CN115802769A - Perovskite solar cell and preparation method thereof - Google Patents
Perovskite solar cell and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a perovskite solar cell comprising: a substrate; a first electrode layer on one side surface of the substrate; the first carrier transmission layer is positioned on the surface of one side, away from the substrate, of the first electrode layer; the perovskite layer is positioned on the surface of one side, away from the substrate, of the first carrier transport layer; the passivation layer is positioned on the surface of one side, away from the substrate, of the perovskite layer and contains triethanolamine; the second carrier transmission layer is positioned on the surface of one side, facing away from the substrate, of the passivation layer; and the second electrode layer is positioned on the surface of one side, facing away from the substrate, of the second carrier transmission layer. The passivation layer contains the thiol amine, so that the photoelectric conversion efficiency and the structural stability of the perovskite solar cell are improved.
Description
Technical Field
The invention relates to the technical field of perovskite solar cells, in particular to a perovskite solar cell and a preparation method thereof.
Background
In recent years, environmental pollution and energy shortage have become the focus of world attention, and new energy sources represented by nuclear energy, solar energy, wind energy, tidal energy and the like are receiving more and more attention. Among them, solar energy has the highest utilization value due to the characteristics of high reserve, wide distribution, reproducibility, no pollution and the like. Solar cells, as an effective way of utilizing solar energy, have a fundamental principle of directly converting solar radiation energy into electric energy using the photovoltaic effect. The Perovskite Solar Cell (PSC) is a novel solar cell, has the remarkable advantages of low manufacturing cost, high photoelectric conversion efficiency and the like, the photoelectric conversion efficiency is improved from 3.8% to more than 25% in only ten years, and the development is rapid.
As the light absorbing layer of the perovskite solar cell, the quality of the perovskite layer directly affects the photoelectric conversion efficiency of the perovskite solar cell. However, the surface of the perovskite layer prepared by the prior art has a lot of defects, and the defects can capture photon-generated carriers to cause carrier loss, so that the photoelectric conversion efficiency of the perovskite solar cell is finally reduced.
Disclosure of Invention
Therefore, the technical problem to be solved by the present invention is how to improve the photoelectric conversion efficiency of a perovskite solar cell, thereby providing a perovskite solar cell and a preparation method thereof.
The present invention provides a perovskite solar cell comprising: a substrate; a first electrode layer on one side surface of the substrate; the first carrier transmission layer is positioned on one side surface of the first electrode layer, which is far away from the substrate; a perovskite layer located on a surface of the first carrier transport layer on a side facing away from the substrate; the passivation layer is positioned on the surface of one side, away from the substrate, of the perovskite layer and contains triethanolamine; the second carrier transmission layer is positioned on the surface of one side, away from the substrate, of the passivation layer; and the second electrode layer is positioned on the surface of one side, facing away from the substrate, of the second carrier transmission layer.
Optionally, the passivation layer contains dithiolamine.
Optionally, the material of the passivation layer is a halide salt containing dithiolamine.
Optionally, the material of the passivation layer comprises at least one of dithioamines such as o-phenylenedithiol amine hydrochloride, o-phenylenedithiol amine hydroiodide, 1, 5-pentanedithiol amine hydrochloride, 1, 5-pentanedithiol amine hydroiodide, 1, 2-ethanedithiol amine hydrochloride, benzene-1, 4-dithioamine hydroiodide, biphenyl-4, 4 '-dithioamine hydrochloride, biphenyl-4, 4' -dithioamine hydroiodide, 2, 3-butanedithioamine hydrochloride, 2, 3-butanedithioamine hydroiodide, 1, 8-octanedithiol amine hydrochloride, 1, 8-octanedithiol amine hydroiodide, 1, 9-nonanedithiol amine hydrochloride, 1, 9-nonanedithiol amine hydroiodide and the like.
Optionally, the thickness of the passivation layer is 2nm to 60nm.
Optionally, the thickness of the passivation layer is 5nm to 25nm.
Optionally, the perovskite layer material contains monovalent cations, and the monovalent cations comprise a methylamine group and/or a formamidine group.
Optionally, the substrate includes glass, a flexible substrate, a heterojunction cell, a crystalline silicon cell, or a thin film solar cell.
The invention also provides a preparation method of the perovskite solar cell, which comprises the following steps: providing a substrate; forming a first electrode layer on one side surface of the substrate; forming a first carrier transmission layer on the surface of one side, away from the substrate, of the first electrode layer; forming a perovskite layer on the surface of one side, away from the substrate, of the first carrier transport layer; forming a passivation layer on the surface of one side, away from the substrate, of the perovskite layer, wherein the passivation layer contains triethanolamine; forming a second carrier transmission layer on the surface of one side, away from the substrate, of the passivation layer; and forming a second electrode layer on the surface of one side, which is far away from the substrate, of the second carrier transmission layer.
