CN111509128A - Perovskite solar cell based on composite hole transport layer and preparation method thereof - Google Patents

Perovskite solar cell based on composite hole transport layer and preparation method thereof Download PDF

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CN111509128A
CN111509128A CN202010515438.9A CN202010515438A CN111509128A CN 111509128 A CN111509128 A CN 111509128A CN 202010515438 A CN202010515438 A CN 202010515438A CN 111509128 A CN111509128 A CN 111509128A
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pedot
transport layer
pss
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章文峰
林埔安
黄跃龙
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Southwest Petroleum University
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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Abstract

The invention provides a perovskite solar cell based on a composite hole transport layer and a preparation method thereof, and belongs to the technical field of perovskite solar cells. The composite hole transport layer comprises a PEDOT PSS layer, a hole modification layer is arranged on the PEDOT PSS layer, the hole modification layer is a film prepared from amphiphilic molecules, two ends of the amphiphilic molecules are respectively a polar group and a non-polar group, and the amphiphilic molecules further comprise ester groups. The perovskite solar cell prepared based on the composite hole transport layer improves the yield of PEDOT: the conductivity of the PSS layer improves PEDOT: the PSS is matched with the interface energy level of the perovskite active layer, and meanwhile, the ester group in the amphiphilic molecule inhibits the defects generated on the interface, reduces carrier capture sites, and greatly improves the energy conversion efficiency of the titanium ore solar cell.

Description

Perovskite solar cell based on composite hole transport layer and preparation method thereof
Technical Field
The invention relates to the technical field of perovskite solar cells, in particular to a perovskite solar cell based on a composite hole transport layer and a preparation method thereof.
Background
The generalized perovskite has an ABX3 structure, typically cubic or octahedral, and the A ion is usually referred to as an organic cation, most commonly
Figure BDA0002529932040000011
(methylamino), others such as
Figure BDA0002529932040000012
(formamidine) and
Figure BDA0002529932040000013
(ethylamino) also has application where the B ion refers to a metal cation, primarily Pb2+And Sn2+The X ion being a halide anion, i.e. I-、Br-、Cl-And the like. Perovskite Solar Cells (PSCs) have the advantages of being adaptable to flexible substrates due to excellent photoelectric properties, so that flexible devices can be manufactured, efficiency and cost can be considered, the Perovskite solar cells are judged to be one of ten years of technological progress by scientific magazines in 2013, and the Perovskite solar cells are one of the most potential materials in third-generation solar cells. The high-performance perovskite solar cell is mainly determined by the material properties of all components, mainly determined by the material properties of three main functional layers of a core part hole transmission layer/a perovskite light absorption layer/an electron transmission layer and the matching degree among the three main functional layers, wherein the matching degree can influence the transmission process of current carriers on an interface, a plurality of deep level defects exist at the interface and are sites for recombination reaction of electrons and holes, and therefore interface modification becomes one of main directions for improving the photoelectric conversion efficiency of the perovskite solar cell.
Wherein the weight ratio is based on PEDOT: the trans structure of the PSS hole transport layer is suitable for the preparation of flexible batteries, but PEDOT: the perovskite solar cell with the PSS as the hole transport layer has some disadvantages, namely PEDOT: PSS also has a low mobility, which slows the extraction of holes from the perovskite active layer, while PEDOT: the PSS and the perovskite active layer are not well matched in energy level, and the photoelectric conversion efficiency of the titanium ore solar cell is further reduced.
In view of this, a simpler and more convenient way of increasing PEDOT: (ii) mobility of PSS or improvement of PEDOT: the PSS is matched with the energy level of the perovskite active layer, so that the energy conversion efficiency of the perovskite solar cell is improved, and the perovskite solar cell has important economic value and scientific research value.
Disclosure of Invention
In order to solve the technical problems, the invention provides a perovskite solar cell based on a composite hole transport layer and a preparation method thereof.
The technical scheme of the invention is as follows:
the composite hole transport layer comprises a PEDOT PSS layer, wherein a hole modification layer is arranged on the PEDOT PSS layer and is a thin film prepared from amphiphilic molecules;
the amphiphilic molecule comprises a polar group and a nonpolar group, wherein the polar group and the nonpolar group are positioned at two ends of the amphiphilic molecule, and the amphiphilic molecule further comprises an ester group.
