Disclosure of Invention
In order to solve the above problems, an object of the present invention is to provide a stacked perovskite solar cell and a method for manufacturing the same, which can simplify the structure and the manufacturing process and greatly reduce the cost and energy consumption on the premise of obtaining a high-performance solar cell.
The invention is realized by the following technical scheme:
the invention discloses a laminated perovskite solar cell, which comprises a high-transparency glass layer, a transparent electrode layer, a hole transport layer, a first perovskite active layer, a first electron transport layer, a multifunctional tin oxide layer, a second perovskite active layer, a second electron transport layer and a metal counter electrode layer which are sequentially connected to form the whole solar cell; the thickness of the multifunctional tin oxide layer is 10-50nm, and the diameter of the tin oxide nanoparticles in the multifunctional tin oxide layer is 5-20 nm.
Preferably, the transparent electrode layer is FTO, ITO or AZO.
Preferably, the material of the hole transport layer is Spiro-OMeTAD, PTAA, nickel oxide, cuprous iodide, PEDOT: PSS, polytereene, polythiophene, polysilane, triphenylmethane, triarylamine, hydrazone, pyrazoline, carbazole, or butadiene, and the thickness of the hole transport layer is 100 nm.
Preferably, the material of the first perovskite active layer is FAPBBr3The thickness of the first perovskite active layer is 300-600 nm.
Preferably, the material of the first electron transport layer and the second electron transport layer is PC71BM, the thickness of the first electron transport layer is 200-400 nm.
Preferably, the material of the second perovskite active layer is MAPbI3The thickness of the second perovskite active layer is 500-750 nm.
Preferably, the material of the metal counter electrode layer is gold, silver, aluminum or platinum, and the thickness of the metal counter electrode layer is 80-150 nm.
The invention discloses a preparation method of the laminated perovskite solar cell, which comprises the following steps:
step 1: preparing a hole transport layer on the high-transparency glass layer attached with the transparent electrode layer by adopting a scraper coating method;
step 2: preparing a first perovskite active layer on the hole transport layer;
and step 3: preparing a first electron transport layer on the first perovskite active layer by adopting a scraper coating method;
and 4, step 4: preparing a multifunctional tin oxide layer on the first electron transport layer by adopting atomic deposition, vapor deposition, magnetron sputtering or spin coating;
and 5: preparing a second perovskite active layer on the multifunctional tin oxide layer;
step 6: preparing a second electron transport layer on the second perovskite active layer by adopting a scraper coating method;
and 7: and preparing a metal counter electrode layer on the second electron transmission layer by adopting a thermal evaporation method, a magnetron sputtering method, an atomic deposition method, a laser deposition method or a roll-to-roll method.
Preferably, the spin coating method is adopted in the step 4, and specifically comprises the following steps: taking the suspension of tin oxide nanoparticles with the diameter of 5-20nm as spin coating liquid, and spin-coating the suspension on the substrate for 30-60s at the rotating speed of 3500-5000 rpm.
Preferably, steps 2 and 5 employ spin coating, vapor deposition, magnetron sputtering, or a roll-to-roll method.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention discloses a laminated perovskite solar cell, which takes a narrow-band gap perovskite solar cell as a bottom cell and a wide-band gap perovskite solar cell as a top cell to form a composite laminated cell structure2) A nanomaterial film. Tin oxide has a low conduction band energy level and high carrier mobility, and can effectively extract charges in the perovskite material and conduct the charges to an external circuit. On the other hand, the tin oxide film prepared under the appropriate conditions can also be used as a transparent electrode of a solar cell, the square resistance of the tin oxide film is less than 15 omega, and meanwhile, the light transmittance can reach more than 85 percent. The laminated solar cell constructed on the basis can simplify the structure of the solar cell.
According to the preparation method of the laminated perovskite solar cell disclosed by the invention, the multifunctional tin oxide layer can be prepared under a low temperature condition (less than 200 ℃), and the cost, the energy consumption and the process are greatly reduced and simplified. Other functional layers can also be prepared by adopting a mature process such as a coating method, so that the method is suitable for being popularized and used as a manufacturing process of large-area flexible products, and the manufacturing cost, the energy consumption and the process are greatly reduced and simplified.
Detailed Description
The invention is described in further detail below with reference to the following figures and examples:
referring to fig. 1, the stacked perovskite solar cell of the present invention comprises a high-transparency glass layer 102, a transparent electrode layer 104, a hole transport layer 106, a first perovskite active layer 108, a first electron transport layer 110, a multifunctional tin oxide layer 112, a second perovskite active layer 114, a second electron transport layer 116 and a metal counter electrode layer 118, which are connected in sequence to form an integral solar cell device.
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.
The hole transport layer 106 prepared on the transparent electrode layer 104 is characterized by an organic and inorganic material that is energy level-matched with the perovskite active material, 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, dilution in proportion, wherein the coating speed of a scraper is 10-35mm/s, and is preferably 20 mm/s; the coating temperature is 40-80 ℃, and preferably 60 ℃; the distance between the scraper and the substrate is 50 mu m; after coating, annealing at 80-100 deg.C for 10-20 min, preferably 90 deg.C for 15min in nitrogen. The resulting hole-transporting layer 106 is approximately 100nm thick.
A first perovskite active layer 108 of the structure ABX prepared on the hole transport layer 106nY3-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 FAPBR is used3Usually by spin coatingMethods such as vapor deposition, magnetron sputtering, and the like, or roll-to-roll processes suitable for flexible and large-scale production, i.e., slurry of the active material is formed by slit coating, blade coating, screen printing, gravure printing, inkjet coating, inkjet printing, and 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 room temperature; 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 thickness of the obtained first perovskite active layer is about 300-600 nm.
