CN108922971B - Process for rapidly improving performance of perovskite solar cell based on organic hole transport layer - Google Patents
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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
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
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- 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
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- 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
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
-
- 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
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- Photovoltaic Devices (AREA)
Abstract
The invention relates to a process for rapidly improving the performance of a perovskite solar cell based on an organic hole transport layer. A preparation method of a perovskite solar cell comprises the steps of coating a solution containing an organic hole transport material on a perovskite light absorption layer, and then annealing by adopting heat treatment to prepare the hole transport layer, wherein the heat treatment temperature is 80-120 ℃, and the treatment time is 30-120 seconds.
Description
Technical Field
The invention belongs to the technical field of solar cells, particularly relates to a process for improving the performance of a solar cell, and more particularly relates to a perovskite solar cell based on a hole transport layer and a process for improving the performance.
Background
Organic-inorganic halide perovskite solar cells are of high interest due to their ultra-high efficiency and low cost, ease of fabrication and manufacture. Nevertheless, the stability problems of perovskite solar cells have hindered further development of commercialization. Therefore, stability is one of the important issues in the study of perovskite solar cells. This includes the long-term stability, i.e. lifetime, of the device and also the stability, i.e. reproducibility, repeatability, of the manufacturing process of the device.
The organic-inorganic halide perovskite material has optical and electrical characteristics of high light absorption coefficient, relatively low exciton binding energy, high carrier migration, long transmission distance, bipolar transmission of electrons and holes and the like, and the highest authentication efficiency of the perovskite battery reaches 23.3 percent in short years. Among the key materials for forming the perovskite solar cell, the film forming quality of the perovskite active layer and the selection and optimization of the electron and hole transport layers are particularly important for improving the efficiency and stability of the perovskite solar cell, so that the perovskite solar cell is always a research hotspot in the field of perovskite solar cells.
At present, the traditional high-efficiency planar n-i-p type perovskite solar cell generally adopts Spiro-OMeTAD as a hole transport material of the perovskite solar cell, the intrinsic hole mobility of the material is low, and the electrical characteristics of the perovskite solar cell are generally improved by doping Li salt. However, the Li salt has certain hygroscopicity and is not stable enough in the atmospheric atmosphere, which is one of the reasons for poor stability of the perovskite battery, and further limits the industrial development and application of the perovskite battery. The crystallinity and the oxidation degree of the Spiro-OMeTAD film are not controlled, and the performance of the film can be exerted only after the film is placed for a plurality of days, so that a preparation process for rapidly improving the performance is needed to shorten the production period of the battery and reduce the manufacturing cost. In addition, the instability of the Li salt doped Spiro-OMeTAD material also causes poor repeatability of the device preparation process.
Disclosure of Invention
The invention aims to solve the problems that the crystallinity and the oxidation degree of the traditional Spiro-OMeTAD film reported in the literature are not controlled, the treatment temperature and time are difficult to accurately control, the surface of the film is rough, the quality of the film is not high, the process repeatability is poor and the like, and provides a preparation method of a perovskite solar cell, namely a novel process for rapidly improving the performance of the perovskite solar cell based on an organic hole transport layer.
The first invention relates to a preparation method of a perovskite solar cell, which is characterized in that a solution containing an organic hole transport material is coated on a perovskite light absorption layer, and then annealing is carried out by adopting heat treatment to prepare the hole transport layer, wherein the heat treatment temperature is 80-120 ℃, and the treatment time is 30-120 seconds.
According to the first invention, the hole transport layer thin film is prepared by annealing, and in the preparation process, because the annealing process generally affects the charge generation/recombination kinetics of the device, the annealing heating enables the additive solvent to be rapidly volatilized, and the crystallinity and the hole mobility are increased. The hole transport layer film prepared according to the invention has the advantages of smooth and even surface and excellent photoelectric conversion performance.
Preferably, the organic hole transport material is at least one of Spiro-OMeTAD, PTAA, P3HTP and PEDOT PSS.
Preferably, the solution containing the organic hole transport material contains: Spiro-OMeTAD, lithium bis (trifluoromethane) sulfonimide, 4-tert-butylpyridine and cobalt complex FK 209.
Preferably, the perovskite light absorption layer is prepared by the following method: preparing an organic-inorganic hybrid perovskite precursor by using metal halide and organic amine halide as raw materials; coating the prepared organic-inorganic hybrid perovskite precursor on a substrate.
