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CN119095453A - Buried interface modification layer and its preparation, flexible perovskite solar cell small module - Google Patents

Buried interface modification layer and its preparation, flexible perovskite solar cell small module Download PDF

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Publication number
CN119095453A
CN119095453A CN202411210831.1A CN202411210831A CN119095453A CN 119095453 A CN119095453 A CN 119095453A CN 202411210831 A CN202411210831 A CN 202411210831A CN 119095453 A CN119095453 A CN 119095453A
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interface modification
layer
flexible
buried
solution
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李冬梅
孟庆波
李一明
刘政昊
罗艳红
吴会觉
石将建
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Institute of Physics of CAS
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/40—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising a p-i-n structure, e.g. having a perovskite absorber between p-type and n-type charge transport layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/84—Layers having high charge carrier mobility
    • H10K30/86—Layers having high hole mobility, e.g. hole-transporting layers or electron-blocking layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/811—Controlling the atmosphere during processing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

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Abstract

The invention provides a buried bottom interface modification layer, a preparation method thereof and a flexible perovskite solar cell small module comprising the buried bottom interface modification layer. The preparation method comprises the steps of mixing a self-assembled hole transport material and an interface modification material in a solvent to obtain an interface modification mixed solution, coating the interface modification mixed solution on a flexible conductive substrate or a flexible conductive substrate covered with nickel oxide to obtain a wet film, or preparing a solution of the self-assembled hole transport material and a solution of the interface modification material by using the solvent respectively, coating the solution of the self-assembled hole transport material and the solution of the interface modification material on the flexible conductive substrate or the flexible conductive substrate covered with nickel oxide in sequence to obtain the wet film, and drying the wet film by a low-temperature heating or vacuumizing method to obtain the modified hole transport layer serving as a buried interface modification layer. The invention improves the conversion efficiency and stability of the flexible perovskite solar cell and the small module.

Description

Buried interface modification layer, preparation method thereof and flexible perovskite solar cell small module
Technical Field
The invention relates to the technical field of solar cells, in particular to a buried bottom interface modification layer, a preparation method thereof and a flexible perovskite solar cell small module comprising the buried bottom interface modification layer.
Background
Perovskite solar cells (Perovskite Solar Cells, abbreviated as PSCs) are receiving a great deal of attention as a new type of thin film solar cells. Through more than 10 years of development, the photoelectric conversion efficiency of perovskite solar cells has been approaching 27%, approaching or exceeding that of existing commercial solar cells (such as crystalline silicon, copper Indium Gallium Selenide (CIGS), cadmium telluride (CdTe) solar cells, and the like). PSCs cells are of a wide variety and can be classified, for example, into hybrid perovskite cells and all-inorganic perovskite cells, perovskite cells of formal and trans structures, flexible cells and rigid cells, single junction and stacked cells, and the like. Meanwhile, the stability of perovskite solar cells is also gradually improving. Promoting the industrialization of perovskite solar cells and pushing them to large-scale applications has been proposed on the calendar.
Realizing the industrialization of perovskite solar cells not only puts higher demands on device efficiency and stability, but also needs to continuously reduce the preparation cost, including the cost of various related materials and production processes. In addition, in order to meet the requirements of future multi-scene applications of perovskite solar cells, the development of high-efficiency and high-stability flexible perovskite solar cells is an important development direction, such as application to portable electronic products and the like. Currently, small-area flexible perovskite solar cell efficiencies have exceeded 25% in the prior art. Further development of a high-efficiency flexible perovskite battery module is particularly necessary, and is a necessary way for realizing industrialization of flexible perovskite batteries.
However, the highest efficiency of the current flexible perovskite battery small module is only 20.64%, which is lower than that of the rigid module, and related researches are less. Therefore, there is a need to improve the efficiency and stability of flexible perovskite batteries and modules.
