CN112358430B - Schiff base metal complex and preparation method thereof, perovskite solar cell and preparation method thereof - Google Patents

Schiff base metal complex and preparation method thereof, perovskite solar cell and preparation method thereof Download PDF

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CN112358430B
CN112358430B CN202011202557.5A CN202011202557A CN112358430B CN 112358430 B CN112358430 B CN 112358430B CN 202011202557 A CN202011202557 A CN 202011202557A CN 112358430 B CN112358430 B CN 112358430B
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许家驹
许宗祥
王玉珍
叶文康
胡启锟
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Southwest University of Science and Technology
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Abstract

The invention relates to a Schiff base metal complex and a preparation method thereof, and a perovskite solar cell and a preparation method thereof. The Schiff base metal complex has the following structural formula:
Figure DDA0002755839430000011
wherein M is a divalent metal ion, R 1 、R 2 、R 3 And R 4 Each independently selected from hydrogen or alkoxy, and R 1 、R 2 、R 3 And R 4 At least one of them is an alkoxy group. The Schiff base metal complex is low in price, has excellent semiconductor characteristics and good solubility in an organic solvent, can be prepared into a doping-free hole transport layer of the perovskite solar cell by adopting a low-cost liquid phase spin coating process, and can effectively improve the stability of devices of the perovskite solar cell. And the alkoxy substituent group on the periphery of the Schiff base metal complex is beneficial to improving the hydrophobic property of the material, can effectively resist the invasion of water molecules, can effectively protect the perovskite light absorption layer, and can further improve the service life and the stability of the device.

Description

Schiff base metal complex and preparation method thereof, perovskite solar cell and preparation method thereof
Technical Field
The invention relates to the field of solar cells, in particular to a Schiff base metal complex and a preparation method thereof, and a perovskite solar cell and a preparation method thereof.
Background
Fossil fuels are still the main energy source of human society at present, but with the large-scale exploitation and use for more than one hundred years, the fossil fuels face the dilemma of becoming exhausted, and meanwhile, the fossil energy brings about serious environmental pollution problems in the use process. Therefore, the development of clean and renewable energy sources is urgent for the sustainable development of human society. As a new photovoltaic technology, perovskite solar cells have attracted wide attention worldwide due to their advantages of high photoelectric conversion efficiency, simple preparation, environmental protection, low cost, and the like. Over the past decade, the technology has evolved dramatically, with photovoltaic conversion efficiencies ranging from the first 3.8% to over 25% of the present, approaching that of commercial silicon-based solar cells. Further reducing the production cost and improving the long-term stability of the device are key scientific problems to be solved urgently in large-scale application of the perovskite solar cell.
In the construction of perovskite solar cells, the hole transport layer is usually an integral component. The high-performance hole transport material is important for optimizing an interface, improving the extraction and transmission efficiency of hole carriers, improving the photoelectric conversion efficiency of a device and prolonging the service life of the device.
Currently, the widely used hole transport materials for perovskite solar cells can be mainly classified into three types:
(1) inorganic hole transport materials have the following advantages: the material has the advantages of low price, stable performance and higher conductive capability; the disadvantages are that: the carrier recombination rate is too high, the filling factor of the device is easy to reduce, and meanwhile, the electronic energy level of the material is difficult to regulate and control, so that a high-performance solar cell device is difficult to obtain;
(2) the organic polymer semiconductor material has the advantages that: the organic solvent is easy to dissolve, and the hole transport layer can be prepared by a low-temperature liquid phase process; the disadvantages are that: the material has the advantages of high difficulty in controlling the molecular weight, difficult determination of the structure, complex synthesis and difficult purification, and is not beneficial to batch large-scale production;
(3) the organic micromolecule semiconductor material has the advantages that: the material has strong controllability of molecular structure, easy synthesis and purification, and can be prepared into a film by adopting a thermal evaporation or liquid phase spin coating process.
The reported high-efficiency perovskite solar cells mostly use organic small-molecule materials as hole transport layers. The material is obtained by the reaction of spirofluorene and aniline, and is expensive, so that the popularization and the application of the material are limited. In addition, the hole mobility and the conductivity of such materials are low, and dopants such as lithium salt and the like are usually added to improve the conductivity, and the introduction of the dopants can cause adverse effects on the long-term stability of the device. At present, the future industrial application of the organic small molecule hole transport material is restricted by expensive price and unstable factors.
Disclosure of Invention
Based on the above, there is a need for a schiff base metal complex which is low in cost and can be used in a perovskite solar cell to improve the stability of a device, and a preparation method thereof.
In addition, a perovskite solar cell and a preparation method thereof are also needed to be provided.