Preferably, the perovskite light absorption layer is Cs0.05(FA0.83MA0.17)0.95Pb(I0.83Br0.17)3、MAPbI3At least one of (1).
A second invention is a perovskite solar cell manufactured according to any one of the above manufacturing methods.
According to the second invention, the surface of the hole transport layer thin film in the perovskite solar cell is flat, smooth and uniform, so that the perovskite solar cell has excellent photoelectric conversion performance.
The perovskite solar cell may include in order from bottom to top: transparent conductive substrate, electron transport layer, perovskite light absorption layer, hole transport layer, metal counter electrode.
According to the invention, the hole transport layer is subjected to short annealing treatment, so that the prepared film has the advantages of smooth surface, high quality, good crystallinity and high photoelectric conversion performance. The annealing treatment can increase the filling factor of the device, promote the oxidation process of the hole transport material such as Spiro-OMeTAD, and improve the performance of the battery. The preparation method provided by the invention has the advantages of short time consumption, low energy consumption, high production efficiency, simple process, mild preparation conditions, easiness in operation and wide application prospect.
Drawings
FIG. 1 shows scanning electron micrographs of Spiro-OMeTAD films prepared in examples and comparative examples.
FIG. 2 shows the steady state fluorescence spectra of the Spiro-OMeTAD films obtained in the examples and comparative examples.
Fig. 3 shows J-V curves of perovskite solar cells based on a Spiro-OMeTAD thin film prepared in examples and comparative examples.
Detailed Description
The present invention is further described below in conjunction with the following embodiments and the accompanying drawings, it being understood that the drawings and the following embodiments are illustrative of the invention only and are not limiting thereof.
The invention relates to a process for rapidly improving the performance of a perovskite solar cell based on an organic hole transport layer. The invention adopts an annealing treatment method to prepare the hole transport layer film in the perovskite solar cell.
In one embodiment, a solution containing an organic hole transport material is coated on a perovskite light absorbing layer and then annealed using a thermal process to prepare a hole transport layer.
Organic hole transport materials include, but are not limited to, Spiro-OMeTAD (2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene), PTAA (poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ]), P3HT (poly (3-hexylthiophene)), PEDOT: PSS (poly 3, 4-ethylenedioxythiophene: polystyrene sulfonate), and the like, with Spiro-OMeTAD being particularly preferred.
The solution containing the organic hole transporting material may contain, in addition to the organic hole transporting material, organic additives such as organic lithium salt, TBP (4-tert-butylpyridine), cobalt complex FK209, and the like. Examples of the organic lithium salt include lithium bis (trifluoromethane) sulfonimide. The molar ratio of organic hole transport material to organic lithium salt may be, for example, 1: (0.2-2). The molar ratio of organic hole transport material to TBP may be, for example, 1: (1-3). The molar ratio of organic hole transport material to FK209 may be, for example, 1: (0.05-0.3). In one example, a solution containing an organic hole transport material is formulated by: uniformly mixing a chlorobenzene solution of Spiro-OMeTAD, an acetonitrile solution of lithium bis (trifluoromethane) sulfimide, TBP and FK209 to obtain a solution containing the organic hole transport material. The concentration of the chlorobenzene solution of the Spiro-OMeTAD can be 30-100 mg/mL. The concentration of the acetonitrile solution of the lithium bis (trifluoromethane) sulfonimide can be 200-800 mg/mL.
The method for coating the solution containing the organic hole transport material on the perovskite light absorbing layer is not particularly limited, and for example, a solution method such as spin coating or dipping may be used. In the spin coating method, the rotation speed can be 1000-6000 rpm, and the spin coating time can be 10-60 s.
The heat treatment may be carried out by heating the film on a hot plate. The heat treatment temperature can be 80-120 ℃. If it is lower than 80 ℃, the hole transport material cannot be sufficiently oxidized in a short time; above 120 c, it may have a destructive effect on the perovskite thin film, causing decomposition of the perovskite light absorbing material and causing evaporation of the hole transporting material. More preferably, the heat treatment temperature is 90-110 ℃.
The heat treatment time may be 30 seconds to 120 seconds. If the heat treatment time is too short, the hole transport material cannot be sufficiently oxidized; if the heat treatment time is too long, evaporation of the hole transport material may be caused to destroy the hole transport layer, and there may be a destructive effect on the perovskite thin film, causing decomposition of the perovskite light absorbing material. More preferably, the heat treatment time is 30 seconds to 60 seconds.