Disclosure of Invention
In view of the above, the present invention provides a buried bottom interface modification layer, a method for preparing the same, and a flexible perovskite solar cell module including the buried bottom interface modification layer, which overcome or at least partially solve the above problems.
The invention aims to provide a buried interface modification layer and a preparation method thereof, which are used for solving the technical problems of contact and energy level matching of a single-molecule self-assembly layer in a flexible perovskite solar cell and a buried interface of a flexible substrate, thereby improving the conversion efficiency and stability of the flexible perovskite solar cell and a small module.
The invention further aims to provide a flexible perovskite solar cell small module adopting the buried bottom interface modification layer, which has improved conversion efficiency and stability.
According to one aspect of the invention, there is provided a method for preparing a buried interface modification layer, comprising:
Mixing self-assembled hole transport material and interface modification material in solvent to obtain interface modification mixed solution, and coating the interface modification mixed solution on flexible conductive substrate or flexible conductive substrate covered with nickel oxide to obtain wet film, or
Preparing a solution of a self-assembled hole transport material and a solution of an interface modification material respectively by using a solvent, and sequentially coating the solution of the self-assembled hole transport material and the solution of the interface modification material on a flexible conductive substrate or a flexible conductive substrate covered with nickel oxide to obtain a wet film;
and drying the wet film by a low-temperature heating or vacuumizing method to obtain the modified hole transport layer serving as the buried bottom interface modification layer.
Optionally, the interface modifying material comprises one or more of polypyrrole, polyaniline, polyethylene terephthalate, graphene oxide, poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] (PTAA), carbon quantum dots, and carbon nanotubes.
Optionally, the concentration of the self-assembled hole transport material in the interface modification mixed solution or the solution of the self-assembled hole transport material is a value in the range of 0.05-20 mM;
And the concentration of the interface modification material in the interface modification mixed solution or the interface modification material solution is within the range of 0.1-50 mM.
Alternatively, the coating is performed by a knife coating method or a slit coating method,
The coating conditions are that the total coating solution amount is 100-200 mu l, the coating speed is 5 mm.s -1, and the coating times are 1 time.
Optionally, the low-temperature heating condition is that a heating table is used for heating at 80-100 ℃ for 5-20 min;
the vacuumizing condition is that the vacuum is maintained for 5-10 min under 80-100 Pa.
Optionally, the self-assembled hole transporting material comprises one or more of (2- (9H-carbazol-9-yl) ethyl) phosphonic acid (2 PACz), [2- (3, 6-dimethoxy-9H-carbazol-9-yl) ethyl ] phosphonic acid (MeO-2 PACz), (2- (4- (10H-phenothiazin-10-yl) phenyl) -1-cyanovinyl) phosphonic acid (PTZ-CPA), and [4- (3, 6-dimethyl-9H-carbazol-9-yl) butyl ] phosphoric acid (Me-4 PACz).
According to another aspect of the present invention, there is also provided a buried interface modification layer, which is produced by the production method of any one of the foregoing.
Optionally, the area of the buried interface modification layer is 1-1000 cm 2.
According to still another aspect of the present invention, there is further provided a flexible perovskite solar cell module, including a flexible transparent substrate, a conductive layer, a buried bottom interface modification layer, a perovskite absorption layer, an electron transport layer, and a counter electrode, which are sequentially stacked from bottom to top, wherein the buried bottom interface modification layer is the buried bottom interface modification layer described above.
Alternatively, the flexible perovskite solar cell is a trans perovskite solar cell.
According to the preparation method of the buried interface modification layer, the mixed liquid of the hole transport material (self-assembled layer) and the interface modification material is coated (or deposited) on the flexible substrate, or the two materials are sequentially coated (or deposited), so that good contact performance between the two materials can be realized, and interface modification is realized on the buried interface (flexible substrate conducting layer/hole transport layer interface) of the flexible perovskite solar cell. By forming the buried interface modification layer, the technical problem that a single molecule self-assembly layer in the flexible perovskite solar cell is contacted with a buried interface of a flexible substrate and energy level matching is solved.