A schiff base metal complex having the formula:
Figure BDA0002755839410000021
wherein M is a divalent metal ion, R 1 、R 2 、R 3 And R 4 Each independently selected from hydrogen or alkoxy, and R 1 、R 2 、R 3 And R 4 At least one of which is an alkoxy group.
In one embodiment, M is Co 2+ 、Cu 2+ 、Zn 2+ 、Ni 2+ 、Pt 2+ 、Pd 2+ 、Pb 2+ 、Sn 2+ Or Mn 2 (ii) a And/or the alkoxy is-OCH 3 、-OC 2 H 5 or-OC 3 H 7 。
In one embodiment, R 1 And R 4 Is hydrogen, R 2 And R 3 Is an alkoxy group.
A preparation method of Schiff base metal complexes comprises the following steps: mixing substituted o-phenylenediamine, divalent metal salt, pyrrole-2-formaldehyde and an organic solvent for reaction to prepare a Schiff base metal complex, wherein the divalent metal salt can be dissolved in the organic solvent, and the structural formula of the substituted o-phenylenediamine is shown in the specification
Figure BDA0002755839410000031
The structural formula of the Schiff base metal complex is shown as
Figure BDA0002755839410000032
Wherein M is a divalent metal ion, R 1 、R 2 、R 3 And R 4 Each independently selected from hydrogen or alkoxy, and R 1 、R 2 、R 3 And R 4 At least one of them is an alkoxy group.
In one embodiment, the divalent metal salt is an acetate or chloride; and/or the metal ion in the divalent metal salt is Co 2+ 、Cu 2+ 、Zn 2+ 、Ni 2+ 、Pt 2+ 、Pd 2+ 、Pb 2+ 、Sn 2+ Or Mn 2 (ii) a And/or the alkoxy is-OCH 3 、-OC 2 H 5 or-OC 3 H 7 。
In one embodiment, R 1 And R 4 Is hydrogen, R 2 And R 3 Is an alkoxy group.
In one embodiment, the molar ratio of the substituted o-phenylenediamine, the metal ion in the divalent metal salt and the pyrrole-2-carbaldehyde is (1-5): 1-2): 2-3.
In one embodiment, the organic solvent is ethanol, chloroform, dimethylformamide or dimethylsulfoxide.
In one embodiment, the reaction temperature is 10-80 ℃, and the reaction time is 2-15 h.
The perovskite solar cell comprises a substrate layer, an electron transport layer, a perovskite light absorption layer, a hole transport layer and an electrode layer which are arranged in a stacked mode, wherein the hole transport layer is made of the Schiff base metal complex or is prepared by the preparation method of the Schiff base metal complex.
In one embodiment, the material of the substrate layer is FTO, and the thickness of the substrate layer is 5 nm-20 nm; and/or the material of the electron transmission layer is tin dioxide, and the thickness of the electron transmission layer is 5 nm-30 nm; and/or the perovskite light absorption layer is made of CH 3 NH 3 PbI 3 The thickness of the perovskite light absorption layer is 100 nm-800 nm; and/or the thickness of the hole transport layer is 30 nm-100 nm; andor the electrode layer is made of gold, and the thickness of the electrode layer is 30 nm-150 nm.
A preparation method of a perovskite solar cell comprises the following steps: an electron transport layer, a perovskite light absorption layer, a hole transport layer and an electrode layer are sequentially formed on the substrate layer, and the hole transport layer is made of the Schiff base metal complex or is prepared by the preparation method of the Schiff base metal complex.
In one embodiment, the hole transport layer is formed by vacuum evaporation or liquid phase spin coating.
In one embodiment, the rate of vacuum evaporation is
Figure BDA0002755839410000041
In one embodiment, the material of the electron transport layer is tin dioxide, and the step of forming the electron transport layer includes: spin-coating an ethanol solution of stannous chloride on the substrate layer, and then performing annealing treatment to form the electron transport layer; and/or;
the electrode layer is made of gold, and the step of forming the electrode layer comprises the following steps: and evaporating gold on the side of the hole transport layer far away from the substrate layer to form the electrode layer.
In one embodiment, the perovskite light absorption layer is made of CH 3 NH 3 PbI 3 The step of forming the perovskite light absorption layer comprises: and spin-coating a mixed solution of lead iodide, methyl ammonium iodide, dimethyl sulfoxide and dimethyl formamide on one side of the electron transport layer, which is far away from the substrate layer, and then carrying out annealing treatment to form the perovskite light absorption layer.
In one embodiment, the mass ratio of the lead iodide, the methyl ammonium iodide, the dimethyl sulfoxide and the dimethylformamide in the mixed solution is (400-500): 100-200): 50-100: (500-800).