Further, the thickness of the PEDOT/PSS layer is 20-100 nm.
Further, the thickness of the hole modification layer is 2-15 nm.
Further, the amphipathic molecule comprises 1-octanoyl-rac-glycerol (C)11H22O4) Mono-capric acid glyceride (C)13H26O4) Lauric acid glyceride (C)15H30O4) And monoglyceride (C)17H34O4) 1-palmitic acid monoglyceride (C)19H38O4) Linoleic acid glyceride (C)21H38O4) Glycerol monooleate (C)21H40O4) Glyceryl monostearate (C)21H42O4) Vitamin C stearate (C)24H42O7) Glycerol erucic acid ester (C)25H48O4) And Flat oleic acid glyceride (C)25H50O4) One or more of them.
A method of making a composite hole transport layer comprising the steps of:
step 1: coating aqueous solution of PEDOT and PSS on a substrate, and annealing to form a PEDOT and PSS layer;
step 2: and coating the solution of the amphiphilic molecules on the PEDOT PSS layer to form a hole modification layer.
Furthermore, the weight ratio of PEDOT to PSS in the aqueous solution of PEDOT to PSS is 1: 2-1: 8.
Further, the concentration of the solute in the solution of the amphiphilic molecules is 0.1 mg/ml-1 mg/ml.
The perovskite solar cell based on the composite hole transport layer sequentially comprises a transparent substrate, a transparent electrode, a composite hole transport layer, a perovskite active layer, an electron transport layer, a hole blocking layer and a counter electrode from bottom to top, wherein a PEDOT layer of the composite hole transport layer is connected with the transparent electrode, and a hole modification layer of the composite hole transport layer is connected with the perovskite active layer.
A method of making a perovskite solar cell, comprising the steps of:
step 1: preparing a substrate: depositing the transparent electrode on the upper surface of the transparent substrate, wherein the transparent substrate and the transparent electrode form a substrate of the composite hole transport layer; respectively cleaning the substrate with deionized water, ethanol, acetone, isopropanol and ethanol, blow-drying the substrate with nitrogen, and then treating the substrate with ultraviolet ozone for 15 min;
step 2: preparing a composite hole transport layer: coating a solution of PEDOT and PSS on a substrate, and annealing to form a PEDOT and PSS layer; coating the solution of amphiphilic molecules on the PEDOT, namely PSS layer to form a film-shaped hole modification layer; obtaining a composite hole transport layer comprising the PEDOT, the PSS layer and the hole modification layer;
and step 3: preparing a perovskite active layer: mixing a mixture of 1: dissolving lead iodide and methyl ammonium iodide of 1 in a mixed solvent of dimethyl sulfoxide and dimethyl formamide, wherein the volume ratio of the dimethyl formamide to the dimethyl sulfoxide is (7): 3, stirring for 12 hours at 60 ℃ under the protection of inert gas to obtain a perovskite precursor MAPbI3 solution, spin-coating the obtained perovskite precursor solution on the composite hole transport layer at normal temperature by a one-step solution spin-coating method, wherein the spin-coating parameters are 4000rpm, the spin-coating time is 40s, dropwise adding an anti-solvent in the spin-coating process, and then annealing for 5min on a 100 ℃ hot stage to obtain the perovskite active layer;
and 4, step 4: preparing an electron transport layer: dissolving [6,6] -phenyl-C61-isopropyl butyrate in a chlorobenzene solvent to obtain a [6,6] -phenyl-C61-isopropyl butyrate solution, wherein the dissolving concentration is 20mg/ml, and spin-coating the [6,6] -phenyl-C61-isopropyl butyrate solution on the perovskite active layer, wherein the spin-coating parameter is 2000rpm, and the spin-coating time is 40s to obtain the electron transport layer;
and 5: preparing a hole blocking layer: dissolving bathocuproine in an isopropanol solvent to obtain bathocuproine solution, wherein the dissolving concentration is 0.5mg/ml, and spin-coating the bathocuproine solution on the electron transport layer for 40s at the spin-coating parameter of 5000rpm to obtain the hole blocking layer;
step 6: preparing a counter electrode: and under the vacuum condition, silver with the thickness of 80nm is evaporated on the hole blocking layer to be used as the counter electrode, and the perovskite solar cell based on the composite hole transport layer is obtained.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
the invention is characterized in that the ratio of PEDOT: the PSS layer is coated with a layer of amphiphilic molecules to form a composite hole transport layer, so that the yield of PEDOT is improved: the conductivity of the PSS layer, and the perovskite solar cell prepared by the prepared composite hole transport layer improves the conductivity of PEDOT: the interface of the PSS and the perovskite active layer simultaneously solves the problems of PEDOT: PSS is used as the defect of the perovskite solar cell of the hole transport layer, and the energy conversion efficiency of the titanium ore solar cell is greatly improved.