Optionally, the step of forming a passivation layer on a surface of the perovskite layer facing away from the substrate includes: preparing a passivation solution, wherein the solute of the passivation solution contains triethanolamine; forming a passivation liquid film on the surface of the perovskite layer, which is far away from the first carrier transmission layer, by using the passivation solution; and annealing the passivation liquid film.
Optionally, the annealing temperature is 80-150 ℃, and the annealing time is 8-18 min.
Optionally, in the passivation solution, the concentration of the solute is 0.08mg/ml to 0.5mg/ml, and the solvent includes at least one of methanol and isopropanol.
Optionally, the process of forming the passivation liquid film on the surface of the perovskite layer away from the first carrier transport layer includes a spin coating process, a blade coating process, a slit coating process, or a spray coating process.
Optionally, the process parameters for forming the passivation liquid film by using a spin coating process include: the rotating speed is 3000rpm-6000rpm, and the rotating time is 20s-60s.
Optionally, the process of forming the passivation layer on the surface of the perovskite layer on the side away from the substrate is a vacuum evaporation process, and the deposit to be deposited contains triethanolamine.
Optionally, the deposition rate of the passivation layer is
The technical scheme of the invention has the following advantages:
1. in the perovskite solar cell provided by the invention, the passivation layer positioned between the perovskite layer and the second carrier transmission layer contains the thioalkanolamine, and the sulfur element in the thioalkanolamine and the metal cations which are not coordinated on the surface of the perovskite layer have a chelating effect, so that the surface defects of the perovskite layer can be passivated, the loss of photo-generated carriers can be reduced, and the photoelectric conversion efficiency of the perovskite solar cell can be improved; meanwhile, the sulfur element in the thioalkanolamine is used as a hydrophobic element, so that external moisture can be prevented from contacting with the perovskite layer, the perovskite layer is prevented from reacting with water to be decomposed, and the structural stability of the perovskite solar cell is improved. In addition, the amino group in the thioamine can form a hydrogen bond with halogen ions on the surface of the perovskite layer, so that the surface defects of the perovskite layer can be passivated to improve the photoelectric conversion efficiency of the perovskite solar cell, and the structural stability of the perovskite solar cell can be improved.
2. In the perovskite solar cell provided by the invention, the passivation layer contains the dithiolamine, so that the surface defects of the perovskite layer can be effectively passivated, and the photoelectric conversion efficiency and the structural stability of the perovskite solar cell are effectively improved.
3. According to the perovskite solar cell provided by the invention, the material of the perovskite layer contains univalent cations, the univalent cations comprise a methylamine group and/or a formamidine group, and a sulfur element in the thioalkanolamine can form a hydrogen bond with a hydrogen element in a nitrogen hydrogen bond in the univalent cations, so that the structural stability of the perovskite solar cell can be improved.
4. According to the preparation method of the perovskite solar cell, the passivation layer is formed between the perovskite layer and the second carrier transmission layer and contains the triethanolamine, so that the photoelectric conversion efficiency and the structural stability of the perovskite solar cell are improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a schematic structural diagram of a perovskite solar cell provided in an embodiment of the invention;
FIG. 2 is a flow chart of a perovskite solar cell fabrication process provided by an embodiment of the invention;
description of reference numerals:
1. a substrate; 2. a first electrode layer; 3. a first carrier transport layer; 4. a perovskite layer; 5. a passivation layer; 6. a second carrier transport layer; 7. a second electrode layer.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, the terms "upper", "lower", "inner", "outer", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience in describing the present invention and simplifying the description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention. The terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
Unless otherwise specifically stated, various starting materials, reagents, instruments and equipment used in the present invention are commercially available or prepared by existing methods.
Referring to fig. 1, the present embodiment provides a perovskite solar cell, including:
a substrate 1;
a first electrode layer 2 on one side surface of the substrate 1;
a first carrier transmission layer 3 positioned on the surface of one side of the first electrode layer 2, which is far away from the substrate 1;
a perovskite layer 4 located on a surface of the first carrier transport layer 3 on a side facing away from the substrate 1;
a passivation layer 5 located on a surface of the perovskite layer 4 facing away from the substrate 1, wherein the passivation layer 5 contains a thiol amine;
a second carrier transport layer 6 located on a surface of the passivation layer 5 on a side facing away from the substrate 1;
and the second electrode layer 7 is positioned on one side surface of the second carrier transport layer 6, which faces away from the substrate 1.
