the perovskite cell main body are respectively produced and then combined with the cell main body in a heat treatment mode, so that the production efficiency is improved. On the basis, the perovskite solar cell with the improved metal electrode is constructed, and on the premise of ensuring good performance, the structure of the solar cell can be simplified, the production efficiency can be improved, and the cost can be reduced.
The perovskite solar cell with the improved metal electrode prepared by the preparation method disclosed by the invention is simple in structure, convenient for batch production and good in application prospect.
Drawings
Fig. 1 is a schematic view of the overall structure of the present invention.
In the figure, 102-high transparent glass layer, 104-transparent electrode layer, 106-electron transport layer, 108-perovskite active layer, 110-hole transport layer, 112-barrier layer, 114-barrier layer.
Detailed Description
The invention is described in further detail below with reference to the following figures and examples:
referring to fig. 1, the perovskite solar cell with the improved metal electrode of the present invention comprises a high-permeability glass layer 102, a transparent electrode layer 104, an electron transport layer 106, a perovskite active layer 108, a hole transport layer 110, a barrier layer 112 and a metal electrode layer 114 which are connected in sequence to form an integral solar cell.
High-transmittance glass layer 102 and transparent electrode layer 104: the product can be used in large-scale products, an FTO (or ITO, AZO and the like) transparent electrode deposited on high-transparency glass is used as a substrate of a device, the area is not limited, and the shape, the area, the thickness and the like of the FTO and other transparent electrodes can be controlled by a process means; before use, the surface of the electrode is sequentially treated by deionized water, acetone and isopropanol for 15 minutes, then cleaned by an ultraviolet light cleaning machine for 10 minutes, and dried by nitrogen flow for later use.
A perovskite active layer 108 prepared on the electron transport layer 106 and having the structure ABXnY3-n(A ═ Cs or RNH3Or mixtures thereof in any proportion, R is a suitable hydrocarbyl group; b ═ Pb or Sn or a mixture thereof in any proportion; x, Y ═ Cl, Br, I; n is a real number of 0 to 3), preferably FAPBI is used3The coating layer is generally formed by spin coating, vapor deposition, magnetron sputtering, or the like, and may be formed by a roll-to-roll process suitable for flexible and large-scale production, that is, a slurry of an active material is formed by slit coating, blade coating, screen printing, gravure printing, inkjet coating, inkjet printing, or the like. In particular, in the blade coating method, DMF is used as a solvent, and the perovskite is prepared into slurry with the mass fraction of 15-30%, preferably 25%; the blade coating speed is 10-40mm/s, preferably 20 mm/s; the coating temperature is roomWarming; the distance between the scraper and the substrate is 50 mu m; after coating, annealing at 100-150 ℃ for 20-40 min, preferably 120 ℃ for 30min in nitrogen. The resulting thickness of the perovskite active layer 108 was about 300-600 nm.
The hole transport layer 110 prepared on the perovskite active layer 108 is characterized by organic and inorganic materials matched with the perovskite active material energy level, such as Spiro-OMeTAD, PTAA, nickel oxide, cuprous iodide, PEDOT: PSS, polyparaphenylenes, polythiophenes, polysilanes, triphenylmethanes, triarylamines, hydrazones, pyrazolines, carbazoles, butadienes, and the like. In particular, the layer was prepared using a knife coating method: the slurry used was commercial PEDOT: PSS (AI 4083) in aqueous solution, using isopropanol, according to a 1:3, proportioning and diluting, wherein the coating speed of a scraper is 10-35mm/s, preferably 25 mm/s; the coating temperature is 50-80 ℃, and preferably 60 ℃; the distance between the scraper and the substrate is 50 mu m; after coating, annealing at 85-100 deg.C for 10-30min, preferably 95 deg.C for 20min in nitrogen. The resulting hole transport layer 110 was about 100nm thick.
The metal electrode layer 114 formed on the back sheet substrate, which is a part of the assembly prepared separately from the main body part of the perovskite battery, can be prepared in a large area and cut, and thus can be prepared in large quantities. The backplane substrate may typically use a non-conductive glass/polymer plastic (e.g., PET) or the like. The metal electrode can be a common metal electrode such as gold/silver/copper/aluminum, and the like, and the comprehensive consideration of cost and performance is combined, in the embodiment, the metal electrode can be prepared by using metal silver and performing patternable preparation by using a physical deposition (evaporation) method and the like, and the thickness can be 60-120nm, and is preferably 100 nm; and cutting the perovskite battery according to the shape of the main body part of the perovskite battery and the circuit design after the deposition is finished.
And (3) combining the electrode main body with the heat treatment of the perovskite battery main body: and aligning and overlapping the perovskite battery main body and the metal electrode, carrying out heat treatment at the temperature of 100-150 ℃ for 10-30min, such as 120 ℃ and 15min, and then slowly cooling to room temperature to obtain the final battery device.
