CN114695681A - Tin-based perovskite solar cell, preparation method and green solvent system - Google Patents

Tin-based perovskite solar cell, preparation method and green solvent system Download PDF

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CN114695681A
CN114695681A CN202210327040.1A CN202210327040A CN114695681A CN 114695681 A CN114695681 A CN 114695681A CN 202210327040 A CN202210327040 A CN 202210327040A CN 114695681 A CN114695681 A CN 114695681A
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perovskite
spin
coating
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solar cell
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郝锋
何良刚
唐直月
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University of Electronic Science and Technology of China
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    • H—ELECTRICITY
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    • 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
    • H—ELECTRICITY
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    • 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
    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • 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
    • H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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Abstract

The invention provides a green solvent system for preparing a tin-based perovskite solar cell and a preparation method of the cell. The low-toxicity solvent and stannous iodide have weak coordination, and can induce the precursor solution to be rapidly crystallized in the spin coating process. The tin-based perovskite solar cell prepared based on the green solvent system has the advantages of low cost, simple preparation process, low toxicity, environmental friendliness, small damage to the health of organisms, high photoelectric conversion efficiency and large-scale production, manufacture and application prospects.

Description

Tin-based perovskite solar cell, preparation method and green solvent system
Technical Field
The invention belongs to the field of perovskite solar cells, relates to a green solvent system for efficient tin-based perovskite solar cells, and particularly relates to a green solvent for preparing a perovskite layer of a tin-based perovskite solar cell, a preparation method of the tin-based perovskite solar cell and the obtained tin-based perovskite solar cell.
Background
The world has become increasingly dependent on burning fossil fuels, which are slowly depleting and emitting harmful gases into the atmosphere. At present, the development of new energy is mainly focused on renewable energy sources such as solar energy, wind energy, hydrogen energy and the like. Among numerous new energy sources, solar energy is receiving attention with the advantages of abundant reserves, wide distribution, renewability and the like. The utilization of renewable energy solar energy can solve energy sustainability issues and negative environmental impacts. The solar cell can directly convert inexhaustible solar energy into electric energy. Crystalline silicon solar cells dominate the market, but factors such as expensive manufacturing process and expensive raw materials have prompted researchers to propose a new photovoltaic technology that combines high efficiency and low cost manufacturing. Perovskite Solar Cells (PSCs) do not require any complex processing conditions and they can be synthesized in the laboratory using wet chemistry methods with the aid of simple, low-cost techniques such as spin coating, dip coating, screen printing, bipolar source evaporation techniques, etc. PSCs are of great interest because of their ease of preparation in solution and superior photovoltaic performance. The Power Conversion Efficiency (PCE) of PSCs has increased from 3.8% to 25.7% over more than a decade, making it a potential leading force for the next generation of sustainable energy.
In addition to the unique properties of perovskites themselves, innovation in the preparation of high quality perovskite thin films is another important driving force for rapid progress of PCE. Among all methods for preparing perovskite thin films, solvent engineering techniques have become an important method for preparing high-quality perovskite thin films. In a typical solvent engineering approach, a perovskite precursor solution is usually prepared using a mixture of N, N-Dimethylformamide (DMF) as a host solvent due to its excellent solubility, and Dimethylsulfoxide (DMSO) as a ligand solvent due to its strong coordination ability. The solvent engineering technology is a breakthrough for realizing high-performance PSCs. However, solvent engineering strongly relies on the use of toxic solvents, such as DMF and Chlorobenzene (CB). With the commercialization of PSCs, these toxic solvents may pose a threat to production health and environmental safety, which has hindered their large-scale production and use. Therefore, it is urgently required to simultaneously screen green solvents to prepare high-quality perovskite thin films, so as to prepare efficient solar cells, thereby ensuring the production health and environmental safety.
Disclosure of Invention
Aiming at the problems in the background technology of the invention, a green solvent is provided for preparing a tin-based perovskite solar cell. According to the invention, a toxic solvent dimethyl formamide (DMF) of a perovskite precursor solution is replaced by a green solvent diethyl formamide (DEF) or gamma-butyrolactone (GBL) or Acetonitrile (ACN) or ethanol (EtOH), so that the high-efficiency tin-based perovskite solar cell is prepared, and the large-scale production and application of the future perovskite solar cell are favorably met.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a green solvent system for preparing a tin-based perovskite solar cell comprises a conductive substrate, a hole transport layer, a perovskite light absorption layer, an electron transport layer, a buffer layer and a counter electrode from bottom to top, wherein a perovskite precursor solvent for forming the perovskite light absorption layer is a nontoxic solvent mixed by diethylformamide and dimethyl sulfoxide, or a nontoxic solvent mixed by gamma butyrolactone and dimethyl sulfoxide, or a nontoxic solvent mixed by acetonitrile and dimethyl sulfoxide, or a nontoxic solvent mixed by ethanol and dimethyl sulfoxide.
Preferably, the volume ratio of diethylformamide to dimethyl sulfoxide is 4:1 or 6:4, the volume ratio of gamma-butyrolactone to dimethyl sulfoxide is 4:1, the volume ratio of acetonitrile to dimethyl sulfoxide is 4:1, and the volume ratio of ethanol to dimethyl sulfoxide is 4: 1.