In the perovskite solar cell, the passivation layer 5 positioned between the perovskite layer 4 and the second carrier transmission layer 6 contains thioalkanolamine, and the sulfur element in the thioalkanolamine and metal cations which are not coordinated on the surface of the perovskite layer 4 have a chelating effect, so that the surface defects of the perovskite layer 4 can be passivated, the loss of photo-generated carriers is reduced, and the photoelectric conversion efficiency of the perovskite solar cell can be improved; meanwhile, the sulfur element in the thioalkanolamine is used as a hydrophobic element, so that external moisture can be prevented from contacting the perovskite layer 4, the perovskite layer 4 is prevented from reacting with water to be decomposed, and the structural stability of the perovskite solar cell is improved. In addition, the amino group in the thiol amine can form a hydrogen bond with the halogen ion on the surface of the perovskite layer 4, so that the surface defect of the perovskite layer 4 can be passivated to improve the photoelectric conversion efficiency of the perovskite solar cell, and the structural stability of the perovskite solar cell can be improved.
In this embodiment, the general structural formula of the material of the perovskite layer 4 is ABX 3 A is a monovalent cation, B is a divalent cation, and X is a halogen anion; wherein A contains a methylamino group (MA) + ) And/or formamidine groups (FA) + ) Optionally cesium ions (Cs) + ) Etc., B includes but is not limited to Pb 2+ 、Sn 2+ . The sulfur element in the thioalkanolamine can form a hydrogen bond with the hydrogen element in the nitrogen hydrogen bond in the monovalent cation, so that the structural stability of the perovskite solar cell can be improved.
As a preferred embodiment, the passivation layer 5 contains dithiolamine, which can effectively passivate surface defects of the perovskite layer 4, and effectively improve the photoelectric conversion efficiency and structural stability of the perovskite solar cell. Specifically, the passivation layer 5 is made of a halide salt containing dithiolamine; the material of the passivation layer 5 includes at least one of dithioamines such as o-phenylenedithiol amine hydrochloride, o-phenylenedithiol amine hydroiodide, 1, 5-pentanedithiol amine hydrochloride, 1, 5-pentanedithiol amine hydroiodide, 1, 2-ethanedithiol amine hydrochloride, benzene-1, 4-dithioamine hydroiodide, biphenyl-4, 4 '-dithioamine hydrochloride, biphenyl-4, 4' -dithioamine hydroiodide, 2, 3-butanedithioamine hydrochloride, 2, 3-butanedithioamine hydroiodide, 1, 8-octanedithiol amine hydrochloride, 1, 8-octanedithiol amine hydroiodide, 1, 9-nonanedithiol amine hydrochloride, and 1, 9-nonanedithiol amine hydroiodide.
Further, the thickness of the passivation layer 5 is 2nm-60nm; illustratively, the thickness of the passivation layer 5 may be 2nm, 3nm, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 53nm, 57nm, or 60nm. Preferably, the thickness of the passivation layer 5 is 5nm to 25nm.
In the present embodiment, the substrate 1 includes, but is not limited to, glass, a flexible substrate, a heterojunction cell, a crystalline silicon cell, or a thin film solar cell; flexible substrates include, but are not limited to, polyethylene naphthalate (PEN), polyethylene terephthalate (PET); the thin film solar cell includes but is not limited to copper indium gallium selenide thin film solar cell, cadmium telluride thin film solar cell, gallium arsenide thin film solar cell, perovskite solar cell; crystalline silicon cells include, but are not limited to, N-type single crystal passivated contact cells (TopCon cells). When the substrate 1 is made of glass or a flexible substrate, the finally prepared battery is a single-junction perovskite battery; when the substrate 1 adopts a heterojunction cell, a crystalline silicon cell or a thin-film solar cell, the finally prepared cell is a laminated cell.
The material of the first electrode layer 2 includes, but is not limited to, fluorine-doped tin oxide (FTO) or Indium Tin Oxide (ITO).
One of the first carrier transport layer 3 and the second carrier transport layer 6 is a hole transport layer, and the other is an electron transport layer; when the first carrier transport layer 3 is a hole transport layer and the second carrier transport layer 6 is an electron transport layer, the perovskite solar cell is a trans-perovskite solar cell; when the first carrier transport layer 3 is an electron transport layer and the second carrier transport layer 6 is a hole transport layer, the perovskite solar cell is a formal perovskite solar cell.