The Schiff base metal complex is low in price, has excellent semiconductor characteristics, does not need to add a dopant, can be prepared into a doping-free hole transport layer of the perovskite solar cell by adopting a low-cost liquid-phase spin coating process or a low-cost evaporation process, and can effectively improve the stability of the perovskite solar cell. And the alkoxy substituent group on the periphery of the Schiff base metal complex is beneficial to improving the hydrophobic property of the material, can effectively resist the invasion of water molecules, can effectively protect a perovskite light absorption layer when being applied to a perovskite solar cell, and can further improve the service life and the stability of a device. Therefore, the Schiff base metal complex is low in price, can improve the stability of devices when being used in the perovskite solar cell, and provides a novel hole transport material for the perovskite solar cell.
Drawings
FIG. 1 is a schematic structural diagram of an embodiment of a perovskite solar cell;
FIG. 2 is a scanning electron micrograph of a hole transport layer in the perovskite solar cell obtained in example 10;
FIG. 3 is an I-V curve of the perovskite solar cell obtained in example 10;
FIG. 4 is a graph showing the change of the photoelectric conversion efficiency of the perovskite solar cell obtained in example 10 in air with time;
fig. 5 is a graph showing the change of the photoelectric conversion efficiency of the perovskite solar cell obtained in comparative example 1 in air with time.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description taken in conjunction with the accompanying drawings. The detailed description sets forth the preferred embodiments of the invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
In order to solve the problems of high price and poor stability caused by the introduction of a dopant in a hole transport material of a traditional perovskite solar cell, one embodiment of the invention provides a schiff base metal complex, which has the following structural formula:
Figure BDA0002755839410000061
wherein M is a divalent metal ion. Specifically, M is Co 2+ 、Cu 2+ 、Zn 2+ 、Ni 2+ 、Pt 2+ 、Pd 2+ 、Pb 2+ 、Sn 2+ Or Mn 2 。R 1 、R 2 、R 3 And R 4 Each independently selected from hydrogen or alkoxy, and R 1 、R 2 、R 3 And R 4 At least one of them is an alkoxy group. In one embodiment, R 1 、R 2 、R 3 And R 4 Two of which are alkoxy groups. Further, R 1 And R 4 Is hydrogen, R 2 And R 3 Is an alkoxy group. It is understood that the number of alkoxy groups is not limited to 2, but may also be 1, 3 or 4, and is not limited to R 2 And R 3 Is an alkoxy group, and may also be R 1 And R 4 Is alkoxy, or R 1 And R 2 Is alkoxy, or R 1 And R 3 Is an alkoxy group. The alkoxy substituent group on the periphery of the Schiff base metal complex is beneficial to improving the hydrophobic property of the material, can effectively resist the invasion of water molecules, can effectively protect a perovskite light absorption layer when being applied to a perovskite solar cell, and can further improve the service life and the stability of a device.
Further, alkoxy is-OCH 3 、-OC 2 H 5 or-OC 3 H 7 . It is to be understood that alkoxy is not limited to the above substituents, but may also be alkoxy having greater than 3 carbon atoms, such as-OC 4 H 9 、-OC 5 H 11 And the like.
The Schiff base metal complex has low price, excellent semiconductor characteristics and good solubility in an organic solvent, can be prepared into a doping-free hole transport layer of the perovskite solar cell by adopting a low-cost liquid phase spin coating process or a vacuum evaporation method, and can effectively improve the stability of devices of the perovskite solar cell.
One embodiment of a method for preparing a schiff base metal complex includes the steps of:
mixing substituted o-phenylenediamine, divalent metal salt, pyrrole-2-formaldehyde and an organic solvent for reaction to obtain a Schiff base metal complex, wherein the structural formula of the substituted o-phenylenediamine is shown in the specification
Figure BDA0002755839410000071
The structural formula of the Schiff base metal complex is shown as
Figure BDA0002755839410000072
Wherein M is a divalent metal ion, R 1 、R 2 、R 3 And R 4 Each independently selected from hydrogen or alkoxy, and R 1 、R 2 、R 3 And R 4 At least one of which is an alkoxy group. Further, alkoxy is-OCH 3 、-OC 2 H 5 or-OC 3 H 7 . In one embodiment, R 1 、R 2 、R 3 And R 4 Two of which are alkoxy groups. Further, R 1 And R 4 Is hydrogen, R 2 And R 3 Is alkoxy, and the substituted o-phenylenediamine is 4, 5-dialkoxy o-phenylenediamine. It is understood that the number of alkoxy groups in the substituted o-phenylenediamine is not limited to 2, but may also be 1, 3 or 4, and is not limited to R 2 And R 3 Is an alkoxy group, and may also be R 1 And R 4 Is alkoxy, or R 1 And R 2 Is alkoxy, or R 1 And R 3 Is an alkoxy group.