Preferably, the light absorbing layer comprises a raw material for forming the perovskite light absorbing layer and the perovskite precursor solvent; the raw materials for forming the light-absorbing layer of the perovskite layer comprise formamidine iodine FAI, methylamine bromine MABr and stannous iodide SnI2SnF (stannous fluoride)2And phenethylamine iodide salt PEAI.
Preferably, the perovskite light absorption layer has the component of FA0.75MA0.25SnI2.75Br0.25Or FASnI3The concentration of FAI is 0.5-0.9M, the concentration of MABr is 0.16-0.3M, SnI2The concentration of (A) is 0.67-1M, SnF2The concentration of the PEAI is 0.1-0.18M and the concentration of the PEAI is 0.1-0.18M.
The invention also provides a preparation method of the tin-based perovskite solar cell, which adopts the green solvent system and comprises the following steps: the method comprises the steps of firstly spin-coating a hole transport layer on a substrate, then spin-coating a perovskite light absorption layer, then spin-coating an electron transport layer, then spin-coating a buffer layer, and finally evaporating a metal electrode.
Preferably, the hole transport layer comprises NiOxPEDOT is a PSS layer; PSS hole transport layer of the spin-coating PEDOT comprises the following process parameters: 1000-4000 rpm; the annealing process parameters are as follows: the annealing temperature is 80-100 ℃, and the annealing temperature is 80-140 ℃.
As a preferred mode, the perovskite light absorption layer spin coating process parameters are as follows: rotating at 6000-9000 rpm for 60-80 s; the annealing process parameters are as follows: the annealing temperature is 70-100 ℃, and the time is 10-15 min.
As a preferable mode, the perovskite intrinsic light absorption layer is required to be dripped with an anti-solvent chlorobenzene or toluene in a spin coating mode.
Preferably, the hole transport layer is PC61BM, and/or the buffer layer is BCP material, and/or the electrode is silver or aluminum.
The invention also provides a tin-based perovskite solar cell prepared by the green solvent system.
The invention provides a green solvent DEF or GBL or ACN or EtOH for preparing a tin-based perovskite solar cell, a preparation method of a perovskite layer of the tin-based perovskite solar cell and the tin-based perovskite solar cell. The method for preparing the tin-based perovskite solar cell by adopting the green solvent is beneficial to meeting the environmental requirements, and has important significance for preparing the perovskite solar cell by green chemistry.
The invention has the beneficial effects that: compared with the prior art, the method solves the problems that the solvent (DMF) for preparing the perovskite of the tin-based perovskite solar cell at present still has toxicity and is not in accordance with green chemistry, and the tin-based perovskite solar cell prepared by the toxic solvent is not beneficial to large-scale production and application. The invention creatively provides that a toxic solvent DMF is replaced by a green solvent DEF or GBL or ACN or EtOH, and not only can a PCE equivalent to a DMF device be prepared, but also the invention is more environment-friendly. PSCs prepared by using DEF or GBL or ACN or EtOH solvents have important significance for industrial mass production and promotion of commercialization of tin-based perovskite solar cells. Experimental results show that the efficiency of the tin-based perovskite solar cell prepared by the green solvent provided by the invention can be comparable to that of a device prepared by a conventional toxic solvent.
Drawings
FIG. 1 is a dynamic light scattering spectrum of a perovskite precursor solution of the present invention using DEF and DMF as solvents, respectively;
FIG. 2 shows DEF, DMF and SnI added to them2A post Fourier infrared spectrogram;
FIG. 3 is an X-ray diffraction pattern of a perovskite precursor solution of the present invention using DEF and DMF as solvents, respectively, after spin coating for 60s without annealing;
FIG. 4 is a graph of photoelectric property tests performed at the same scanning rate for example 1 and comparative example 1;
FIG. 5 is an X-ray diffraction pattern of perovskite thin films of example 1 and comparative example 1;
FIG. 6 is a graph of photoelectric properties measured at the same scanning rate for example 2 and comparative example 2;
FIG. 7 is an X-ray diffraction pattern of the perovskite thin films of example 2 and comparative example 2.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
The embodiment provides a green solvent system for preparing a tin-based perovskite solar cell, the perovskite solar cell structurally comprises a conductive substrate, a hole transport layer, a perovskite light absorption layer, an electron transport layer, a buffer layer and a counter electrode from bottom to top, and perovskite precursor solvents for forming the perovskite light absorption layer are non-toxic solvents mixed by diethylformamide DEF and dimethyl sulfoxide DMSO, or non-toxic solvents mixed by gamma butyrolactone GBL and dimethyl sulfoxide DMSO, or non-toxic solvents mixed by acetonitrile ACN and dimethyl sulfoxide DMSO, or non-toxic solvents mixed by ethanol EtOH and dimethyl sulfoxide DMSO.
The volume ratio of the diethyl formamide to the dimethyl sulfoxide is 4:1 or 6:4, the volume ratio of the gamma butyrolactone to the dimethyl sulfoxide is 4:1, the volume ratio of the acetonitrile to the dimethyl sulfoxide is 4:1, and the volume ratio of the ethanol to the dimethyl sulfoxide is 4: 1.