Drawings
FIG. 1 is a schematic diagram of a perovskite solar cell structure;
FIG. 2 is a schematic diagram of the molecular structure of glyceryl monostearate;
fig. 3 is a voltage-current characteristic curve of a perovskite solar cell obtained according to an example of the present invention and a comparative example;
FIG. 4 is a graph of energy levels of perovskite battery materials obtained according to examples of the present invention and comparative examples;
description of the drawings: 1-transparent substrate, 2-transparent electrode, 31-PEDOT, PSS layer, 32-hole modification layer, 4-perovskite active layer, 5-electron transmission layer, 6-hole barrier layer and 7-counter electrode.
Detailed Description
All features disclosed in this specification may be combined in any combination, except features and/or steps that are mutually exclusive.
The present invention will be described in detail with reference to the accompanying drawings.
The invention provides a composite hole transport layer, which can improve the yield of PEDOT: conductivity of the PSS layer 31. The composite hole transport layer comprises a PEDOT PSS layer 31, wherein the PEDOT PSS is poly (3, 4-vinyl dioxythiophene) poly (styrene sulfonate); PSS layer 31 is provided with a hole modification layer 32, and the hole modification layer 32 is a film prepared from amphiphilic molecules; the amphiphilic molecule comprises a polar group and a nonpolar group, wherein the polar group and the nonpolar group are positioned at two ends of the amphiphilic molecule, and the amphiphilic molecule further comprises an ester group. The amphiphilic molecule comprises one or more of 1-octanoyl-rac-glycerol (C11H22O4), glyceryl monocaprate (C13H26O4), glyceryl laurate (C15H30O4), glyceryl monomyristate (C17H34O4), glyceryl 1-palmitate (C19H38O4), glyceryl linoleate (C21H38O4), glyceryl monooleate (C21H40O4), glyceryl monostearate (C21H42O4), vitamin C stearate (C24H42O7), glyceryl erucate (C25H48O4) and glyceryl linoleate (C25H50O 4).
The PEDOT PSS layer 31 has a thickness of 20-100nm, preferably 20-60 nm.
The thickness of the hole modification layer 32 is 2-15nm, and the preferable thickness is 5-10 nm.
Further, a preparation method of the composite hole transport layer is provided, which comprises the following steps:
step 1: coating a PEDOT/PSS aqueous solution on a substrate, and annealing to form a PEDOT/PSS layer 31, wherein the weight ratio of PEDOT to PSS in the PEDOT/PSS aqueous solution is 1: 2-1: 8, preferably 1: 6;
step 2: and coating the solution of the amphiphilic molecules on the PEDOT PSS layer 31 to form a hole modification layer 32, wherein the concentration of solute in the solution of the amphiphilic molecules is 0.1-1 mg/ml, and the preferable concentration is 0.25-0.75 mg/ml.
Further, fig. 1 provides a perovskite solar cell based on a composite hole transport layer, which sequentially comprises a transparent substrate 1, a transparent electrode 2, a composite hole transport layer, a perovskite active layer 4, an electron transport layer 5, a hole blocking layer 6 and a counter electrode 7 from bottom to top. The upper surface of the transparent substrate 1 is provided with a transparent electrode 2, the transparent electrode 2 is preferably FTO or ITO, the upper surface of the transparent electrode 2 is provided with a PEDOT/PSS layer 31, the upper surface of the PEDOT/PSS layer 31 is provided with a hole modification layer 32, the upper surface of the hole modification layer 32 is provided with a perovskite active layer 4, the upper surface of the perovskite active layer 4 is provided with an electron transport layer 5, the electron transport layer 5 is preferably [6,6] -phenyl-C61-isopropyl butyrate (PCBM), the upper surface of the electron transport layer 5 is provided with a hole blocking layer 6 Bathocuproine (BCP), the upper surface of the bathocuproine layer is provided with a counter electrode 7, and the counter electrode 7 is preferably silver, so that the perovskite solar cell is obtained.