The heat treatment environment is preferably a dry environment, so that moisture absorption of lithium salt in the hole transport material can be avoided, and the performance of the battery can be reduced.
By the preparation method, the performance of the perovskite solar cell based on the organic hole transport layer can be rapidly improved.
The chemical formula of the perovskite light absorption layer can be represented as ABX3Wherein A may be a monovalent cation or a mixed cation, including but not limited to CH3NH3+、NH2-CH＝NH2 +、Cs+、Li+、C4H9NH3 +、CH6N3 +、Na+、K+And the like. B can adopt Pb2+、Sn2+、Ge2 +、Co2+、Fe2+、Mn2+、Cu2+And Ni2+B may be one of these ions, or may be a mixed structure of any two or more of these ions. X may adopt Cl-、Br-、I-、SCN-、BF4 -That is, X may be a single ion or a mixed ion, for example, a mixture of any two of the ions. For example, the chemical composition includes, but is not limited to, methylaminolead iodide, formamidine lead iodide, mixtures of methylaminoformamidine lead iodide, cesium formamidine lead iodide, cesium methylaminoformamidine lead iodide, and the like. Preferably, the perovskite light absorbing layer is selected from Cs0.05(FA0.83MA0.17)0.95Pb(I0.83Br0.17)3、MAPbI3At least one of (1). Wherein FA represents NH2-CH＝NH2 +MA represents CH3NH3 +。MAPbI3Is the most commonThe perovskite light absorption material is simple and convenient to prepare and excellent and stable in performance. And Cs0.05(FA0.83MA0.17)0.95Pb(I0.83Br0.17)3Has higher photoelectric conversion efficiency (more than 20 percent) and better device durability.
The perovskite light absorption layer is preferably smooth and flat, so that the hole transmission layer prepared on the perovskite light absorption layer is more flat and compact, the interface quality of the hole transmission material and the perovskite light absorption layer and the interface quality of the hole transmission material and the metal counter electrode are improved, and the interface carrier separation efficiency and the battery conversion efficiency are improved.
The perovskite light-absorbing layer (perovskite thin film) can be prepared by, for example, a vapor deposition method or a solution deposition method. From the viewpoint of reducing the production cost and simplifying the production process, the solution deposition method is preferable. For example, a perovskite thin film can be obtained by a one-step solution method, a two-step method, or the like.
Taking a one-step solution method as an example, ABX is synthesized by dispersing halide of A and halide of B in a solvent and stirring3Precursor solution, and mixing the ABX3Precursor solution coating (e.g., spin coating) on a substrate to form ABX3A film.
Obtaining ABX3After the film is formed, it is preferably not subjected to a heat treatment, directly in ABX3The film is coated with a solution containing an organic hole transport material and then subjected to the above-described annealing treatment. On one hand, the process is simplified, two-step annealing is not needed, and simultaneously, the one-step annealing helps the hole transport material to penetrate into a part of the perovskite light absorption layer and promotes the carrier separation on the interface.
In one embodiment, the perovskite solar cell comprises, from bottom to top: transparent conductive substrate, electron transport layer, perovskite light absorption layer, hole transport layer, metal counter electrode.
The transparent conductive electrode may be made of rigid or flexible materials, such as FTO glass and ITO glass, or flexible transparent conductive films made of metal (sputtering type or metal grid type) or oxide films such as ITO, which are based on polymer films such as polyethylene naphthalate (PEN), polyethylene terephthalate (PET), Polyimide (PI), Polycarbonate (PC), polyaniline, polypyrrole, or the like. The thickness of the film can be 0.1-10 mm.
The composition of the electron transport layer includes, but is not limited to, at least one of dense titanium oxide, zinc oxide, cobalt oxide, nickel oxide, or dopants thereof. The electron transport layer can be prepared by spin coating, spray coating, blade coating, magnetron sputtering, atomic layer deposition and the like.
The perovskite light absorbing layer and the method of making the same may be as described above.
The hole transport layer and the method for preparing the same may be as described above.
The metal counter electrode may be gold, silver, copper, aluminum, or the like. The hole transport layer can be evaporated with a metal counter electrode, or MoO can be evaporated between the hole transport layer and the metal counter electrode3And the metal oxide is an intermediate layer.