The green solvent system comprises a raw material for forming the perovskite light absorption layer and the perovskite precursor solvent; the raw materials for forming the light-absorbing layer of the perovskite layer comprise formamidine iodine FAI, methylamine bromine MABr and stannous iodide SnI2SnF (stannous fluoride)2And phenethylamine iodide salt PEAI.
The perovskite light absorption layer has the component of FA0.75MA0.25SnI2.75Br0.25Or FASnI3The concentration of FAI is 0.5-0.9M, the concentration of MABr is 0.16-0.3M, SnI2The concentration of (A) is 0.67-1M, SnF2The concentration of the PEAI is 0.1-0.18M and the concentration of the PEAI is 0.1-0.18M.
The embodiment also provides a preparation method of the tin-based perovskite solar cell, which adopts the green solvent system and comprises the following steps: the method comprises the steps of firstly spin-coating a hole transport layer on a substrate, then spin-coating a perovskite light absorption layer, then spin-coating an electron transport layer, then spin-coating a buffer layer, and finally evaporating a metal electrode.
The hole transport layer comprises NiOxPEDOT is a PSS layer; the technological parameters of the spin-coating PEDOT-PSS hole transport layer are as follows: 1000-4000 rpm; the annealing process parameters are as follows: the annealing temperature is 80-100 ℃, and the annealing temperature is 80-140 ℃.
The perovskite light absorption layer spin coating process parameters are as follows: rotating at 6000-9000 rpm for 60-80 s; the annealing process parameters are as follows: the annealing temperature is 70-100 ℃, and the time is 10-15 min.
And adding an anti-solvent chlorobenzene or toluene dropwise in the spin coating of the perovskite intrinsic light absorption layer.
The hole transport layer is PC61BM, and/or the buffer layer is BCP material, and/or the electrode is silver or aluminum.
The embodiment also provides a tin-based perovskite solar cell prepared by the green solvent system.
Example 1
The embodiment provides a green solvent system for preparing a tin-based perovskite solar cell, the perovskite solar cell structurally comprises a conductive substrate, a hole transport layer, a perovskite light absorption layer, an electron transport layer, a buffer layer and a counter electrode from bottom to top, and a perovskite precursor solvent for forming the perovskite light absorption layer is a non-toxic solvent mixed by diethylformamide DEF and dimethyl sulfoxide DMSO.
The volume ratio of the diethyl formamide to the dimethyl sulfoxide is 4:1 or 6:4,
the green solvent system comprises a raw material for forming a perovskite light absorption layer and the perovskite precursor solvent; the raw materials for forming the light-absorbing layer of the perovskite layer comprise formamidine iodine FAI, methylamine bromine MABr and stannous iodide SnI2SnF (stannous fluoride)2And phenethylamine iodide salt PEAI.
The perovskite light absorption layer has the component of FA0.75MA0.25SnI2.75Br0.25Or FASnI3The concentration of FAI is 0.5-0.9M, the concentration of MABr is 0.16-0.3M, SnI2The concentration of (A) is 0.67-1M, SnF2The concentration of the PEAI is 0.1-0.18M and the concentration of the PEAI is 0.1-0.18M.
The embodiment also provides a preparation method of the tin-based perovskite solar cell, which adopts the green solvent system and comprises the following steps: the method comprises the steps of firstly spin-coating a hole transport layer on a substrate, then spin-coating a perovskite light absorption layer, then spin-coating an electron transport layer, then spin-coating a buffer layer, and finally evaporating a metal electrode.
In this example, ITO is used as the substrate, PEDOT: PSS is used as the hole transport layer, FA0.75MA0.25SnI2.75Br0.25Is perovskite light absorption layer, PCBM is electronThe preparation method of the perovskite solar cell with the transmission layer, BCP as a buffer layer and silver as a counter electrode comprises the following steps:
the method comprises the following steps: cleaning the surface of the purchased ITO glass by using deionized water, absolute ethyl alcohol, acetone and isopropanol in sequence, and drying the ITO glass by using nitrogen for later use;
step two: and (4) putting the ITO in the step one into ultraviolet ozone for 15 minutes. Taking 90 mu L of PEDOT, namely PSS solution to spin on ITO conductive glass, spin-coating for 50s at the speed of 3000rpm, and then putting on a heating table at 100 ℃ to anneal for 10 min;
step three: 1.2M of SnI20.9M FAI, 0.3M MABr, 0.18M SnF20.18M PEAI and 6mg/mL Sn powder. Adding a DEF/DMSO (v: v ═ 4:1) mixed solvent to prepare a 1.2M perovskite precursor solution;
step four: dropwise adding 50 mu L of perovskite precursor solution on the hole transport layer obtained in the step three to completely cover the hole transport layer, spin-coating at 6000rpm for 60s, dropwise adding chlorobenzene after 15s, and then transferring the hole transport layer to a heating table at 80 ℃ for annealing for 10 minutes;
step five: spin coating PC on the perovskite layer obtained in the fourth step61BM Electron transport layer, PC6120mg/mL PC of BM spin coating solution61BM chlorobenzene solution. Spin-coating at 2000r/min for 30 s;
step six: spin-coating BCP on the surface of the electron transport layer obtained in the fifth step, wherein the BCP is 1mg/ml isopropanol solution, spin-coating at 6000rpm for 30s, and annealing for 10 minutes after the spin-coating is finished to obtain a buffer layer;
step seven: evaporating to coat with a thickness of 100 nm and an effective area of 0.096cm2The metallic silver electrode of (1).