Specifically, the divalent metal salt can be dissolved in an organic solvent. The divalent metal salt is Co 2+ 、Cu 2+ 、Zn 2+ 、Ni 2+ 、Pt 2+ 、Pd 2+ 、Pb 2+ 、Sn 2+ Or Mn 2+ . Further, the divalent metal salt is acetate or chloride.
Further, the molar ratio of the substituted o-phenylenediamine, the metal ion in the divalent metal salt and the pyrrole-2-formaldehyde is (1-1.5): (1-1.2): 2-3. In one embodiment, the molar ratio of the substituted o-phenylenediamine, the metal ion in the divalent metal salt, and the pyrrole-2-carbaldehyde is 1:1:2, 1.1:1.1:2.4, 1.2:1.1:2.5, or 1.5:1.2: 3.
Preferably, the reaction temperature is between room temperature and 80 ℃ and the reaction time is between 2 and 15 hours. In one embodiment, room temperature is 10 ℃ to 30 ℃. The reaction temperature is 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃ or 80 ℃. The reaction time is 2h, 3h, 5h, 10h, 12h or 15 h.
Preferably, the organic solvent is ethanol, chloroform, dimethylformamide or dimethyl sulfoxide.
Further, after the reaction is finished, a purification step is also included. Specifically, the purification step comprises: and filtering and washing a product after reaction, and then carrying out column chromatography separation, concentration and recrystallization. In one embodiment, the washing is carried out with the above-mentioned organic solvent. The column chromatography separation process may be adjusted according to conventional means in the art, for example, the eluent used may be a mixture of ethanol and dichloromethane. The reagent used in the recrystallization process may be a mixture of ethanol and dichloromethane. It will be appreciated that the above list only shows one common processing parameter, which can also be adjusted to the actual situation. The product can be further purified by the above steps.
The preparation method of the Schiff base metal complex is simple in process, easy for industrial production, low in price of the adopted raw materials, excellent in semiconductor characteristics of the prepared Schiff base metal complex, good in solubility in an organic solvent, capable of being prepared into a hole transport layer of the doping-free perovskite solar cell by adopting a low-cost liquid phase spin coating process, and capable of effectively improving the stability of devices of the perovskite solar cell without doping lithium salt.
Referring to fig. 1, the present invention further provides a perovskite solar cell 100, which includes a substrate layer 110, an electron transport layer 120, a perovskite light absorption layer 130, a hole transport layer 140, and an electrode layer 150, which are stacked, wherein the material of the hole transport layer 140 is the schiff base metal complex of the above embodiment or is prepared by the preparation method of the schiff base metal complex of the above embodiment.
Specifically, the thickness of the substrate layer 110 is 5nm to 20 nm. In one embodiment, substrate layer 110 has a thickness of 5nm, 10nm, 15nm, or 20 nm. The material of the substrate layer 110 is a transparent conductive material commonly used in the perovskite solar cell 100 in the art, for example, the material of the substrate layer 110 is Indium Tin Oxide (ITO) or fluorine-doped tin dioxide (FTO). Further, the material of substrate layer 110 is FTO.
Specifically, the thickness of the electron transport layer 120 is 5nm to 30 nm. In one embodiment, the electron transport layer 120 has a thickness of 5nm, 10nm, 15nm, 20nm, 25nm, or 30 nm. The material of the electron transport layer 120 is tin dioxide. It is to be understood that the material of the electron transport layer 120 is not limited to tin dioxide, but may be other materials commonly used in the art.
The material of the perovskite light absorbing layer 130 may be a perovskite light absorbing material commonly used in the art for perovskite solar cells 100, such as CH 3 NH 3 PbI 3 Or CH 3 NH 3-x PbCl x . Specifically, the thickness of the perovskite light absorption layer 130 is 100nm to 800 nm. In one embodiment, the thickness of the perovskite light absorbing layer 130 is 100nm, 200nm, 400nm, 500nm, 600nm, or 800 nm.
The thickness of the hole transport layer 140 is 30nm to 100 nm. In one embodiment, the hole transport layer 140 has a thickness of 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, or 100 nm.
The material of the electrode layer 150 may be an electrode material of the perovskite solar cell 100 commonly used in the art, such as gold. Specifically, the thickness of the electrode layer 150 is 30nm to 150 nm. In one embodiment, the thickness of the electrode layer 150 is 30nm, 60nm, 90nm, 100nm, 120nm, or 150 nm.
The hole transport layer 140 of the perovskite solar cell 100 is made of schiff base metal complexes which are low in cost, excellent in semiconductor performance and good in solubility, so that the extraction and the transmission of photoproduction holes of the perovskite light absorption layer 130 are facilitated, the electron-hole recombination probability is reduced, and the performance of devices is improved; in the Schiff base metal complex molecule provided by the invention, alkoxy substituent groups on the periphery of the Schiff base metal complex molecule are beneficial to improving the hydrophobic property of the material, can effectively resist the invasion of water molecules, can effectively protect a perovskite active layer, and is beneficial to improving the service life and stability of a device.