In the method, the hole transport layer film is prepared in an annealing treatment mode, in the preparation process, because in the annealing heating process, a sample is heated more uniformly, the heat treatment time is shorter, the treatment time is easier to accurately control, and the effect of improving the performance of a device can be achieved through the annealing treatment in shorter time. Therefore, the film has the advantages of smooth surface, large particles, less crystal boundary, good crystallinity and sufficient oxidation, and can effectively collect and transmit holes and block the recombination of electrons and holes. The high-performance thin film and the perovskite solar cell prepared by the method have high photoelectric conversion efficiency and are suitable for large-scale production and application.
Moreover, the heat treatment mode in the method is easy to realize, the heat treatment time is greatly shortened, and the method is particularly suitable for assembly line operation and realizes large-scale production and application of the perovskite solar cell.
The perovskite solar cell obtained by adopting the heat treatment process has the photoelectric conversion efficiency reaching 16.47 percent, is higher than that of a traditional treatment mode by 14.02 percent, and the preparation time of the hole transport layer is greatly shortened. The process for preparing the hole transport layer by the heat treatment process is greatly shortened in processing time on the premise of ensuring the efficiency of the battery, and is more suitable for large-scale production and application.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
(1) And (3) preparing a hole transport layer film without heat treatment. And ultrasonically cleaning the FTO glass for thirty minutes by using alkali liquor, deionized water and acetone respectively, blow-drying and carrying out ultraviolet irradiation treatment for 15 minutes. Then preparing TiO on the FTO glass substrate2The precursor solution solvent of the compact layer is ethanol, and the compact layer comprises the following components: tetraisopropyl titanate (0.3mol/L), acetylacetone (0.45mol/L), hydrochloric acid (0.09mol/L), and water (1.8 mol/L). And (3) sucking the precursor solution, dropwise adding the precursor solution on a cleaned FTO substrate to enable the solution to be spread on the whole FTO surface, and forming a film by adopting a spin-coating method, wherein the spin-coating speed is 3000rpm, and the time is 20 s. Then sintered in a muffle furnace at 510 ℃ for 30 min. Then, 461 mg of lead iodide (PbI) was measured2) 159 mg of CH3NH3Powder I, 78 mg of dimethyl sulfoxide was mixed with 600 mg of N, N-Dimethylformamide (DMF), and the mixture was stirred at room temperature for 2 hours to form CH3NH3PbI3A perovskite precursor solution. The precursor solution was used as spin coating solution to prepare perovskite thin films by spin coating at 5000rpm for 20s, wherein 0.5 ml of diethyl ether was added dropwise to the spinning substrate at 6 s. The obtained perovskite thin film is spin-coated with a hole transport layer solution, and the perovskite thin film comprises the following components: 72.3mg/mL of 2,2',7,7' -tetrakis [ N, N-di (4-methoxyphenyl) amino]A solution of-9, 9' -spirobifluorene in chlorobenzene, comprising 20 μ L of 520mg/mL of a solution of lithium bis (trifluoromethane) sulfonimide in acetonitrile and 20 μ L of 4-tert-butylpyridine and 29 μ L of cobalt complex (FK209) as additives, at 4000rpm for 20 s.
(2) And (2) placing the film prepared in the step (1) on a hot plate, setting the temperature to be 100 ℃, and carrying out heat treatment for 30 seconds to obtain the Spiro-OMeTAD hole transport layer film.
(3) And preparing the perovskite solar cell. Finally evaporating a 120nm thick Ag counter electrode on the sample obtained in the step (2) to obtain CH3NH3PbI3Perovskite solar cell.
Comparative example 1
(1) And (3) preparing a hole transport layer film without heat treatment. The same as in example 1.
(2) And (2) placing the perovskite thin film prepared in the step (1) in the air for 10 minutes to obtain a Spiro-OMeTAD hole transport layer thin film.
(3) And preparing the perovskite solar cell. The same as in example 1.
Fig. 1 shows SEM photographs of the Spiro-OMeTAD thin films obtained in example 1 and comparative example 1, in which (a) is example 1 and (b) is comparative example 1. As can be seen from FIG. 1, the surface of the Spiro-OMeTAD film of example 1 is more flat and dense than that of comparative example 1, which shows that the perovskite film is not damaged by spin coating the hole transport material on the perovskite film and then annealing treatment, and the prepared Spiro-OMeTAD film has better surface appearance. Fig. 2 shows the steady-state fluorescence spectrum curves of the spiro-OMeTAD thin films prepared in example 1 and comparative example 1, and it can be seen that the fluorescence peak intensity of example 1 is significantly lower than that of comparative example 1, which shows that after the hole transport material is annealed, the interface carrier extraction capability is enhanced and the fluorescence quenching degree is greater. Solar simulator using standard xenon lamp (AM1.5, 100 mW/cm)2) Open circuit voltage Voc, short circuit current density Jsc, fill factor FF, and conversion efficiency η of the perovskite solar cell were measured fig. 3 shows J-V curves of the perovskite solar cells based on the Spiro-OMeTAD thin film manufactured in example 1 and comparative example 1, and it can be seen that the perovskite solar cell of example 1 has a photoelectric conversion efficiency of 16.47%, which is much higher than 14.02% of the comparative example.