Hole transport layers include, but are not limited to, poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine](PTAA), 2', 7' -tetrakis [ N, N-di (4-methoxyphenyl) amino]-9,9' -spirobifluorene (Spiro-OMeTAD), poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT: PSS), nickel oxide (NiO) x ) Molybdenum oxide (MoO) x ) Tungsten oxide (WO) x ) At least one of materials such as cuprous thiocyanate (CuSCN) and cuprous iodide (CuI), and the thickness of the hole transport layer is 5nm-40nm; illustratively, the hole transport layer can have a thickness of 5nm, 10nm,15nm, 20nm, 25nm, 30nm, 35nm or 40nm.
Electron transport layers include, but are not limited to, titanium dioxide (TiO) 2 ) Tin dioxide (SnO) 2 ) Zinc oxide (ZnO), fullerene derivatives (e.g. PCBM, C) 60 ) At least one of (1), the thickness of the electron transport layer is 5nm-40nm; illustratively, the electron transport layer can have a thickness of 5nm, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, or 40nm.
The thickness of the perovskite layer 4 is 200nm to 1000nm. Illustratively, the thickness of the perovskite layer 4 may be 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, or 1000nm.
The material of the second electrode layer 7 includes but is not limited to gold, silver, aluminum, the thickness of the second electrode layer 7 is 100nm-150nm; illustratively, the thickness of the second electrode layer 7 may be 100nm, 110nm, 120nm, 130nm, 140nm, or 150nm.
Referring to fig. 2, this embodiment further provides a method for manufacturing the perovskite solar cell, including the following steps:
step S1, providing a substrate 1;
step S2, forming a first electrode layer 2 on one side surface of the substrate 1;
s3, forming a first carrier transmission layer 3 on the surface of one side, away from the substrate 1, of the first electrode layer 2;
s4, forming a perovskite layer 4 on the surface of one side, away from the substrate 1, of the first carrier transport layer 3;
s5, forming a passivation layer 5 on the surface of one side, away from the substrate 1, of the perovskite layer 4, wherein the passivation layer 5 contains triethanolamine;
s6, forming a second carrier transmission layer 6 on the surface of one side, away from the substrate 1, of the passivation layer 5;
and S7, forming a second electrode layer 7 on the surface of the second carrier transmission layer 6, which is far away from the substrate 1.
In step S2, a process of forming the first electrode layer 2 on one side surface of the substrate 1 includes, but is not limited to, a magnetic sputtering process or a chemical vapor deposition process, and the specific process may be selected according to the material of the first electrode layer 2. It should be understood that when the substrate 1 is made of glass or PEN, and the material of the first electrode layer 2 is FTO or ITO, commercially available FTO conductive glass, ITO conductive glass, PEN/ITO can be directly used.
In step S3, a method of forming the first carrier transport layer 3 includes, but is not limited to, a spin coating method, a vacuum evaporation method, a magnetron sputtering method. The specific method may be selected depending on the material of the first carrier transport layer 3 and the like.
In step S4, the process of forming the perovskite layer 4 includes, but is not limited to, a vacuum evaporation process, a spin coating process, and a slit coating process. Spin coating processes include two-step and one-step processes (also known as antisolvent processes).
In step S5, the step of forming a passivation layer 5 on a surface of the perovskite layer 4 on a side facing away from the substrate 1 includes:
s51, preparing a passivation solution, wherein a solute of the passivation solution contains triethanolamine; specifically, in the passivation solution, the concentration of the solute is 0.08mg/ml-0.5mg/ml, and the solvent comprises at least one of methanol and isopropanol; in an exemplary response, the solute may be at a concentration of 0.08mg/ml, 0.1mg/ml, 0.15mg/ml, 0.2mg/ml, 0.25mg/ml, 0.3mg/ml, 0.35mg/ml, 0.4mg/ml, 0.45mg/ml, or 0.5mg/ml.
Step S52, forming a passivation liquid film on the surface of the perovskite layer 4, which is far away from the first carrier transmission layer 3, by using the passivation solution; specifically, the process of forming the passivation liquid film on the surface of the perovskite layer 4 away from the first carrier transport layer 3 includes a spin coating process, a blade coating process, a slit coating process or a spraying process. Wherein, the technological parameters for forming the passivation liquid film by adopting the spin coating process comprise: the rotating speed is 3000rpm-6000rpm, and the rotating time is 20s-60s; illustratively, the rotation speed is 3000rpm, 3500rpm, 4000rpm, 4500rpm, 5000rpm, 5500rpm or 6000rpm, and the rotation time is 20s, 30s, 40s, 50s or 60s.