Comparative example 1
Using ITO as substrate, PEDOT PSS as hole transport layer, FA0.75MA0.25SnI2.75Br0.25The preparation method of the perovskite solar cell comprises the following steps of (1) taking a light absorption layer, PCBM as an electron transmission layer, BCP as a buffer layer and silver as a counter electrode:
the method comprises the following steps: cleaning the surface of the purchased ITO glass by using deionized water, absolute ethyl alcohol, acetone and isopropanol in sequence, and drying the ITO glass by using nitrogen for later use;
step two: and (4) putting the ITO in the step one into ultraviolet ozone for 15 minutes. Taking 90 mu L of PEDOT, namely PSS solution to spin on ITO conductive glass, spin-coating for 50s at the speed of 3000rpm, and then putting on a heating table at 100 ℃ to anneal for 10 min;
step three: 1.2M of SnI20.9M FAI, 0.3M MABr, 0.18M SnF20.18M PEAI and 6mg/mL Sn powder. Adding a DMF/DMSO (v: v ═ 4:1) mixed solvent to prepare a 1.2M perovskite precursor solution;
step four: dropwise adding 50 mu L of perovskite precursor solution on the hole transport layer obtained in the step three to completely cover the hole transport layer, spin-coating at 6000rpm for 60s, dropwise adding chlorobenzene after 15s, and then transferring the hole transport layer to a heating table at 80 ℃ for annealing for 10 minutes;
step five: spin-coating PC on the perovskite layer obtained in the fourth step61BM Electron transport layer, PC6120mg/mL PC of BM spin coating solution61BM chlorobenzene solution. Spin-coating at 2000r/min for 30 s;
step six: spin-coating BCP on the surface of the electron transport layer obtained in the fifth step, wherein the BCP is 1mg/ml isopropanol solution, spin-coating for 30s at 6000rpm, and annealing for 10 minutes after the spin-coating is finished to obtain a buffer layer;
step seven: evaporating to obtain a film with a thickness of 100 nm and an effective area of 0.096cm2The metallic silver electrode of (3).
Performance comparison
FIG. 1 is a dynamic light scattering spectra of a perovskite precursor solution; the results shown in the figure are pure DEF and pure DMF as solvents, respectively. As can be seen from fig. 1, green solvent DEF can increase the colloidal particle size of the precursor and make the distribution more uniform. FIG. 2 shows DEF, DMF and SnI added to the two solutions2The later infrared spectrogram; as can be seen from FIG. 2, after adding SnI2After that, both DEF and DMF had only a small angular shift from C ═ O bond, indicating that both are SnI2The coordination of (A) is weak. FIG. 3 is an X-ray diffraction pattern; the results shown in the figure are obtained by spin-coating the precursor solution on a conductive substrate without dropping during the spin-coating process, using pure DEF and pure DMF as solvents, respectivelyAnti-solvent, and subsequently not annealed. As shown in FIG. 3, DEF and SnI2The weak coordination of (2) enables a perovskite precursor prepared from DEF to generate more nucleation sites in the spin coating process, and a better crystallization effect than DMF (dimethyl formamide) is obtained before anti-solvent is not dripped and annealing is not carried out. Fig. 4 shows the X-ray diffraction patterns of example 1 and comparative example 1, and as can be seen from fig. 4, the X-ray diffraction patterns of example 1 and comparative example 1 have substantially the same intensity, indicating that the perovskite thin film of example 1 is equivalent to the perovskite thin film of comparative example 1 in terms of crystallization. FIG. 5 is a graph comparing the IV curves of the perovskite solar cells obtained in example 1 and comparative example 1; the light-absorbing layer of the perovskite solar cell obtained in example 1 and the light-absorbing layer of the perovskite solar cell obtained in comparative example 1 were respectively subjected to a reaction at AM1.5G,100mW/cm2The xenon lamp is used for carrying out IV test under irradiation, wherein the scanning voltage is 0-1.2V, and the scanning speed is 10 mV/s. As can be seen from fig. 5, at the same scanning speed, the perovskite solar cell of example 1 is substantially equivalent to the perovskite solar cell of comparative example 1 in terms of open-circuit voltage, short-circuit current and fill factor, so that the photoelectric conversion efficiency of the devices of the two cells is substantially the same. It is shown that the performance of example 1 prepared by using a green solvent can be compared favorably with that of comparative example 1 prepared by using a toxic solvent on the premise of reducing toxicity and being environment-friendly.
Figure BDA0003573926160000061
Example 2
The embodiment provides a green solvent system for preparing a tin-based perovskite solar cell, the perovskite solar cell structurally comprises a conductive substrate, a hole transport layer, a perovskite light absorption layer, an electron transport layer, a buffer layer and a counter electrode from bottom to top, a perovskite precursor solvent for forming the perovskite light absorption layer is a non-toxic solvent mixed by diethylformamide DEF and dimethyl sulfoxide DMSO,
the volume ratio of the diethyl formamide to the dimethyl sulfoxide is 6:4,
the green solvent system comprises a raw material for forming a perovskite light absorption layer and a perovskite precursorA solvent; the raw materials for forming the light-absorbing layer of the perovskite layer comprise formamidine iodine FAI, methylamine bromine MABr and stannous iodide SnI2SnF (stannous fluoride)2And phenethylamine iodide salt PEAI.