The invention also provides a preparation method of the perovskite solar cell, which comprises the following steps: an electron transport layer, a perovskite light absorption layer, a hole transport layer and an electrode layer are sequentially formed on the substrate, and the material of the hole transport layer is the Schiff base metal complex in the embodiment or is prepared by the preparation method of the Schiff base metal complex in the embodiment.
Specifically, the hole transport layer is formed by vacuum evaporation or liquid phase spin coating. In one embodiment, the rate of vacuum evaporation is
Figure BDA0002755839410000091
For example, the rate of evaporation is
Figure BDA0002755839410000092
Figure BDA0002755839410000094
Or
Figure BDA0002755839410000093
The thickness of the hole transport layer is 30 nm-100 nm.
Specifically, the material of the substrate layer is FTO. The method further comprises the step of washing the substrate layer before the step of sequentially forming the electron transport layer, the perovskite light absorption layer, the hole transport layer and the electrode layer on the substrate. And specifically, sequentially carrying out ultrasonic treatment on the etched substrate in a cleaning agent, deionized water, absolute ethyl alcohol, acetone and isopropanol for 15min, taking out, drying by using nitrogen, putting into an oven, drying for 8h at 120 ℃, and carrying out ultraviolet/ozone treatment for 30min to obtain the substrate layer. The above list only shows one process parameter in the washing process, but the above list is not limited thereto, and the process parameter may be one commonly used in the art. Further, the thickness of the substrate layer is 5 nm-20 nm.
The material of the electron transport layer is tin dioxide. In one embodiment, the step of forming the electron transport layer comprises: and spin-coating an ethanol solution of stannous chloride on the substrate layer, and then carrying out annealing treatment to form the stannic oxide electron transport layer. Specifically, in one embodiment, the concentration of the ethanol solution of stannous chloride is 0.1 mol/L. The spin speed during spin coating was 3000rpm for 40 s. The temperature of the annealing treatment is 180 ℃ and the time is 1 h. It should be understood that the above list only shows one common process parameter, but the above list is not limited thereto, and the above list can be adjusted according to the parameters such as the thickness of the electron transport layer to be formed. Specifically, the thickness of the electron transport layer is 5nm to 30 nm.
The material of the perovskite light absorption layer is CH 3 NH 3 PbI 3 . Specifically, the step of forming the perovskite light absorption layer includes: and spin-coating a mixed solution of lead iodide, methyl ammonium iodide, dimethyl sulfoxide and dimethyl formamide on the side of the tin dioxide electron transport layer, which is far away from the substrate layer, and then carrying out annealing treatment to obtain the perovskite light absorption layer. In one embodiment, the mass ratio of lead iodide, methyl ammonium iodide, dimethyl sulfoxide and dimethylformamide in the mixed solution is (400-500): 100-200): 50-100): 500-800. For example, the mass ratio of lead iodide, methyl ammonium iodide, dimethyl sulfoxide and dimethylformamide is 461: 159: 78:600. The spin coating was carried out at 4000rpm for 20 s. The annealing treatment comprises annealing at 65 deg.C for 2min, and then annealing at 100 deg.C for 5 min. It is understood that the above list only shows one common process parameter, but the process is not limited thereto, and may be adjusted according to the thickness of the perovskite light absorption layer to be formed. Specifically, the thickness of the perovskite light absorption layer is 100 nm-800 nm.
Further, in the step of forming the perovskite light absorption layer, ether or chlorobenzene is added during the spin coating process to improve the film quality. For example, 0.5mL of diethyl ether or 0.3mL of chlorobenzene is added.
The material of the electrode layer is gold. The step of forming the electrode layer includes: and evaporating gold on the side of the hole transport layer away from the FTO substrate layer to form an electrode layer. In one embodiment, the rate of evaporation is
Figure BDA0002755839410000101
For example, the rate of evaporation is
Figure BDA0002755839410000103
Or
Figure BDA0002755839410000102
The thickness of the electrode layer is 30nm to 150 nm.
Further, in one embodiment, the method for manufacturing the perovskite solar cell specifically includes the following steps:
spin-coating an ethanol solution of stannous chloride on the substrate layer, and then carrying out annealing treatment to form an electron transport layer;
spin-coating a mixed solution of lead iodide, methyl ammonium iodide, dimethyl sulfoxide and dimethyl formamide on one side of the electron transport layer, which is far away from the substrate layer, and then carrying out annealing treatment to form a perovskite light absorption layer;
evaporating Schiff base metal complexes on one side of the perovskite light absorption layer, which is far away from the substrate layer, so as to form a hole transport layer;
and (4) evaporating gold on the side of the hole transport layer far away from the substrate layer to form an electrode layer, and preparing the perovskite solar cell.