Further, a preparation method of the perovskite solar cell is provided, which comprises the following steps:
step 1: preparing a substrate: depositing the transparent electrode 2 on the upper surface of the transparent substrate 1, wherein the transparent substrate 1 and the transparent electrode 2 form a base of the composite hole transport layer; respectively cleaning the substrate with deionized water, ethanol, acetone, isopropanol and ethanol, blow-drying the substrate with nitrogen, and then treating the substrate with ultraviolet ozone for 15 min;
step 2: preparing a composite hole transport layer: coating a solution of PEDOT and PSS on a substrate, and annealing to form a PEDOT and PSS layer 31; coating the solution of the amphiphilic molecules on the PEDOT, PSS layer to form a hole modification layer 32; obtaining a composite hole transport layer comprising the PEDOT, the PSS layer 31 and the hole modification layer 32;
and step 3: preparation of the perovskite active layer 4: mixing a mixture of 1: dissolving lead iodide and methyl ammonium iodide of 1 in a mixed solvent of dimethyl sulfoxide and dimethyl formamide, wherein the volume ratio of the dimethyl formamide to the dimethyl sulfoxide is (7): 3, stirring for 12 hours at 60 ℃ under the protection of inert gas to obtain a perovskite precursor MAPbI3 solution, spin-coating the obtained perovskite precursor solution on the composite hole transport layer at normal temperature by a one-step solution spin-coating method, wherein the spin-coating parameters are 4000rpm, the spin-coating time is 40s, dropwise adding an anti-solvent in the spin-coating process, and then annealing for 5min on a 100 ℃ hot stage to obtain the perovskite active layer 4;
and 4, step 4: preparation of the electron transport layer 5: dissolving [6,6] -phenyl-C61-isopropyl butyrate in a chlorobenzene solvent to obtain a [6,6] -phenyl-C61-isopropyl butyrate solution, wherein the dissolving concentration is 20mg/ml, and spin-coating the [6,6] -phenyl-C61-isopropyl butyrate solution on the perovskite active layer 4, wherein the spin-coating parameter is 2000rpm, and the spin-coating time is 40s to obtain the electron transport layer 5;
and 5: preparing a hole blocking layer 6: dissolving bathocuproine in isopropanol solvent to obtain bathocuproine solution, wherein the dissolving concentration is 0.5mg/ml, and spin-coating the bathocuproine solution on the electron transport layer 5 for 40s at the spin-coating parameter of 5000rpm to obtain the hole blocking layer 6;
step 6: preparation of counter electrode 7: and under the vacuum condition, silver with the thickness of 80nm is evaporated on the hole blocking layer 6 to be used as the counter electrode 7, and the perovskite solar cell based on the composite hole transport layer is obtained.
Example 1
To further illustrate the effect of amphiphilic molecules as the hole modification layer 32 to prepare the composite hole transport layer, the amphiphilic molecules in this embodiment are glyceryl monostearate (C21H42O4), and the molecular diagram of the amphiphilic molecules is shown in fig. 2, wherein one end of the amphiphilic molecules contains a polar group (hydrophilic end) and the other end of the amphiphilic molecules contains a non-polar group (hydrophobic end), and the amphiphilic molecules further include an ester group.
The present embodiment provides a specific composite hole transport layer and a method for preparing the same.
The composite hole transport layer includes a PEDOT PSS layer 31 and glyceryl monostearate (abbreviated as GMS), the thickness of the PEDOT PSS layer 31 is 40 nm; the thickness of the GMS layer was 8 nm.