The perovskite light absorption layer has the component of FA0.75MA0.25SnI2.75Br0.25Or FASnI3The concentration of FAI is 0.5-0.9M, the concentration of MABr is 0.16-0.3M, SnI2The concentration of (A) is 0.67-1M, SnF2The concentration of the PEAI is 0.1-0.18M and the concentration of the PEAI is 0.1-0.18M.
The embodiment also provides a preparation method of the tin-based perovskite solar cell, which adopts the green solvent system and comprises the following steps: the method comprises the steps of firstly spin-coating a hole transport layer on a substrate, then spin-coating a perovskite light absorption layer, then spin-coating an electron transport layer, then spin-coating a buffer layer, and finally evaporating a metal electrode.
In this example, ITO is used as the substrate, PEDOT: PSS is used as the hole transport layer, FA0.75MA0.25SnI2.75Br0.25Is a light absorbing layer, PC61The preparation method of the perovskite solar cell with BM as an electron transport layer, BCP as a buffer layer and silver as a counter electrode comprises the following steps:
the method comprises the following steps: cleaning the surface of the purchased ITO glass by using deionized water, absolute ethyl alcohol, acetone and isopropanol in sequence, and drying the ITO glass by using nitrogen for later use;
step two: and (4) putting the ITO in the step one into ultraviolet ozone for 15 minutes. Taking 90 mu L of PEDOT, namely, spin-coating PSS solution on ITO conductive glass, spin-coating 50s at the speed of 3000rpm, and then annealing for 10 minutes on a heating table at the temperature of 80 ℃;
step three: 1.2M of SnI20.9M FAI, 0.3M MABr, 0.18M SnF20.18M PEAI and 6mg/mL Sn powder. Adding a DEF/DMSO (v: v ═ 6:4) mixed solvent to prepare a 1.2M perovskite precursor solution;
step four: dropwise adding 50 mu L of perovskite precursor solution on the hole transport layer obtained in the step three to completely cover the hole transport layer, spin-coating at 6000rpm for 60s, dropwise adding chlorobenzene after 15s, and then transferring the hole transport layer to a heating table at 80 ℃ for annealing for 10 minutes;
step five: spin coating PC on the perovskite layer obtained in the fourth step61BM Electron transport layer, PC61BM spin-coating solution is 20mg/mL PC61BM chlorobenzene solution. Spin-coating at 2000r/min for 30 s;
step six: spin-coating BCP on the surface of the electron transport layer obtained in the fifth step, wherein the BCP is 1mg/ml isopropanol solution, spin-coating at 6000rpm for 30s, and annealing for 10 minutes after the spin-coating is finished to obtain a buffer layer;
step seven: evaporating to obtain a film with a thickness of 100 nm and an effective area of 0.096cm2The metallic silver electrode of (1).
Comparative example 2
Using ITO as substrate, PEDOT PSS as hole transport layer, FA0.75MA0.25SnI2.75Br0.25The preparation method of the perovskite solar cell comprises the following steps of (1) taking a light absorption layer, PCBM as an electron transport layer, BCP as a buffer layer and silver as a counter electrode:
the method comprises the following steps: cleaning the surface of the purchased ITO glass by using deionized water, absolute ethyl alcohol, acetone and isopropanol in sequence, and drying the ITO glass by using nitrogen for later use;
step two: and (4) putting the ITO in the step one into ultraviolet ozone for 15 minutes. Taking 90 mu L of PEDOT, namely PSS solution to spin on ITO conductive glass, spin-coating for 50s at the speed of 3000rpm, and then putting on a heating table at the temperature of 80 ℃ to anneal for 10 minutes;
step three: 1.2M of SnI20.9M FAI, 0.3M MABr, 0.18M SnF20.18M PEAI and 6mg/mL Sn powder. Adding a DMF/DMSO (v: v ═ 6:4) mixed solvent to prepare a 1.2M perovskite precursor solution;
step four: dropwise adding 50 mu L of perovskite precursor solution on the hole transport layer obtained in the step three to completely cover the hole transport layer, spin-coating at 6000rpm for 60s, dropwise adding chlorobenzene after 15s, and then transferring the hole transport layer to a heating table at 80 ℃ for annealing for 10 minutes;
step five: spin coating PC on the perovskite layer obtained in the fourth step61BM Electron transport layer, PC6120mg/mL PC of BM spin coating solution61BM chlorobenzene solution. Spin-coating at 2000r/min for 30 s;
step six: spin-coating BCP on the surface of the electron transport layer obtained in the fifth step, wherein the BCP is 1mg/ml isopropanol solution, spin-coating at 6000rpm for 30s, and annealing for 10 minutes after the spin-coating is finished to obtain a buffer layer;
step seven: evaporating to coat with a thickness of 100 nm and an effective area of 0.096cm2The metallic silver electrode of (1).