The hole transport layer of the perovskite solar cell is beneficial to the extraction and transmission of photoproduction holes of the perovskite light absorption layer by the hole transport layer, is beneficial to reducing the electron-hole recombination probability and is more beneficial to improving the performance of a device; in the Schiff base metal complex molecule provided by the invention, alkoxy substituent groups on the periphery of the Schiff base metal complex molecule are beneficial to improving the hydrophobic property of the material, can effectively resist the invasion of water molecules, can effectively protect a perovskite active layer, and is beneficial to improving the service life and stability of a device.
Experiments prove that the optimum photoelectric conversion efficiency parameters of the perovskite solar cell of the embodiment are as follows: open circuit voltage 1.07V, short circuit current density 22.7mA/cm 2 Fill factor 62%, conversion efficiency 15.24%. After the device is stored in the atmospheric environment for 1100 hours, the initial efficiency is still maintained to be more than 80%.
The following are specific examples:
example 1
The preparation process of the schiff base metal complex of the embodiment is specifically as follows:
(1) 1.48g (6.14mmol) of 4, 5-dimethoxyo-phenylenediamine, 0.80g (6.14mmol) of anhydrous CoCl 2 1.17g (12.28mmol) of pyrrole-2-carbaldehyde and 50mL of absolute ethanol were placed in a 100mL flask, stoppered and stirred at room temperature for 2 h.
(2) The reaction mixture obtained in the above step (1) was filtered, the solid on the filter paper was washed with 100mL of ethanol, and the solid on the filter paper was air-dried.
(3) Purifying the product of step (2) by column chromatography using SiO 2 Packing the chromatographic column, using a mixed solvent of ethanol and dichloromethane (volume ratio of 1/3) as an eluent, collecting a product solution, and evaporating the solvent in the product solution to dryness by using a rotary evaporator.
(4) And (3) further recrystallizing the product obtained in the step (3) in an ethanol/dichloromethane solvent system to obtain a final product shown in a formula II, namely the Schiff base metal complex of the embodiment.
Examples 2 to 9
The preparation process of the schiff base metal complexes of examples 2 to 9 is similar to that of the schiff base metal complex of example 1 except that: the raw materials, the mixture ratio, the reaction temperature and time and other parameters used are different, and are specifically shown in table 1. Wherein the molar ratio represents the molar ratio of the substituted o-phenylenediamine, the divalent metal salt and the pyrrole-2-carbaldehyde.
TABLE 1 Process parameters for Schiff base metal complexes of examples 2 to 9
Figure BDA0002755839410000121
Example 10
The preparation process of the perovskite solar cell of the embodiment is specifically as follows:
(1) preparation of FTO substrate layer
Sequentially carrying out ultrasonic treatment on the etched transparent conductive substrate FTO in a cleaning agent, deionized water, absolute ethyl alcohol, acetone and isopropanol for 15min, taking out, and then using nitrogen (N) 2 ) Drying, placing in an oven, drying at 120 ℃ for 8h, and carrying out ultraviolet/ozone treatment for 30min to obtain the FTO substrate layer.
(2) Preparation of tin dioxide electron transport layer
Preparing 0.1mol/L stannous chloride (SnCl) 2 .2H 2 O) ethanol solution, spin-coating the solution on the FTO substrate layer at 3000rpm for 40s during the spin-coating process. And then annealing the prepared film in air at 180 ℃ for 1h to obtain the tin dioxide electron transport layer, wherein the thickness of the tin dioxide electron transport layer is 15 nm.
(3) Preparation of CH 3 NH 3 PbI 3 Perovskite light-absorbing layer
At N 2 In the ambient, 461mg of lead iodide (PbI) 2 ) 159mg of methylammonium iodide (CH) 3 NH 3 I) And 78mg of dimethyl sulfoxide (DMSO) were mixed and dissolved in 600mg of Dimethylformamide (DMF), and the mixture was stirred at room temperature for 1 hour to form a solution. And (3) spin-coating 100 mu L of the solution on the tin dioxide electron transport layer by using a spin coater, wherein the rotation speed is 4000rpm and the time is 20s in the spin-coating process, and 0.5mL of diethyl ether or 0.3mL of chlorobenzene is added in the spin-coating process to improve the quality of the film. The obtained CH is 3 NH 3 PbI 3 Annealing the film at 65 deg.C for 2min, and annealing at 100 deg.C for 5min to obtain CH 3 NH 3 PbI 3 A perovskite light absorbing layer having a thickness of 600 nm.