The preparation process according to the invention is further explained below by means of a specific example:
taking a high-transparency glass substrate with an ITO transparent electrode layer attached on the substrate, wherein the area of the high-transparency glass substrate is 3cm multiplied by 3 cm; directly taking commercial tin oxide nanoparticle (diameter is 2-10nm) suspension as spin coating liquid, preparing a tin oxide layer on a substrate at 4200rpm for 60s, and annealing at 180 ℃ for 10 min; to FAPBI3Preparing a solution with the mass fraction of 25%, wherein DMF is used as a solvent; the coating speed of a scraper is 20 mm/s; the coating temperature is room temperature; the distance between the scraper and the substrate is 50 mu m; annealing at 120 deg.C for 30min in nitrogen after coating; preparing PEDOT: PSS aqueous solution is diluted by isopropanol according to the proportion of 1:3, film coating is carried out by adopting a scraper coating mode under the conditions of 25mm/s, the coating temperature of 60 ℃, the distance between a scraper and a substrate of 50 mu m, and annealing is carried out for 20min at 95 ℃ under nitrogen atmosphere in a glove box; thermally evaporating a gold electrode with the thickness of 100nm on a glass backboard substrate, preparing a barrier layer on the gold electrode by adopting a spin-coating method, preparing r-GO (with the diameter of 0.5-2.0 mu m and the thickness of 2-5nm) into 1mg/mL slurry, and taking chlorobenzene as a solvent; preparing the barrier layer on the substrate by using the spin coating parameters of 3000rpm and 60 s; the two parts are annealed in register at 120 ℃ for 15 min.
The effective area of the obtained battery unit is 1.0cm2And through detection, the maximum photoelectric conversion efficiency of the battery can reach 12.9%.
It should be noted that the above description is only one embodiment of the present invention, and all equivalent changes of the system described in the present invention are included in the protection scope of the present invention. Persons skilled in the art to which this invention pertains may substitute similar alternatives for the specific embodiments described, all without departing from the scope of the invention as defined by the claims.
Claims (10)
1. A method of making a perovskite solar cell having an improved metal electrode, comprising:
preparing a transparent electrode layer (104) on a high-transparency glass layer (102), preparing and forming an electron transport layer (106) on the transparent electrode layer (104), preparing a perovskite active layer (108) on the electron transport layer (106), and preparing a hole transport layer (110) on the perovskite active layer (108) to obtain a perovskite battery main body;
carrying out patternable batch preparation on a backboard substrate by adopting physical deposition, cutting according to the shape and the circuit of a main body part of the perovskite battery after the deposition is finished to obtain a metal electrode layer (114), and preparing a barrier layer (112) on the metal electrode layer (114) to obtain an electrode main body;
and aligning and superposing the perovskite cell main body and the electrode main body, carrying out heat treatment at 100-150 ℃ for 10-30min, and slowly cooling to room temperature to obtain the perovskite solar cell with the improved metal electrode.
2. The method for preparing a perovskite solar cell with an improved metal electrode as claimed in claim 1, characterized in that the transparent electrode layer (104) is FTO, ITO or AZO.
3. The preparation method of the perovskite solar cell with the improved metal electrode as claimed in claim 1, wherein before the preparation of the electron transport layer (106) on the transparent electrode layer (104), the surface of the flexible transparent electrode substrate (102) is sequentially subjected to ultrasonic treatment for 15min by using deionized water, acetone and isopropanol, then is cleaned for 10min by using ultraviolet light, and is dried by using nitrogen flow.
4. The method for preparing a perovskite solar cell with an improved metal electrode as claimed in claim 1, characterized in that the electron transport layer (106) is prepared by atomic deposition, vapor deposition, magnetron sputtering or spin coating; the electron transport layer (106) comprises tin oxide or titanium oxide nanoparticles, the diameter of the tin oxide or titanium oxide nanoparticles is 2-10nm, and the thickness of the electron transport layer (106) is 10-40 nm.
5. The method of claim 1, wherein the perovskite active layer (108) is FAPbI3The thickness of the perovskite active layer (108) is 300 to 600 nm.
6. The method for preparing a perovskite solar cell with an improved metal electrode as claimed in claim 1, wherein the material of the hole transport layer (110) is selected from the group consisting of Spiro-OMeTAD, PTAA, Nickel oxide, cuprous iodide, PEDOT: PSS, polytereylenes, polythiophenes, polysilanes, triphenylmethanes, triarylamines, hydrazones, pyrazolines, carbazoles, or butadienes; the thickness of the hole transport layer (110) was 100 nm.
7. The method for preparing a perovskite solar cell with an improved metal electrode as claimed in claim 1, characterized in that the backplane substrate of the metal electrode layer (114) is non-conductive glass or polymer plastic, and the metal electrode is gold, silver, copper or aluminum; the thickness of the metal electrode layer (114) is 60 to 120 nm.
8. The method for preparing the perovskite solar cell with the improved metal electrode as claimed in claim 1, wherein the barrier layer (112) is a reduced graphene oxide layer, and the thickness of the barrier layer (112) is 10-20 nm.
9. The method for preparing a perovskite solar cell with an improved metal electrode as claimed in claim 8, wherein the barrier layer (112) is prepared by a solution spin coating method, specifically: adopting chlorobenzene solvent, preparing reduced graphene oxide with the diameter of 0.2-1.0 mu m and the thickness of less than 5nm into slurry with the concentration of 0.5-2mg/mL, and spin-coating the slurry on a substrate for 40-60s at the rotating speed of 1000-4000 rpm.
10. The perovskite solar cell with the improved metal electrode prepared by the preparation method according to any one of claims 1 to 9, which is characterized by comprising a high-transparency glass layer (102), a transparent electrode layer (104), an electron transport layer (106), a perovskite active layer (108), a hole transport layer (110), a barrier layer (112) and a metal electrode layer (114) which are sequentially connected to form the whole solar cell.
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CN113481485A (en) * | 2021-07-13 | 2021-10-08 | 南方科技大学 | Tin oxide film and preparation method thereof, and solar cell and preparation method thereof |
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