A first electron transport layer 110 of PC prepared on the first perovskite layer 10871BM, the slurry is a chloroform dispersion of 15-20 g/L. The blade coating speed is 15-25mm/s, preferably 20 mm/s; the coating temperature is room temperature; the distance between the scraper and the substrate is 80-100 mu m; after coating, the coating was naturally dried in nitrogen for 20 minutes. The thickness is about 200-400 nm.
Multifunctional tin oxide (SnO)2) Layer 112: the core part of the invention can be prepared by methods such as atomic deposition, vapor deposition, magnetron sputtering, spin coating and the like. In particular, the layer is prepared by a solution spin coating method, commercial tin oxide nanoparticle (diameter 5-20nm) suspension can be directly used as spin coating liquid, tin oxide layers (10-50nm) with different thicknesses can be prepared on a glass substrate by using spin coating parameters of 3500-5000rpm and 30-60s, and particularly, the multifunctional tin oxide layer 112 with the thickness of about 10-15nm can be obtained by using spin coating parameters of 5000rpm and 60 s.
In multifunctional tin oxide (SnO)2) A second perovskite active layer 114, of structure ABX, prepared on layer 112nY3-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 from 0 to 3), a perovskite battery core layer with a narrow band gap is usually selected, and MAPbI is preferably used3(ii) a The coating is usually formed by spin coating, vapor deposition, magnetron sputtering, and the like, and can also be applied to flexible and large-scale productionThe prepared roll-to-roll process is prepared by forming a slurry of the active material by slit coating, blade coating, screen printing, gravure printing, inkjet coating, inkjet printing, and the like. In particular, in the blade coating method, the solvent is DMF, and the perovskite is prepared into slurry with the mass fraction of 20-30%, preferably 25%; the blade coating speed is 30-60mm/s, preferably 50 mm/s; the coating temperature is room temperature; the distance between the scraper and the substrate is 100 mu m; after coating, annealing at 100-150 ℃ for 20-60 min, preferably 120 ℃ for 40min in nitrogen. The resulting second perovskite active layer 114 has a thickness of about 500-750 nm.
A second electron transport layer 116 made of PC on the second perovskite layer 11471BM, the slurry is a chloroform dispersion of 15-20 g/L. The blade coating speed is 15-25mm/s, preferably 20 mm/s; the coating temperature is room temperature; the distance between the scraper and the substrate is 80-100 mu m; after coating, the coating was naturally dried in nitrogen for 20 minutes. The thickness is about 200-400 nm.
The metal counter electrode layer 118 formed on the second electron transport layer 116 is made of metal such as gold, silver, aluminum, platinum, and the like, and can be prepared by thermal evaporation, magnetron sputtering, atomic deposition, laser deposition, and the like, and in the flexible preparation process, the metal counter electrode layer can also be prepared by using a roll-to-roll process, that is, a slurry of a conductive metal electrode material is formed by slit coating, blade coating, screen printing, gravure printing, inkjet coating, inkjet printing, and the like. In particular, the material used is commercial silver nanowire sol, the solvent is isopropanol, the concentration is 20g/L, the diameter of the silver nanowire is about 100nm, and the length of the silver nanowire is 50-150 μm. The blade coating speed is 20-50mm/s, preferably 40 mm/s; the coating temperature is room temperature; the distance between the scraper and the substrate is 50-100 mu m; after coating, annealing at 80-100 deg.C for 10-20 min, preferably 85 deg.C for 20 min in nitrogen. The thickness is about 80-150 nm.
The preparation process according to the invention is further explained below by means of a specific example:
taking a high-transmittance glass substrate attached with a transparent conductive layer, wherein the area of the high-transmittance glass substrate is 3cm multiplied by 3 cm; preparing PEDOT: PSS aqueous solution, diluting with isopropanol at a ratio of 1:3, and coating on the transparent conductive electrode by knife coating method under the condition that20mm/s, coating temperature 60 ℃, distance between a scraper and a substrate of 50 mu m, annealing for 15min at 90 ℃ under nitrogen atmosphere in a glove box. FAPBBr3Preparing 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; after coating, annealing at 120 ℃ for 30min in nitrogen. Compounding of PC71A chloroform dispersion with BM concentration of 15 g/L. 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 80 mu m; after coating, the coating was naturally dried in nitrogen for 20 minutes. The preparation of the tin oxide layer was carried out on a glass substrate at 5000rpm for 60s using a suspension of tin oxide nanoparticles (diameter 5-20nm) as spin coating liquid directly. MAPbI is added3Preparing a solution with the mass fraction of 25%, wherein DMF is used as a solvent; the coating speed of a scraper is 50 mm/s; the coating temperature is room temperature; the distance between the scraper and the substrate is 100 mu m; after coating, annealing at 120 ℃ for 40min in nitrogen. Compounding of PC71A chloroform dispersion with BM concentration of 15 g/L. 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 80 mu m; after coating, the coating was naturally dried in nitrogen for 20 minutes. Finally, a gold back electrode with the thickness of 100nm is evaporated in a thermal evaporation mode.
The effective area of the obtained laminated cell is 4.0cm2The detection shows that the overall photoelectric conversion efficiency of the battery can reach 10-12% on average, and the highest efficiency can reach 14.6%.
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.