And S53, annealing the passivation liquid film. Specifically, the annealing temperature is 80-150 ℃, and the annealing time is 8-18 min; illustratively, the annealing temperature can be 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃ or 150 ℃, and the annealing time can be 8min, 10min, 12min, 14min, 16min or 18min. The higher the annealing temperature, the shorter the annealing time.
In step S5, a vacuum evaporation process may also be used to form the passivation layer 5 on a surface of the perovskite layer 4 facing away from the substrate 1, where the deposit to be formed contains thiol amine, and the deposition rate of the passivation layer 5 is
Illustratively, the deposition rate of the passivation layer 5 may be
Or
It is to be understood that the method of forming the passivation layer 5 includes, but is not limited to, the above method.
In step S6, the method of forming the second carrier transport layer 6 includes, but is not limited to, spin coating, vacuum evaporation, and magnetron sputtering. The preparation method may be selected depending on the material of the second carrier transport layer 6 and the like.
In step S7, a method of forming the second electrode layer 7 includes, but is not limited to, a vacuum evaporation method.
The following specific examples are provided to clearly and completely describe the technical scheme of the invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment provides a preparation method of a perovskite solar cell, which comprises the following steps:
providing FTO conductive glass, forming an electron transport layer on the surface of the FTO layer of the FTO conductive glass by adopting a spin-coating method, wherein the electron transport layer is made of TiO 2 The thickness is 10nm;
forming a perovskite layer on the surface of the electron transport layer by adopting a spin coating method, and the method specifically comprises the following steps: preparing a perovskite precursor solution, wherein the perovskite precursor solution contains 1.125mol/L of FAI (amiodamidine) and 1.2375mol/L of PbI 2 0.225mol/L MABr (bromomethylamine), 0.225mol/L PbBr 2 The solvent is a DMF (N, N-dimethylformamide)/DMSO (dimethyl sulfoxide) mixed solvent, and the volume ratio of the DMF to the DMSO is 4; dropwise adding the perovskite precursor solution on the surface of an electron transport layer, rotating at 4000rpm for 30s, and dropwise adding 0.3ml of chlorobenzene in the 20 th to 25 th s of rotation; annealing at 150 ℃ for 10min after the spin coating is finished to obtain a perovskite layer with the thickness of 430nm;
forming a passivation layer on the surface of the perovskite layer, and the specific steps comprise: preparing a passivation solution, wherein the solute of the passivation solution is o-phenylenedithiol amine hydrochloride, the solvent is isopropanol, and the concentration of the solute is 0.08mg/ml; dropwise adding the passivation solution on the surface of the perovskite layer, and rotating at 4000rpm for 30s to obtain a passivation liquid film; annealing the passivation liquid film at 80 ℃ for 18min to obtain a passivation layer with the thickness of 5nm;
forming a hole transport layer on the surface of the passivation layer by adopting a spin-coating method, wherein the hole transport layer is made of CuSCN and has the thickness of 15nm;
and forming a second electrode layer on the surface of the hole transport layer by adopting a vacuum evaporation process, wherein the second electrode layer is made of silver and has the thickness of 100nm, so as to obtain the perovskite solar cell.
The prepared perovskite solar cell is subjected to photoelectric conversion efficiency test, the initial efficiency is 20.91%, the open-circuit voltage is 1.15V, and the short-circuit current density is 23.12mA/cm 2 The fill factor is 78.62%; the perovskite solar cell prepared maintains 94% of the initial efficiency after operating for 2700h under the conditions of 85 ℃ and 85% RH.
Example 2
The embodiment provides a preparation method of a perovskite solar cell, which comprises the following steps:
providing ITO conductive glass, forming a hole transport layer on the surface of the ITO layer of the ITO conductive glass by adopting a spin coating method, wherein the hole transport layer is made of NiO x The thickness of the hole transport layer is 10nm;
forming a perovskite layer on the surface of the hole transport layer by adopting a spin coating method, and the method specifically comprises the following steps: preparing perovskite precursor solution, wherein each 1mL of perovskite precursor solution contains 36.4mg CsI, 216.7mg FAI (iodoformamidine) and 700mg PbI 2 The solvent is a DMF (N, N-dimethylformamide)/DMSO (dimethyl sulfoxide) mixed solvent, and the volume ratio of the DMF to the DMSO is 4; dropwise adding the perovskite precursor solution on the surface of the hole transport layer, rotating at 4000rpm for 40s, and dropwise adding 0.25ml of chlorobenzene in the 25 th to 30 th rotating s; annealing at 130 ℃ for 15min after the spin coating is finished to obtain a perovskite layer, wherein the thickness of the perovskite layer is 400nm;
forming a passivation layer on the surface of the perovskite layer, and the specific steps comprise: preparing a passivation solution, wherein the solute of the passivation solution is 1, 2-ethanedithiol amine hydrochloride, the solvent is isopropanol, and the concentration of the solute is 0.1mg/ml; dropwise adding the passivation solution on the surface of the perovskite layer, and rotating at 4000rpm for 30s to obtain a passivation liquid film; annealing the passivation liquid film at 90 ℃ for 16min to obtain a passivation layer with the thickness of 8 nm;
and sequentially depositing a PCBM layer with the thickness of 20nm, a BCP layer with the thickness of 10nm and a second electrode layer with the thickness of 120nm on the surface of the passivation layer by adopting a vacuum evaporation process, wherein the second electrode layer is made of silver, so that the perovskite solar cell is obtained.