In addition, by selecting appropriate solvents and materials, the underlying hole transport layer is not damaged. Therefore, the preparation method of the buried bottom interface modification layer, the buried bottom interface modification layer and the flexible perovskite solar cell small module provided by the invention can obviously improve the conversion efficiency and stability of the perovskite solar cell, and the preparation process of the interface modification layer and the perovskite solar cell small module is simple, low in cost and easy for large-scale production.
The foregoing description is only an overview of the present invention, and is intended to be implemented in accordance with the teachings of the present invention in order that the same may be more clearly understood and to make the same and other objects, features and advantages of the present invention more readily apparent.
The above, as well as additional objectives, advantages, and features of the present invention will become apparent to those skilled in the art from the following detailed description of a specific embodiment of the present invention when read in conjunction with the accompanying drawings.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. The same reference numbers will be used throughout the drawings to refer to the same or like parts or portions. It will be appreciated by those skilled in the art that the drawings are not necessarily drawn to scale. In the drawings:
FIG. 1 is a schematic flow chart of a method for preparing a buried interface modification layer according to an embodiment of the present invention;
FIG. 2 is a schematic flow chart of a method for preparing a buried interface modification layer according to another embodiment of the present invention;
FIG. 3 is a schematic diagram of a flexible perovskite solar cell module according to one embodiment of the invention;
fig. 4 is a schematic structural view of a flexible perovskite solar cell module according to another embodiment of the invention.
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
The inventor of the application has conducted intensive researches on a buried bottom interface, an existing preparation method for modifying the interface and a small flexible perovskite solar cell module, and found that the buried bottom interface has a larger influence on the conversion efficiency of a flexible perovskite solar cell module, and the main reason is that the perovskite thin film/hole transport layer has larger stress with a flexible substrate, so that the interface contact is poor, the quality of the perovskite thin film is seriously influenced, and the efficiency and the stability of the cell are further influenced. For flexible trans-perovskite solar cells, the buried interface (i.e., the flexible substrate conductive layer (e.g., ITO)/hole transport layer interface) is mainly enhanced by the introduction of a single molecule Self-assembled layer (SAM, self-Assembly Material). Since most of the SAM layer and the flexible substrate are mainly realized by weak actions such as hydrogen bonds, the bond actions are easily broken and fail when heated, and thus the flexible perovskite battery has a problem of poor thermal stability, which is particularly prominent on the flexible battery module.
Moreover, the anchoring effect of the SAM and the ITO substrate through hydrogen bond and the like also determines whether the SAM is uniformly and densely distributed on the ITO, thereby affecting the deposition of the perovskite layer and the growth of crystals. In addition, the anchoring effect of the SAM layer with the ITO substrate or the flexible substrate deposited with NiO x is sensitive to heat and easily desorbed. Therefore, to improve the efficiency and stability of flexible perovskite solar cells and modules, it is desirable to improve the thermal stability of the buried interfaces. In addition, the problem of energy level matching of the buried interface is not ignored. The interface modification is used as an aid and supplement to the action of SAM and ITO, so that the wettability of the buried bottom interface can be greatly improved, the perovskite crystal growth is facilitated, the energy level is more matched, and the performance of the flexible perovskite solar cell module is improved.
Based on the research and the discovery, the invention provides a buried bottom interface modification layer and a preparation method thereof.
Fig. 1 is a schematic flow chart of a method for preparing a buried interface modification layer according to an embodiment of the invention, and fig. 2 is a schematic flow chart of a method for preparing a buried interface modification layer according to another embodiment of the invention.
In one embodiment of the present invention, referring to fig. 1, the preparation method of the buried interface modification layer includes the following steps:
And S101, mixing a self-assembled hole transport material (for simplifying description, hereinafter simply referred to as material H) and an interface modification material (for simplifying description, hereinafter simply referred to as material D) in a solvent to obtain an interface modification mixed solution (for simplifying description, hereinafter simply referred to as H-D mixed solution).