The preparation method comprises the following steps: preparing a substrate with a hole transport layer, namely a transparent electrode 2 (ITO) deposited on the upper surface of a transparent substrate 1 (transparent glass in the position) and used as a substrate of the hole transport layer, respectively cleaning the substrate with deionized water, ethanol, acetone, isopropanol and ethanol, blow-drying the substrate with nitrogen after cleaning is finished, and then treating the substrate with ultraviolet ozone for 15 min;
placing the substrate on a spin coater, filtering an aqueous solution of PEDOT: PSS with the model number of C L EVIOS _ P _ VP _ AI _4083 from Heraeus company by using a 0.45-micron filter membrane, wherein the weight ratio of PEDOT to PSS in the aqueous solution of PEDOT: PSS is 1:6, then uniformly coating the whole substrate at the rotation speed of 4000rpm for 40s, placing the substrate on a hot bench for annealing at 150 ℃ for 10min after the spin coating is finished to obtain a PEDOT: PSS layer with the thickness of about 40nm, then coating the methanol solution of GMS on the PEDOT: PSS layer 31, wherein the concentration of the methanol solution of GMS is 0.5mg/ml, the rotation speed of 5000rpm and the rotation time of 40s, and placing the substrate on the hot bench for annealing at 110 ℃ for 10min after the spin coating is finished to obtain the composite hole transport layer consisting of PEDOT: PSS/GMS.
Example 2
The embodiment provides a preparation method of a perovskite solar cell based on a composite hole transport layer based on embodiment 1, and the preparation method comprises the following steps:
the preparation method comprises the following steps:
(1) preparation work: preparing a substrate with a hole transport layer, namely a transparent electrode 2 (ITO) deposited on the upper surface of a transparent substrate 1 (transparent glass in the position), respectively cleaning the substrate with deionized water, ethanol, acetone, isopropanol and ethanol, blow-drying the substrate with nitrogen after cleaning is finished, and then treating the substrate with ultraviolet ozone for 15 min.
(2) The preparation method of the PEDOT/PSS/GMS composite hole transport layer comprises the steps of placing a substrate on a spin coater, filtering an aqueous solution of the PEDOT/PSS with a 0.45-micron filter membrane, wherein the aqueous solution of the Heraeus is C L EVIOS _ P _ VP _ AI _4083, the weight ratio of the PEDOT to the PSS is 1:6, the whole substrate is uniformly coated, the rotating speed is 4000rpm, the rotating time is 40s, after the spin coating is finished, the substrate is placed on a hot bench and annealed at 150 ℃ for 10min to obtain a PEDOT/PSS layer with the thickness of about 40nm, then a methanol solution of the GMS is coated on the PEDOT/PSS layer 31, the concentration of the methanol solution of the GMS is 0.5mg/ml, the rotating speed is 5000rpm, the rotating time is 40s, after the spin coating is finished, the substrate is placed on the hot bench and annealed at 110 ℃ for 10min to obtain the GMS layer with the thickness of about 8nm, and then the GMS composite hole transport layer composed of.
(3) Preparation of perovskite light absorption layer: the titanium ore active layer is prepared by mixing titanium ore active layer with a molar ratio of 1: 1, dissolving PbI2 and MAI in a mixed solvent of DMSO and DMF, wherein the volume ratio of the DMF to the DMSO is 7: 3, stirring for 12 hours at 60 ℃ under the protection of inert gas (such as N2) to obtain a perovskite precursor MAPbI3 solution, spin-coating the obtained perovskite precursor solution on the composite hole transport layer at normal temperature by a one-step solution spin coating method, wherein the spin coating parameter is 4000rpm, the spin coating time is 40s, dropwise adding an anti-solvent (such as a chlorobenzene solution) in the spin coating process, and then annealing for 5 minutes on a 100 ℃ hot bench to obtain the perovskite light absorption layer with the thickness of about 350 nm;
(4) preparation of the electron transport layer 5: dissolving PCBM in chlorobenzene solvent to obtain PCBM solution with a dissolution concentration of 20mg/ml, and spin-coating the PCBM solution on the perovskite light absorption layer with spin-coating parameters of 2000rpm, spin-coating time of 40s and thickness of about 40nm to obtain the electronic transmission layer 5;
(5) preparation of the hole blocking layer 6: dissolving BCP in isopropanol solvent to obtain BCP solution with the dissolving concentration of 0.5mg/ml, and spin-coating the BCP solution on the electron transport layer 5 with the spin-coating parameter of 5000rpm and the spin-coating time of 40s to obtain a hole blocking layer 6 with the thickness of about 8 nm;
(6) preparation of counter electrode 7: silver with the thickness of 80nm is evaporated on the hole blocking layer 6 as a counter electrode 7 under the vacuum condition, and the perovskite solar cell based on the composite hole transport layer is obtained.