The prepared perovskite solar cell is subjected to photoelectric conversion efficiency test, the initial efficiency is 21.22%, the open-circuit voltage is 1.18V, and the short-circuit current density is 23.26mA/cm 2 Fill factor 77.33%; the perovskite solar cell prepared keeps 95% of the initial efficiency after being operated for 2000 hours under the conditions of 85 ℃ and 85% RH.
Example 3
The embodiment provides a preparation method of a perovskite solar cell, which comprises the following steps:
providing ITO conductive glass, forming a hole transport layer on the surface of the ITO layer of the ITO conductive glass by adopting a spin coating method, wherein the hole transport layer is made of NiO x The thickness of the hole transport layer is 10nm;
forming a perovskite layer on the surface of the hole transport layer by adopting a spin coating method, and the method specifically comprises the following steps: preparing perovskite precursor solution, wherein each 1mL of perovskite precursor solution contains 159mg of MAI (iodomethylamine) and 461mg of PbI 2 The solvent is a DMF (N, N-dimethylformamide)/DMSO (dimethyl sulfoxide) mixed solvent, and the volume ratio of the DMF to the DMSO is 4; dropwise adding the perovskite precursor solution on the surface of the hole transport layer, rotating at 4000rpm for 45s, and dropwise adding 0.2ml of chlorobenzene in the 30s-35s of rotation; annealing at 150 ℃ for 25min after the spin coating is finished to obtain a perovskite layer, wherein the thickness of the perovskite layer is 410nm;
forming a passivation layer on the surface of the perovskite layer, and the specific steps comprise: preparing a passivation solution, wherein the solute of the passivation solution is 2, 3-butanedithiol amine hydroiodide, the solvent is isopropanol, and the concentration of the solute is 0.15mg/ml; dropwise adding the passivation solution on the surface of the perovskite layer, and rotating at 4000rpm for 30s to obtain a passivation liquid film; annealing the passivation liquid film at 100 ℃ for 10min to obtain a passivation layer with the thickness of 10nm;
sequentially depositing C with the thickness of 30nm on the surface of the passivation layer by adopting a vacuum evaporation process 60 The perovskite solar cell comprises a layer, a BCP layer with the thickness of 10nm and a second electrode layer with the thickness of 120nm, wherein the second electrode layer is made of silver, and the perovskite solar cell is obtained.
Carrying out photoelectric conversion efficiency test on the prepared perovskite solar cell, wherein the initial efficiency is 17.3%; the perovskite solar cell prepared keeps 93% of the initial efficiency after running for 2500 hours under the conditions of 85 ℃ and 85% RH.