Performance comparison
FIG. 6 is a graph comparing the IV curves of the perovskite solar cells obtained in example 2 and comparative example 2; the light absorbing layers of the perovskite solar cells obtained in example 2 and comparative example 2 were respectively prepared at AM1.5G,100mW/cm2The xenon lamp is used for carrying out IV test under irradiation, wherein the scanning voltage is 0-1.2V, and the scanning speed is 10 mV/s. As can be seen from fig. 6, the perovskite solar cell of example 2 is equivalent to the perovskite solar cell of comparative example 2 in terms of open-circuit voltage, short-circuit current, and fill factor at the same scanning speed, and the photoelectric conversion efficiency is substantially the same. Fig. 7 shows the X-ray diffraction patterns of example 2 and comparative example 2, and it can be seen from fig. 7 that the X-ray diffraction patterns of example 2 and comparative example 2 have substantially the same intensity, indicating that the perovskite thin film of example 2 is equivalent to the perovskite thin film of comparative example 2 in crystallization. It is shown that the example 2 prepared by using the green solvent not only has the characteristics of low toxicity, environmental friendliness and the like, but also can be compared favorably with the comparative example 2 prepared by using the toxic solvent in the aspect of photoelectric conversion efficiency.
Figure BDA0003573926160000081
Example 3
The embodiment provides a green solvent system for preparing a tin-based perovskite solar cell, the perovskite solar cell structurally comprises a conductive substrate, a hole transport layer, a perovskite light absorption layer, an electron transport layer, a buffer layer and a counter electrode from bottom to top, a perovskite precursor solvent for forming the perovskite light absorption layer is a nontoxic solvent mixed by gamma butyrolactone GBL and dimethyl sulfoxide DMSO,
the perovskite precursor solvent is gamma butyrolactone GBL and dimethyl sulfoxide DMSO with the volume ratio of 4: 1.
The green solvent system comprises a raw material for forming the perovskite light absorption layer and the perovskite precursor solvent; the raw materials for forming the light-absorbing layer of the perovskite layer comprise formamidine iodine FAI, methylamine bromine MABr and stannous iodide SnI2SnF (stannous fluoride)2And phenethylamine iodide salt PEAI.
The perovskite light absorption layer has the component of FA0.75MA0.25SnI2.75Br0.25Or FASnI3The concentration of FAI is 0.5-0.9M, the concentration of MABr is 0.16-0.3M, SnI2The concentration of (A) is 0.67-1M, SnF2The concentration of the (B) is 0.1-0.18M, and the PEAI concentration is 0.1-0.18M.
The embodiment also provides a preparation method of the tin-based perovskite solar cell, which adopts the green solvent system and comprises the following steps: the method comprises the steps of firstly spin-coating a hole transport layer on a substrate, then spin-coating a perovskite light absorption layer, then spin-coating an electron transport layer, then spin-coating a buffer layer, and finally evaporating a metal electrode.
In this example, ITO is used as the substrate, PEDOT: PSS is used as the hole transport layer, FA0.75MA0.25SnI2.75Br0.25Is a light absorbing layer, PC61The preparation method of the perovskite solar cell with BM as an electron transport layer, BCP as a buffer layer and silver as a counter electrode comprises the following steps:
the method comprises the following steps: cleaning the surface of the purchased ITO glass by using deionized water, absolute ethyl alcohol, acetone and isopropanol in sequence, and drying the ITO glass by using nitrogen for later use;
step two: and (4) putting the ITO in the step one into ultraviolet ozone for 15 minutes. Taking 90 mu L of PEDOT, namely, spin-coating PSS solution on ITO conductive glass, spin-coating 50s at the speed of 3000rpm, and then annealing for 10 minutes on a heating table at the temperature of 90 ℃;
step three: 1.2M of SnI20.9M FAI, 0.3M MABr, 0.18M SnF20.18M PEAI and 6mg/mL Sn powder. Adding a gamma butyrolactone GBL/DMSO (v: v ═ 4:1) mixed solvent to prepare a 1.2M perovskite precursor solution;
step four: dropwise adding 50 mu L of perovskite precursor solution on the hole transport layer obtained in the step three to completely cover the hole transport layer, spin-coating at 6000rpm for 60s, dropwise adding chlorobenzene after 15s, and then transferring the hole transport layer to a heating table at 80 ℃ for annealing for 10 minutes;
step five: spin coating PC on the perovskite layer obtained in the fourth step61BM Electron transport layer, PC6120mg/mL PC of BM spin coating solution61BM chlorobenzene solution. Spin-coating at 2000r/min for 30 s;
step six: spin-coating BCP on the surface of the electron transport layer obtained in the fifth step, wherein the BCP is 1mg/ml isopropanol solution, spin-coating for 30s at 6000rpm, and annealing for 10 minutes after the spin-coating is finished to obtain a buffer layer;
step seven: evaporating to coat with a thickness of 100 nm and an effective area of 0.096cm2The metallic silver electrode of (1).
Example 4
The embodiment provides a green solvent system for preparing a tin-based perovskite solar cell, the perovskite solar cell structurally comprises a conductive substrate, a hole transport layer, a perovskite light absorption layer, an electron transport layer, a buffer layer and a counter electrode from bottom to top, and a perovskite precursor solvent for forming the perovskite light absorption layer is a nontoxic solvent mixed by acetonitrile ACN and dimethyl sulfoxide DMSO.