The voltammogram (J-V curve) of the perovskite solar cell prepared in this example under xenon lamp irradiation of 100mW/cm2 is shown in fig. 3, and the energy level diagram of the surface of each layer material of the perovskite solar cell prepared according to this example is shown in fig. 4.
This example provides comparative examples:
preparation of perovskite solar cell based on PEDOT PSS hole transport layer:
(1) preparation work: preparing a substrate with a hole transport layer, namely a transparent electrode 2 (ITO) deposited on the upper surface of a transparent substrate 1 (transparent glass in the position), respectively cleaning the substrate with deionized water, ethanol, acetone, isopropanol and ethanol, blow-drying the substrate with nitrogen after cleaning is finished, and then treating the substrate with ultraviolet ozone for 15 min.
(2) The preparation of the PEDOT: PSS hole transport layer comprises the steps of placing a substrate on a spin coater, filtering an aqueous solution of the PEDOT: PSS with the model number of C L EVIOS _ P _ VP _ AI _4083 of Heraeus company by using a 0.45-micron filter membrane, wherein the weight ratio of the PEDOT to the PSS in the aqueous solution of the PEDOT: PSS is 1:6, then uniformly coating the whole substrate at the rotation speed of 4000rpm for 40s, placing the substrate on a hot bench for annealing at the temperature of 150 ℃ for 10min after the spin coating is finished to obtain the PEDOT: PSS layer with the thickness of about 40nm, and then placing the substrate on the hot bench for annealing at the temperature of 110 ℃ for 10min to obtain the hole transport layer of the PEDOT: PSS layer.
(3) Preparation of perovskite light absorption layer: the titanium ore active layer is prepared by mixing titanium ore active layer with a molar ratio of 1: 1, dissolving PbI2 and MAI in a mixed solvent of DMSO and DMF, wherein the volume ratio of the DMF to the DMSO is 7: 3, stirring for 12 hours at 60 ℃ under the protection of inert gas (such as N2) to obtain a perovskite precursor MAPbI3 solution, spin-coating the obtained perovskite precursor solution on the composite hole transport layer at normal temperature by a one-step solution spin coating method, wherein the spin coating parameter is 4000rpm, the spin coating time is 40s, dropwise adding an anti-solvent (such as a chlorobenzene solution) in the spin coating process, and then annealing for 5 minutes on a 100 ℃ hot bench to obtain the perovskite light absorption layer with the thickness of about 350 nm;
(4) preparation of the electron transport layer 5: dissolving PCBM in chlorobenzene solvent to obtain PCBM solution with a dissolution concentration of 20mg/ml, and spin-coating the PCBM solution on the perovskite light absorption layer with spin-coating parameters of 2000rpm, spin-coating time of 40s and thickness of about 40nm to obtain the electronic transmission layer 5;
(5) preparation of the hole blocking layer 6: dissolving BCP in isopropanol solvent to obtain BCP solution with the dissolving concentration of 0.5mg/ml, and spin-coating the BCP solution on the electron transport layer 5 with the spin-coating parameter of 5000rpm and the spin-coating time of 40s to obtain a hole blocking layer 6 with the thickness of about 8 nm;
(6) preparation of counter electrode 7: silver with the thickness of 80nm is evaporated on the hole blocking layer 6 as a counter electrode 7 under the vacuum condition, and the perovskite solar cell based on the composite hole transport layer is obtained.
The voltammograms (J-V curves) of the perovskite solar cells prepared in examples and comparative examples under 100mW/cm2 xenon lamp irradiation are shown in fig. 3, and the energy level profiles of the layer materials of the perovskite solar cells are shown in fig. 4.