Example 4
The embodiment provides a preparation method of a perovskite solar cell, which comprises the following steps:
providing a heterojunction battery, and forming a first electrode layer on the surface of an electrode of the heterojunction battery by adopting a Physical Vapor Deposition (PVD) process, wherein the first electrode layer is made of ITO (indium tin oxide) and has the thickness of 100nm;
forming a hole transport layer on the surface of the first electrode layer by adopting a spin coating method, wherein the hole transport layer is made of [4- (3, 6-dimethyl-9H-carbazole-9-yl) butyl ] phosphonic acid (Me-4 PACZ) and has the thickness of 12nm;
forming a perovskite layer on the surface of the hole transport layer by adopting a spin-coating method, and specifically comprising the following steps: preparing perovskite precursor solution, wherein each 1mL of perovskite precursor solution contains 37.1mg of FAI (iodoformamidine), 172mg of MAI (iodomethylamine), and 581mg of PbI 2 And 39mg of PbCl 2 The solvent is a mixed solvent of GBL (gamma-butyrolactone)/DMSO (dimethyl sulfoxide), and the volume ratio of GBL to DMSO is 7; dripping the perovskite precursor solution on the surface of the hole transport layer, rotating at 4000rpm for 45s, and dripping 0.3ml of chlorobenzene in the 30s-35s of rotation; annealing at 150 ℃ for 30min after the spin coating is finished to obtain a perovskite layer, wherein the thickness of the perovskite layer is 420nm;
forming a passivation layer on the surface of the perovskite layer, and the specific steps comprise: preparing a passivation solution, wherein the solute of the passivation solution is 1, 9-nonane dithiolamine hydrochloride, the solvent is isopropanol, and the concentration of the solute is 0.2mg/ml; dropwise adding the passivation solution on the surface of the perovskite layer, and rotating at 4000rpm for 40s to obtain a passivation liquid film; annealing the passivation liquid film at 110 ℃ for 10min to obtain a passivation layer with the thickness of 14 nm;
and sequentially depositing a PCBM layer with the thickness of 20nm, a BCP layer with the thickness of 10nm and a second electrode layer with the thickness of 120nm on the surface of the passivation layer by adopting a vacuum evaporation process, wherein the second electrode layer is made of silver, so that the perovskite/heterojunction laminated cell is obtained.
Carrying out a photoelectric conversion efficiency test on the prepared perovskite/heterojunction laminated cell, wherein the initial efficiency is 26.7%; the perovskite/heterojunction laminated cell prepared keeps 96% of the initial efficiency after being operated for 3000 hours under the conditions of 85 ℃ and 85% RH.
Example 5
This example provides a method for fabricating a perovskite solar cell, which is different from the method for fabricating a perovskite solar cell provided in example 1 in that: the concentration of solute in the passivation solution is 0.5mg/ml; dropwise adding a passivation solution on the surface of the perovskite layer, and rotating at 6000rpm for 30s to obtain a passivation liquid film; and annealing the passivation liquid film at 150 ℃ for 8min to obtain a passivation layer with the thickness of 25nm.
The prepared perovskite solar cell is subjected to photoelectric conversion efficiency test, and the initial efficiency is 21.2 percentThe open-circuit voltage was 1.08V and the short-circuit current density was 23.51mA/cm 2 The filling factor is 81%; the perovskite solar cell prepared maintains 95% of the initial efficiency after being operated for 2700 hours under the conditions of 85 ℃ and RH 85%.
Comparative example 1
The present comparative example provides a method of manufacturing a perovskite solar cell, which differs from the method of manufacturing the perovskite solar cell provided in example 1 in that: in this comparative example, after the perovskite layer was formed, the passivation layer was not formed, and the hole transport layer was directly formed.
The prepared perovskite solar cell is subjected to photoelectric conversion efficiency test, the initial efficiency is 16.53%, the open-circuit voltage is 1.06V, and the short-circuit current density is 21.2mA/cm 2 Fill factor is 74%; the perovskite solar cell prepared maintained 76% of the initial efficiency after operating at 85 ℃ and 85% RH for 2700 h.
Comparative example 2
This comparative example provides a method of fabricating a perovskite solar cell, which differs from the method of fabricating a perovskite solar cell provided in example 2 in that: this comparative example formed the PCBM layer directly after the formation of the perovskite layer without forming the passivation layer.
The prepared perovskite solar cell is subjected to photoelectric conversion efficiency test, the initial efficiency is 17.18%, the open-circuit voltage is 1.1V, and the short-circuit current density is 20.9mA/cm 2 The fill factor is 74%; the perovskite solar cell prepared maintains 82% of the initial efficiency after operating at 85 ℃ and 85% RH for 2700 h.
Comparative example 3
The present comparative example provides a method of manufacturing a perovskite solar cell, which differs from the method of manufacturing a perovskite solar cell provided in example 3 in that: this comparative example directly formed C without forming a passivation layer after forming a perovskite layer 60 And (3) a layer.
Carrying out a photoelectric conversion efficiency test on the prepared perovskite/copper indium gallium selenide laminated cell, wherein the initial efficiency is 13.43%; the perovskite solar cell prepared maintained 76% of the initial efficiency after operating at 85 ℃ and 85% RH for 2700 h.
Comparative example 4
This comparative example provides a method of fabricating a perovskite solar cell, which differs from the method of fabricating a perovskite solar cell provided in example 4 in that: this comparative example formed the PCBM layer directly without forming the passivation layer after the formation of the perovskite layer.