The volume ratio of acetonitrile ACN to dimethyl sulfoxide DMSO is 4: 1.
The green solvent system comprises a raw material for forming the perovskite light absorption layer and the perovskite precursor solvent; the raw materials for forming the light-absorbing layer of the perovskite layer comprise formamidine iodine FAI, methylamine bromine MABr and stannous iodide SnI2SnF (stannous fluoride)2And phenethylamine iodide salt PEAI.
The perovskite light absorption layer has the component of FA0.75MA0.25SnI2.75Br0.25Or FASnI3FAI concentration of 0.5-0.9M, MABr concentration of 0.16-0.3M, SnI2The concentration of (A) is 0.67-1M, SnF2The concentration of the PEAI is 0.1-0.18M and the concentration of the PEAI is 0.1-0.18M.
The embodiment also provides a preparation method of the tin-based perovskite solar cell, which adopts the green solvent system and comprises the following steps: the method comprises the steps of firstly spin-coating a hole transport layer on a substrate, then spin-coating a perovskite light absorption layer, then spin-coating an electron transport layer, then spin-coating a buffer layer, and finally evaporating a metal electrode.
In this example, ITO is used as the substrate, PEDOT: PSS is used as the hole transport layer, FA0.75MA0.25SnI2.75Br0.25Is a light absorbing layer, PC61The preparation method of the perovskite solar cell with BM as an electron transport layer, BCP as a buffer layer and silver as a counter electrode comprises the following steps:
the method comprises the following steps: cleaning the surface of the purchased ITO glass by using deionized water, absolute ethyl alcohol, acetone and isopropanol in sequence, and drying the ITO glass by using nitrogen for later use;
step two: and (4) putting the ITO in the step one into ultraviolet ozone for 15 minutes. Taking 90 mu L of PEDOT, namely PSS solution to spin on ITO conductive glass, spin-coating for 50s at the speed of 3000rpm, and then putting on a heating table at 100 ℃ to anneal for 10 min;
step three: 1.2M of SnI20.9M FAI, 0.3M MABr, 0.18M SnF20.18M PEAI and 6mg/mL Sn powder. Adding an ACN/DMSO (v: v ═ 4:1) mixed solvent to prepare a 1.2M perovskite precursor solution;
step four: dropwise adding 50 mu L of perovskite precursor solution on the hole transport layer obtained in the step three to completely cover the hole transport layer, spin-coating at 6000rpm for 60s, dropwise adding chlorobenzene after 15s, and then transferring the hole transport layer to a heating table at 80 ℃ for annealing for 10 minutes;
step five: spin coating PC on the perovskite layer obtained in the fourth step61BM Electron transport layer, PC6120mg/mL PC of BM spin coating solution61BM chlorobenzene solution. Spin-coating at 2000r/min for 30 s;
step six: spin-coating BCP on the surface of the electron transport layer obtained in the fifth step, wherein the BCP is 1mg/ml isopropanol solution, spin-coating at 6000rpm for 30s, and annealing for 10 minutes after the spin-coating is finished to obtain a buffer layer;
step seven: evaporating to coat with a thickness of 100 nm and an effective area of 0.096cm2The metallic silver electrode of (1).
Example 5
The embodiment provides a green solvent system for preparing a tin-based perovskite solar cell, the perovskite solar cell structurally comprises a conductive substrate, a hole transport layer, a perovskite light absorption layer, an electron transport layer, a buffer layer and a counter electrode from bottom to top, and a perovskite precursor solvent for forming the perovskite light absorption layer is a non-toxic solvent mixed by EtOH and dimethyl sulfoxide DMSO.
The volume ratio of ethanol EtOH to dimethyl sulfoxide DMSO is 4: 1.
The green solvent system comprises a raw material for forming the perovskite light absorption layer and the perovskite precursor solvent; the raw materials for forming the light-absorbing layer of the perovskite layer comprise formamidine iodine FAI, methylamine bromine MABr and stannous iodide SnI2SnF (stannous fluoride)2And phenethylamine iodide salt PEAI.
The perovskite light absorption layer has the component of FA0.75MA0.25SnI2.75Br0.25Or FASnI3The concentration of FAI is 0.5-0.9M, the concentration of MABr is 0.16-0.3M, SnI2The concentration of (A) is 0.67-1M, SnF2The concentration of the PEAI is 0.1-0.18M and the concentration of the PEAI is 0.1-0.18M.
The embodiment also provides a preparation method of the tin-based perovskite solar cell, which adopts the green solvent system and comprises the following steps: the method comprises the steps of firstly spin-coating a hole transport layer on a substrate, then spin-coating a perovskite light absorption layer, then spin-coating an electron transport layer, then spin-coating a buffer layer, and finally evaporating a metal electrode.