Example 2
(1) And (3) preparing a hole transport layer film without heat treatment. The same as in example 1.
(2) And (2) placing the film prepared in the step (1) on a hot plate, setting the temperature to be 80 ℃, and carrying out heat treatment for 120 seconds to obtain the Spiro-OMeTAD hole transport layer film.
(3) And preparing the perovskite solar cell. The same as in example 1.
Example 3
(1) And (3) preparing a hole transport layer film without heat treatment. The same as in example 1.
(2) And (2) placing the film prepared in the step (1) on a hot plate, setting the temperature at 120 ℃, and carrying out heat treatment for 30 seconds to obtain the Spiro-OMeTAD hole transport layer film.
(3) And preparing the perovskite solar cell. The same as in example 1.
Comparative example 2
(1) And (3) preparing a hole transport layer film without heat treatment. The same as in example 1.
(2) And (2) placing the film prepared in the step (1) on a hot plate, setting the temperature at 150 ℃, and carrying out heat treatment for 300 seconds to obtain the Spiro-OMeTAD hole transport layer film.
(3) And preparing the perovskite solar cell. The same as in example 1.
TABLE 1 photoelectric conversion parameters of perovskite solar cells prepared in examples 1-3 and comparative examples 1-2
According to the invention, the hole transport layer is prepared by adopting an annealing treatment method, and the photoelectric conversion efficiency of the obtained perovskite solar cell is higher than that of the traditional method. And the heat treatment time is greatly shortened, the method is particularly suitable for assembly line work, is beneficial to the development of related heat treatment equipment, and realizes the large-scale production and application of the perovskite solar cell.
Claims (8)
1. The preparation method of the perovskite solar cell is characterized in that a solution containing an organic hole transport material is coated on a perovskite light absorption layer and then annealing is carried out by adopting heat treatment to prepare a hole transport layer, wherein the heat treatment temperature is 80-120 ℃, and the treatment time is 30-60 seconds; wherein, the perovskite light absorption layer is not subjected to heat treatment, and a solution containing an organic hole transport material is directly coated on the perovskite light absorption layer.
2. The method according to claim 1, wherein the organic hole transport material is at least one of Spiro-OMeTAD, PTAA, P3HT, PEDOT PSS.
3. The method according to claim 1, wherein the solution containing the organic hole transport material contains: Spiro-OMeTAD, lithium bis (trifluoromethane) sulfonimide, 4-tert-butylpyridine and cobalt complex FK 209.
4. The production method according to claim 1, wherein the perovskite light-absorbing layer is produced by: preparing an organic-inorganic hybrid perovskite precursor by using metal halide and organic amine halide as raw materials; coating the prepared organic-inorganic hybrid perovskite precursor on a substrate.
5. The method of claim 1, wherein the perovskite light absorbing layer is an ABX of a type3A light-absorbing material of perovskite structure, wherein A is a monovalent cation and is CH3NH3 +、NH2-CH＝NH2 +、Cs+、Li+、C4H9NH3 +、CH6N3 +、Na+、K+B is a divalent cation and is Pb2+、Cs+、Sn2+、Ge2+、Co2+、Fe2+、Mn2+、Cu2+、Ni2+At least one of (1), X is Cl-、Br-、I-、SCN-、BF4 -At least one of (1).
6. The production method according to claim 5, wherein the perovskite light-absorbing layer is Cs 0.05 (FA0.83MA0.17)0.95Pb(I0.83Br0.17)3、MAPbI3At least one of (1).
7. A perovskite solar cell manufactured according to the manufacturing method of any one of claims 1 to 6.
8. The perovskite solar cell according to claim 7, comprising in order from bottom to top: transparent conductive substrate, electron transport layer, perovskite light absorption layer, hole transport layer, metal counter electrode.
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