Carrying out a photoelectric conversion efficiency test on the prepared perovskite/heterojunction laminated cell, wherein the initial efficiency is 20%; the perovskite solar cell prepared maintains 86% of the initial efficiency after being operated for 2700 hours under the conditions of 85 ℃ and 85% RH.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should it be exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. A perovskite solar cell, comprising:
a substrate;
a first electrode layer on one side surface of the substrate;
the first carrier transmission layer is positioned on the surface of one side, facing away from the substrate, of the first electrode layer;
a perovskite layer located on a surface of the first carrier transport layer on a side facing away from the substrate;
the passivation layer is positioned on the surface of one side, away from the substrate, of the perovskite layer and contains triethanolamine;
the second carrier transmission layer is positioned on the surface of one side, facing away from the substrate, of the passivation layer;
and the second electrode layer is positioned on the surface of one side, facing away from the substrate, of the second carrier transmission layer.
2. The perovskite solar cell as claimed in claim 1, wherein the passivation layer comprises a bisthioamine;
preferably, the material of the passivation layer is a halide salt containing dithiolamine;
preferably, the material of the passivation layer includes at least one of dithioamines such as o-phenylenedithiol amine hydrochloride, o-phenylenedithiol amine hydroiodide, 1, 5-pentanedithiol amine hydrochloride, 1, 5-pentanedithiol amine hydroiodide, 1, 2-ethanedithiol amine hydrochloride, 1, 2-ethanedithiol amine hydroiodide, benzene-1, 4-dithioamine hydrochloride, benzene-1, 4-dithioamine hydroiodide, biphenyl-4, 4 '-dithioamine hydrochloride, biphenyl-4, 4' -dithioamine hydroiodide, 2, 3-butanedithioamine hydrochloride, 2, 3-butanedithioamine hydroiodide, 1, 8-octanedithiol amine hydrochloride, 1, 8-octanedithiol amine hydroiodide, 1, 9-nonanedithiol amine hydrochloride, and 1, 9-nonanedithiol amine hydroiodide.
3. The perovskite solar cell according to claim 1 or 2, wherein the thickness of the passivation layer is between 2nm and 60nm;
preferably, the thickness of the passivation layer is 5nm-25nm.
4. The perovskite solar cell according to claim 1 or 2, characterized in that the material of the perovskite layer contains monovalent cations comprising a methylamine group and/or a formamidine group.
5. The perovskite solar cell of claim 1, wherein the substrate comprises a glass, a flexible substrate, a heterojunction cell, a crystalline silicon cell, or a thin film solar cell.
6. A method of fabricating a perovskite solar cell, comprising:
providing a substrate;
forming a first electrode layer on one side surface of the substrate;
forming a first carrier transmission layer on the surface of one side, away from the substrate, of the first electrode layer;
forming a perovskite layer on the surface of one side, away from the substrate, of the first carrier transport layer;
forming a passivation layer on the surface of the perovskite layer, which faces away from the substrate, wherein the passivation layer contains triethanolamine;
forming a second carrier transmission layer on the surface of one side, away from the substrate, of the passivation layer;
and forming a second electrode layer on the surface of one side, which is far away from the substrate, of the second carrier transmission layer.
7. The method of manufacturing a perovskite solar cell as claimed in claim 6, wherein the step of forming a passivation layer on the surface of the perovskite layer on the side facing away from the substrate comprises:
preparing a passivation solution, wherein the solute of the passivation solution contains triethanolamine;
forming a passivation liquid film on the surface of the perovskite layer, which is far away from the first carrier transmission layer, by using the passivation solution;
annealing the passivation liquid film;
preferably, the annealing temperature is 80-150 ℃, and the annealing time is 8-18 min.
8. The method of fabricating a perovskite solar cell as claimed in claim 7, wherein the concentration of the solute in the passivating solution is between 0.08mg/ml and 0.5mg/ml and the solvent comprises at least one of methanol and isopropanol.
9. The method for producing a perovskite solar cell according to claim 7, wherein the process of forming the passivation liquid film on the surface of the perovskite layer facing away from the first carrier transport layer comprises a spin coating process, a blade coating process, a slit coating process, or a spray coating process;
preferably, the process parameters for forming the passivation liquid film by using a spin coating process include: the rotating speed is 3000rpm-6000rpm, and the rotating time is 20s-60s.
10. The method for manufacturing a perovskite solar cell as claimed in claim 6, wherein the process for forming the passivation layer on the surface of the perovskite layer on the side away from the substrate is a vacuum evaporation process, and the deposit contains thiol amine;
preferably, the deposition rate of the passivation layer is
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