In this example, ITO is used as the substrate, PEDOT: PSS is used as the hole transport layer, FA0.75MA0.25SnI2.75Br0.25Is a light absorbing layer, PC61The preparation method of the perovskite solar cell with BM as an electron transport layer, BCP as a buffer layer and silver as a counter electrode comprises the following steps:
the method comprises the following steps: cleaning the surface of the purchased ITO glass by sequentially adopting deionized water, absolute ethyl alcohol, acetone and isopropanol, and drying by nitrogen for later use;
step two: and (4) putting the ITO in the step one into ultraviolet ozone for 15 minutes. Taking 90 mu L of PEDOT, namely PSS solution to spin on ITO conductive glass, spin-coating for 50s at the speed of 3000rpm, and then putting on a heating table at 100 ℃ to anneal for 10 min;
step three: 1.2M of SnI20.9M FAI, 0.3M MABr, 0.18M SnF20.18M PEAI and 6mg/mL Sn powder. Adding an EtOH/DMSO (v: v ═ 4:1) mixed solvent to prepare a 1.2M perovskite precursor solution;
step four: dropwise adding 50 mu L of perovskite precursor solution on the hole transport layer obtained in the step three to completely cover the hole transport layer, spin-coating at 6000rpm for 60s, dropwise adding chlorobenzene after 15s, and then transferring the hole transport layer to a heating table at 80 ℃ for annealing for 10 minutes;
step five: spin coating PC on the perovskite layer obtained in the fourth step61BM Electron transport layer, PC6120mg/mL PC of BM spin coating solution61BM chlorobenzene solution. Spin-coating at 2000r/min for 30 s;
step six: spin-coating BCP on the surface of the electron transport layer obtained in the fifth step, wherein the BCP is 1mg/ml isopropanol solution, spin-coating for 30s at 6000rpm, and annealing for 10 minutes after the spin-coating is finished to obtain a buffer layer;
step seven: evaporating to coat with a thickness of 100 nm and an effective area of 0.096cm2The metallic silver electrode of (1).
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Those skilled in the art can modify or change the above-described embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.

Claims (10)

1. A green solvent system for preparing a tin-based perovskite solar cell is characterized in that: the perovskite solar cell structurally comprises a conductive substrate, a hole transport layer, a perovskite light absorption layer, an electron transport layer, a buffer layer and a counter electrode from bottom to top, wherein a perovskite precursor solvent for forming the perovskite light absorption layer is a nontoxic solvent mixed by diethylformamide and dimethyl sulfoxide, or a nontoxic solvent mixed by gamma butyrolactone and dimethyl sulfoxide, or a nontoxic solvent mixed by acetonitrile and dimethyl sulfoxide, or a nontoxic solvent mixed by ethanol and dimethyl sulfoxide.
2. The green solvent system for preparing tin-based perovskite solar cell of claim 1, wherein the volume ratio of diethylformamide to dimethyl sulfoxide is 4:1 or 6:4, the volume ratio of gamma butyrolactone to dimethyl sulfoxide is 4:1, the volume ratio of acetonitrile to dimethyl sulfoxide is 4:1, and the volume ratio of ethanol to dimethyl sulfoxide is 4: 1.
3. A green solvent system for making tin-based perovskite solar cells according to claim 1, characterized in that: comprises raw materials for forming a perovskite light absorption layer and the perovskite precursor solvent; the raw materials for forming the light-absorbing layer of the perovskite layer comprise formamidine iodine FAI, methylamine bromine MABr and stannous iodide SnI2SnF (stannous fluoride)2And phenethylamine iodide salt PEAI.
4. The green solvent system for preparing tin-based perovskite solar cells as claimed in claim 3, wherein: the perovskite light absorption layer has the component of FA0.75MA0.25SnI2.75Br0.25Or FASnI3The concentration of FAI is 0.5-0.9M, the concentration of MABr is 0.16-0.3M, SnI2The concentration of (A) is 0.67-1M, SnF2The concentration of the PEAI is 0.1-0.18M and the concentration of the PEAI is 0.1-0.18M.
5. A method of manufacturing a tin-based perovskite solar cell, using the green solvent system of any one of claims 1 to 4, characterized in that the manufacturing method comprises: the method comprises the steps of firstly spin-coating a hole transport layer on a substrate, then spin-coating a perovskite light absorption layer, then spin-coating an electron transport layer, then spin-coating a buffer layer, and finally evaporating a metal electrode.
6. The method according to claim 5, wherein the method comprises: the hole transport layer comprises NiOxPEDOT is a PSS layer; the process for spin coating the PEDOT PSS hole transport layerThe parameters are as follows: 1000-4000 rpm; the annealing process parameters are as follows: the annealing temperature is 80-100 ℃, and the annealing temperature is 80-140 ℃.
7. The method for preparing a tin-based perovskite solar cell according to claim 5, wherein the perovskite light absorption layer spin coating process parameters are as follows: rotating at 6000-9000 rpm for 60-80 s; the annealing process parameters are as follows: the annealing temperature is 70-100 ℃, and the time is 10-15 min.
8. The method according to claim 5, wherein the method comprises: and adding an anti-solvent chlorobenzene or toluene dropwise during spin coating of the intrinsic light absorption layer of the perovskite.
9. The method according to claim 5, wherein the method comprises: the hole transport layer is PC61BM, and/or the buffer layer is BCP material, and/or the electrode is silver or aluminum.
10. The tin-based perovskite solar cell obtained by the preparation method of any one of claims 5 to 9.
CN202210327040.1A 2022-03-30 2022-03-30 Tin-based perovskite solar cell, preparation method and green solvent system Pending CN114695681A (en)

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