And S102, coating the interface modification mixed solution on a flexible conductive substrate or a flexible conductive substrate covered with nickel oxide (NO x) to obtain a wet film.
And S103, drying the wet film by a low-temperature heating or vacuumizing method to obtain the modified hole transport layer serving as the buried interface modification layer.
In another embodiment of the present invention, referring to fig. 2, the preparation method of the buried interface modification layer includes the following steps:
S101', preparing a solution of a self-assembled hole transport material (hereinafter abbreviated as H solution) and a solution of an interface modification material (hereinafter abbreviated as D solution) respectively by using a solvent.
And S102', sequentially coating a solution of the self-assembled hole transport material and a solution of the interface modification material on the flexible conductive substrate or the flexible conductive substrate covered with the nickel oxide to obtain a wet film.
And S103, drying the wet film by a low-temperature heating or vacuumizing method to obtain the modified hole transport layer serving as the buried interface modification layer.
Those skilled in the art will recognize that due to the self-assembling nature of material H, material H will self-assemble to form a single molecule SAM layer from which the hole transport layer is formed in the case where the flexible conductive substrate is not covered with nickel oxide, and from which the hole transport layer is formed by the nickel oxide layer and the single molecule SAM layer in the case where the flexible conductive substrate is covered with nickel oxide. Meanwhile, the material D forms an interface modification layer to modify the hole transport layer. Thus, a buried interface modification layer including the hole transport layer and the interface modification layer was obtained.
According to the preparation method of the buried interface modification layer, provided by the embodiment of the invention, the mixed liquid of the hole transport material (self-assembly layer) and the interface modification material is coated (or deposited) on the flexible substrate, or the two materials are sequentially coated (or deposited), so that good contact performance between the two materials can be realized, and interface modification is realized on the buried interface (flexible substrate conducting layer/hole transport layer interface) of the flexible perovskite solar cell. By forming the buried interface modification layer, the technical problem that a single molecule self-assembly layer in the flexible perovskite solar cell is contacted with a buried interface of a flexible substrate and energy level matching is solved.
In some embodiments, the flexible conductive substrate includes a flexible substrate and a conductive layer on the flexible substrate. The material of the flexible substrate may be, for example, PET (Polyethylene Terephthalate ) or PEN (Polyethylene Naphthalate, polyethylene naphthalate) or the like. The conductive layer may be, for example, an ITO (Indium Tin Oxide) layer or the like. The present invention is not particularly limited thereto.
In some embodiments, the interface modifying material may include, but is not limited to, one or more of polypyrrole, polyaniline, polyethylene terephthalate, graphene oxide, poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] (PTAA), carbon quantum dots, carbon nanotubes.
In some embodiments, the self-assembled hole transporting material is a small molecule SAM material, which may include, but is not limited to, one or more of (2- (9H-carbazol-9-yl) ethyl) phosphonic acid (2 PACz), [2- (3, 6-dimethoxy-9H-carbazol-9-yl) ethyl ] phosphonic acid (MeO-2 PACz), (2- (4- (10H-phenothiazin-10-yl) phenyl) -1-cyanovinyl) phosphonic acid (2- (4- (10H-phenothiazin-10-yl) phenyl) -1-cyanovinyl) phosphonic acid, abbreviated PTZ-CPA), [4- (3, 6-dimethyl-9H-carbazol-9-yl) butyl ] phosphoric acid (Me-4 PACz).
In addition, a suitable solvent is selected to prepare a solution according to the difference in solubility of the materials used. Alternatively, the solvent may be one or more of water, ethanol, methanol, isopropanol, acetonitrile, acetone, tetrahydrofuran, chlorobenzene, dichlorobenzene, toluene, xylene, chloroform, methylene chloride, etc., but is not limited thereto.