(4) Preparation of Schiff base metal complex hole transport layer
Preparing the hollow body on the surface of the perovskite light absorption layer by adopting a high vacuum thermal evaporation methodHole transport layer at 1 × 10 -6 At a vacuum degree of Pa, to
Figure BDA0002755839410000132
The schiff base metal complex prepared in example 1 was evaporated at a rate of (v) to form a hole transport layer, and the thickness of the hole transport layer was controlled to be 80 nm.
(5) Preparation of gold electrode layer
Preparing a gold electrode layer on the surface of the hole transport layer by high vacuum thermal evaporation method at 1 × 10 -6 At a vacuum degree of Pa, to
Figure BDA0002755839410000133
And preparing a gold electrode layer by means of rate evaporation deposition, and controlling the thickness of the electrode layer to be 100nm to obtain the perovskite solar cell of the embodiment.
Examples 11 to 18
The perovskite solar cell fabrication processes of examples 11-18 are similar to the perovskite solar cell fabrication process of example 10, except that: the hole transport layer is of a different material. The materials of the hole transport layers of examples 11 to 18 are shown in table 2 below:
table 2 hole transport layer materials for perovskite solar cells of examples 11 to 18
Figure BDA0002755839410000131
Figure BDA0002755839410000141
Comparative example 1
The perovskite solar cell of comparative example 1 was fabricated in a similar process to that of example 10, except that: the hole transport layer is made of different materials and different preparation processes. Comparative example 1 a material having as a hole transport layer spiro-OMeTAD (2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene); the preparation process of the spiro-OMeTAD hole transport layer is as follows:
in N 2 A100 mg/mL solution of spiro-OMeTAD in chlorobenzene was prepared and 15.92mL of 4-tert-butylpyridine and 9.68mL of a 520mg/mL solution of lithium bis (trifluoromethanesulfonyl) imide in acetonitrile were added directly to 0.3mL of the above solution, respectively. Spin-coating the obtained solution on a perovskite light absorption layer by using a spin coater to form a film, wherein the rotating speed is 4000rpm, the time is 45s, and the thickness of a spiro-OMeTAD hole transport layer is controlled to be 80 nm.
Comparative example 2
The preparation process of the schiff base metal complex of comparative example 2 is similar to that of example 1 except that: in comparative example 2, unsubstituted o-phenylenediamine was used.
Comparative example 3
The perovskite solar cell of comparative example 3 was fabricated in a similar process to that of example 10, except that: the hole transport layer is of a different material. Comparative example 3 the material of the hole transport layer was the schiff s base metal complex prepared in comparative example 2.
The following are test sections:
the perovskite solar cell devices of the above examples and comparative examples had an effective area of 0.08cm 2 . And (3) testing conditions: spectral distribution AM1.5G, illumination intensity 100mW/cm 2 AAA solar simulator (tokoro, tokyo), J-V curve was measured with Keithly model 2400 digital source meter, all devices were simply packaged with uv glue and tested for normal measurement in atmospheric environment.
Fig. 2 is a scanning electron micrograph of a hole transport layer in the perovskite solar cell obtained in example 10. As can be seen from FIG. 2, the Schiff base metal complex hole transport layer has a uniform and compact surface morphology.
Fig. 3 is an I-V curve of the perovskite solar cell obtained in example 10. As calculated from the I-V curve of FIG. 3, the perovskite solar cell obtained in example 10 had an open-circuit voltage of 1.07V and a short-circuit current density of 22.7mA/cm 2 The fill factor was 62% and the conversion efficiency was 15.24%.
Open circuit voltage, short circuit current, fill factor, and conversion efficiency data for the perovskite solar cells of examples 11-18 and comparative example 3 are shown in table 3 below.
TABLE 3
Figure BDA0002755839410000151
Fig. 4 is a graph showing the change of the photoelectric conversion efficiency of the perovskite solar cell obtained in example 10 in the air with time. As can be seen from fig. 4, the device maintained 80% or more of the initial efficiency after being stored in the atmospheric environment for 1100 hours. Experiments prove that the change curves of the photoelectric conversion efficiency of the perovskite solar cells of the examples 11 to 18 in the air are approximately the same as those of the perovskite solar cells of the example 10 along with the time. The perovskite solar cells of examples 11 to 18 maintained 80% or more of the initial efficiency after being left in air for 1100 hours.
Fig. 5 is a graph showing the change of the photoelectric conversion efficiency of the perovskite solar cell obtained in comparative example 1 in air with time. As can be seen from fig. 5, the efficiency of the device is attenuated significantly in the atmospheric environment, and the efficiency is reduced to less than 50% of the initial efficiency after 600 h.
The perovskite solar cell prepared in comparative example 3 was left in air for 1100h, and the efficiency was reduced to below 60% of the initial efficiency.
The experimental data show that the Schiff base metal complex is used as the hole transport material of the perovskite solar cell, so that the cost is low, and the stability and the service life of the device of the perovskite solar cell can be improved.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent should be subject to the appended claims.