According to the above examples and comparative examples, in combination with fig. 3, the photoelectric conversion efficiency of the perovskite solar cell based on the PEDOT: PSS/GMS composite hole transport layer is 16.18%, the photoelectric conversion efficiency of the perovskite solar cell based on the PEDOT: PSS hole transport layer is 12.23%, the efficiency is improved by about 32%, and it can be seen from fig. 3 that the open-circuit voltage Voc, the short-circuit current Jsc and the fill factor FF are improved in the performance parameters, and the improvement of the photoelectric conversion efficiency is derived from three aspects. First, according to the schematic diagram of the molecular structure of GMS in fig. 1, GMS has a hydrophilic end at one end and a hydrophobic end at the other end, and a methanol solution of GMS is spin-coated on a PEDOT: PSS film, so that the surface PEDOT: conformation changes of PEDOT chain and PSS chain in PSS, the content ratio of PEDOT to PSS is increased, and the change causes the ratio of PEDOT: the PSS film has high conductivity and high carrier transport speed. And secondly, the GMS contains ester groups, the MAPbI3 active layer is spin-coated on the PEDOT PSS/GMS composite hole transport layer, and the ester groups in the GMS can inhibit the generation of Pb vacancies at the interface of the PEDOT PSS/MAPbI3 active layer, reduce active sites for capturing carriers to generate recombination reaction, and improve the interface of the hole transport layer and the active layer. Finally, as shown in fig. 4, the energy loss of holes in perovskite transported to the PEDOT: PSS/GMS composite hole transport layer was smaller than the energy loss transported to the PEDOT: PSS hole transport layer based on the fact that the work function of the PEDOT: PSS/GMS composite hole transport layer was 5.31eV, the work function of the PEDOT: PSS hole transport layer based on the fact that the work function of the perovskite active layer 4 was 4.98eV, and the valence band of the perovskite active layer 4 was 5.40 eV. Therefore, the photoelectric conversion efficiency of the perovskite solar cell with the PEDOT-PSS/GMS composite hole transport layer is greatly improved.
The above description is an embodiment of the present invention. The present invention is not limited to the above embodiments, and any structural changes made under the teaching of the present invention shall fall within the protection scope of the present invention, which is similar or similar to the technical solutions of the present invention.

Claims (9)

1. The composite hole transport layer is characterized by comprising a PEDOT PSS layer (31), wherein a hole modification layer (32) is arranged on the PEDOT PSS layer (31), and the hole modification layer (32) is a thin film prepared from amphiphilic molecules;
the amphiphilic molecule comprises a polar group and a nonpolar group, wherein the polar group and the nonpolar group are positioned at two ends of the amphiphilic molecule, and the amphiphilic molecule further comprises an ester group.
2. A composite hole transport layer according to claim 1, characterized in that the thickness of the PEDOT: PSS layer (31) is 20-100 nm.
3. A composite hole-transporting layer according to claim 1, characterised in that the hole-modifying layer (32) has a thickness of 2-15 nm.
4. A composite hole transporting layer according to claim 1, wherein the amphiphilic molecules comprise one or more of 1-octanoyl-rac-glycerol (C11H22O4), glycerol monocaprate (C13H26O4), glycerol laurate (C15H30O4), glycerol monomyristate (C17H34O4), glycerol monopalmitate (C19H38O4), glycerol linoleate (C21H38O4), glycerol monooleate (C21H40O4), glycerol monostearate (C21H42O4), vitamin C stearate (C24H42O7), glycerol erucate (C25H48O4) and glycerol linoleate (C25H50O 4).
5. A method of making a composite hole transport layer according to any of claims 1 to 4, comprising the steps of:
step 1: coating a water solution of PEDOT and PSS on a substrate, and annealing to form a PEDOT and PSS layer (31);
step 2: and coating the solution of the amphiphilic molecules on the PEDOT PSS layer (31) to form a hole modification layer (32).
6. The method for preparing a composite hole transport layer according to claim 5, wherein the weight ratio of PEDOT to PSS in the aqueous solution of PEDOT to PSS is 1:2 to 1: 8.
7. The method of claim 5, wherein the concentration of the amphiphilic molecule solution is 0.1mg/ml to 1 mg/ml.
8. The perovskite solar cell based on the composite hole transport layer of any one of claims 1 to 4, characterized by comprising a transparent substrate (1), a transparent electrode (2), the composite hole transport layer, a perovskite active layer (4), an electron transport layer (5), a hole blocking layer (6) and a counter electrode (7) in sequence from bottom to top, wherein the PEDOT: PSS layer (31) of the composite hole transport layer is connected with the transparent electrode (2), and the hole modification layer (32) of the composite hole transport layer is connected with the perovskite active layer (4).