Claims (11)

1. A schiff base metal complex characterized by having the structural formula shown below:
Figure FDA0003595851380000011
wherein M is a divalent metal ion, R 1 、R 2 、R 3 And R 4 Each independently selected from hydrogen or alkoxy, and R 1 、R 2 、R 3 And R 4 At least one of them is alkoxy, the described alkoxy is-OCH 3 、-OC 2 H 5 or-OC 3 H 7 。
2. Schiff base metal complex according to claim 1, wherein M is Co 2+ 、Cu 2+ 、Zn 2+ 、Ni 2+ 、Pt 2+ 、Pd 2+ 、Pb 2+ 、Sn 2+ Or Mn 2 。
3. A preparation method of Schiff base metal complexes is characterized by comprising the following steps: mixing substituted o-phenylenediamine, divalent metal salt, pyrrole-2-formaldehyde and an organic solvent for reaction to prepare a Schiff base metal complex, wherein the divalent metal salt can be dissolved in the organic solvent, and the structural formula of the substituted o-phenylenediamine is shown in the specification
Figure FDA0003595851380000012
The structural formula of the Schiff base metal complex is shown as
Figure FDA0003595851380000013
Wherein M is a divalent metal ion, R 1 、R 2 、R 3 And R 4 Each independently selected from hydrogen or alkoxy, and R 1 、R 2 、R 3 And R 4 At least one of them is alkoxy, the described alkoxy is-OCH 3 、-OC 2 H 5 or-OC 3 H 7 。
4. A process for the preparation of schiff base metal complexes as claimed in claim 3, wherein the divalent metal salt is acetate or chloride; and/or the metal ion in the divalent metal salt is Co 2+ 、Cu 2+ 、Zn 2+ 、Ni 2+ 、Pt 2+ 、Pd 2+ 、Pb 2+ 、Sn 2+ Or Mn 2 。
5. A process for producing a Schiff base metal complex according to claim 3 or 4, wherein the molar ratio of the substituted o-phenylenediamine, the metal ion in the divalent metal salt and the pyrrole-2-carbaldehyde is (1-1.5): (1-1.2): (2-3); and/or the organic solvent is at least one selected from ethanol, chloroform, dimethylformamide and dimethyl sulfoxide; and/or the reaction temperature is 10-80 ℃, and the reaction time is 2-15 h.
6. A perovskite solar cell is characterized by comprising a substrate layer, an electron transport layer, a perovskite light absorption layer, a hole transport layer and an electrode layer which are arranged in a stacked mode, wherein the hole transport layer is made of the Schiff base metal complex as defined in any one of claims 1-2.
7. The perovskite solar cell of claim 6, wherein the substrate layer is FTO, and the substrate layer has a thickness of 5nm to 20 nm; and/or the material of the electron transmission layer is tin dioxide, and the thickness of the electron transmission layerThe temperature is 5 nm-30 nm; and/or the perovskite light absorption layer is made of CH 3 NH 3 PbI 3 The thickness of the perovskite light absorption layer is 100 nm-800 nm; and/or the thickness of the hole transport layer is 30 nm-100 nm; and/or the electrode layer is made of gold, and the thickness of the electrode layer is 30 nm-150 nm.
8. A preparation method of a perovskite solar cell is characterized by comprising the following steps: an electron transport layer, a perovskite light absorption layer, a hole transport layer and an electrode layer are sequentially formed on the substrate layer, and the material of the hole transport layer is the Schiff base metal complex as claimed in any one of claims 1-2.
9. The method for manufacturing a perovskite solar cell according to claim 8, wherein the hole transport layer is formed by a vacuum evaporation method or a liquid phase spin coating method.
10. The method of manufacturing a perovskite solar cell as claimed in claim 9, wherein the rate of vacuum evaporation is
Figure FDA0003595851380000021
11. The method for preparing a perovskite solar cell according to claims 8 to 10, wherein the material of the electron transport layer is tin dioxide, and the step of forming the electron transport layer comprises: spin-coating an ethanol solution of stannous chloride on the substrate layer, and then carrying out annealing treatment to form the electron transport layer; and/or;
the electrode layer is made of gold, and the step of forming the electrode layer comprises the following steps: evaporating gold on the side of the hole transport layer away from the substrate layer to form the electrode layer; and/or the presence of a catalyst in the reaction mixture,
the perovskite light absorption layer is made of CH 3 NH 3 PbI 3 The step of forming the perovskite light absorption layer comprises: at the far side of the electron transport layerAnd spin-coating a mixed solution of lead iodide, methyl ammonium iodide, dimethyl sulfoxide and dimethyl formamide on one side of the substrate layer, and then carrying out annealing treatment to form the perovskite light absorption layer.
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