9. A method of making the perovskite solar cell of claim 8, comprising the steps of:
step 1: preparing a substrate: depositing the transparent electrode (2) on the upper surface of the transparent substrate (1), wherein the transparent substrate (1) and the transparent electrode (2) form a base of the composite hole transport layer; respectively cleaning the substrate with deionized water, ethanol, acetone, isopropanol and ethanol, blow-drying the substrate with nitrogen, and then treating the substrate with ultraviolet ozone for 15 min;
step 2: preparing a composite hole transport layer: coating a water solution of PEDOT and PSS on a substrate, and annealing to form a PEDOT and PSS layer (31); coating the solution of the amphiphilic molecules on the PEDOT PSS layer to form a hole modification layer (32); obtaining a composite hole transport layer comprising the PEDOT, the PSS layer (31) and the hole modification layer (32);
and step 3: preparation of perovskite active layer (4): mixing a mixture of 1: dissolving lead iodide and methyl ammonium iodide of 1 in a mixed solvent of dimethyl sulfoxide and dimethyl formamide, wherein the volume ratio of the dimethyl formamide to the dimethyl sulfoxide is (7): 3, stirring for 12 hours at 60 ℃ under the protection of inert gas to obtain a perovskite precursor MAPbI3 solution, spin-coating the obtained perovskite precursor solution on the composite hole transport layer at normal temperature by a one-step solution spin-coating method, wherein the spin-coating parameters are 4000rpm, the spin-coating time is 40s, dropwise adding an anti-solvent in the spin-coating process, and then annealing for 5min on a 100 ℃ hot stage to obtain the perovskite active layer (4);
and 4, step 4: preparation of the electron transport layer (5): dissolving [6,6] -phenyl-C61-isopropyl butyrate in a chlorobenzene solvent to obtain a [6,6] -phenyl-C61-isopropyl butyrate solution with the dissolving concentration of 20mg/ml, and spin-coating the [6,6] -phenyl-C61-isopropyl butyrate solution on the perovskite active layer (4) with the spin-coating parameters of 2000rpm and the spin-coating time of 40s to obtain the electron transport layer (5);
and 5: preparation of hole blocking layer (6): dissolving bathocuproine in an isopropanol solvent to obtain bathocuproine solution, wherein the dissolving concentration is 0.5mg/ml, and spin-coating the bathocuproine solution on the electron transport layer (5) for 40s at the spin-coating parameter of 5000rpm to obtain the hole blocking layer (6);
step 6: preparation of counter electrode (7): and (3) evaporating silver with the thickness of 80nm on the hole blocking layer (6) under the vacuum condition to be used as the counter electrode (7), so as to obtain the perovskite solar cell based on the composite hole transport layer.
CN202010515438.9A 2020-06-09 2020-06-09 Perovskite solar cell based on composite hole transport layer and preparation method thereof Pending CN111509128A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111952468A (en) * 2020-08-18 2020-11-17 福州大学 Quantum dot light-emitting diode for removing organic matters in light-emitting layer based on quantum dot anti-solvent and preparation method thereof
CN112614938A (en) * 2020-12-15 2021-04-06 华能新能源股份有限公司 All-inorganic composite hole transport layer with energy level gradient, battery and preparation method

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111952468A (en) * 2020-08-18 2020-11-17 福州大学 Quantum dot light-emitting diode for removing organic matters in light-emitting layer based on quantum dot anti-solvent and preparation method thereof
CN111952468B (en) * 2020-08-18 2024-04-19 福州大学 Organic quantum dot light emitting diode based on quantum dot antisolvent removal in light emitting layer and preparation method thereof
CN112614938A (en) * 2020-12-15 2021-04-06 华能新能源股份有限公司 All-inorganic composite hole transport layer with energy level gradient, battery and preparation method
CN112614938B (en) * 2020-12-15 2023-04-25 华能新能源股份有限公司 All-inorganic composite hole transport layer with energy level gradient, battery and preparation method

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