In some embodiments, the concentration of the self-assembled hole transporting material (material H) in the interface modification mixed solution (H-D mixed solution) or the solution of the self-assembled hole transporting material (H solution) is a value in the range of 0.05 to 20mM, e.g., 0.1, 0.5, 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20mM.
In some embodiments, the concentration of the interface modification material (material D) in the H-D mixed solution or the solution of the interface modification material (D solution) is a value in the range of 0.1 to 50mM, e.g., 0.2, 0.3, 0.4, 0.5, 0.7, 1.0, 5.0, 10, 15, 20, 25, 30, 35, 40, 45, 50mM. Preferably, the material D concentration in the H-D mixed solution or D solution is in the range of 0.1 to 1.0 mM. More preferably, the material D concentration in the H-D mixed solution or D solution is in the range of 0.1 to 0.5 mM.
In some alternative embodiments, the Coating in steps S102 and S102' is a Blade-Coating method (Blade-Coating) or a Slot-Die Coating method (Slot-Die Coating).
In some specific embodiments, the coating conditions are that the total coating solution amount is 100-200 mu l, the coating speed is 5 mm.s -1, and the coating times are 1.
It should be noted that, since the thickness of the interface modification layer formed by the material D is extremely thin, it is difficult to accurately measure and calculate, and therefore, in practical applications, different concentrations of the material D are used to represent the thickness of the interface modification layer.
In some optional embodiments, the low-temperature heating condition in step S103 is 80-100 ℃ heat stage heating for 5-20 min. For example, specific heating temperatures may be 85 ℃, 90 ℃, 95 ℃, 100 ℃, etc. Specific heating times may be 8, 10, 12, 15, 18, 20 minutes, etc.
In other alternative embodiments, the vacuum pumping condition in step S103 is that the vacuum is maintained at 80-100 Pa for 5-10 min.
The invention also provides a buried interface modification layer which is prepared by the preparation method of any embodiment or combination of embodiments.
In some preferred embodiments, the buried interface modification layer can have an area of up to 1-1000cm 2, e.g., 10, 20, 50, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000cm 2. The large-area buried interface modification layer is more suitable for being applied to perovskite solar cell modules.
Based on the same technical concept, the invention also provides the flexible perovskite solar cell small module 100. Fig. 3 is a schematic structural view of a flexible perovskite solar cell module 100 according to an embodiment of the invention, and fig. 4 is a schematic structural view of the flexible perovskite solar cell module 100 according to another embodiment of the invention.
As shown in fig. 3 and 4, the flexible perovskite solar cell small module 100 includes a flexible transparent substrate 101, a conductive layer 102, a buried interface modification layer 110, a perovskite absorption layer 105, an electron transport layer 106, and a counter electrode 107, which are sequentially stacked from bottom to top. The buried interface modification layer 110 is a buried interface modification layer manufactured by the manufacturing method described in any of the foregoing embodiments or combinations of embodiments, and includes the hole transport layer 103 and the interface modification layer 104.
In some embodiments, as shown in fig. 3, the hole transport layer 103 includes a nickel oxide layer 1031 and a single molecule SAM layer 1032 stacked from bottom to top. In other embodiments, as shown in fig. 4, the hole transport layer 103 includes only a single molecule SAM layer 1032.
The following describes each structural layer of the flexible perovskite solar cell module 100 in detail.
The flexible transparent substrate 101 is made of a flexible transparent material such as PET (Polyethylene Terephthalate ) or PEN (Polyethylene Naphthalate, polyethylene naphthalate) or the like. The conductive layer 102 is an ITO (Indium Tin Oxide) layer. The flexible transparent substrate 101 and the conductive layer 102 together constitute a flexible transparent conductive substrate (abbreviated as ITO/PET or ITO/PEN). In preparing the flexible perovskite solar cell module 100, first, patterned P1 etching is performed on the conductive layer 102. The P1 etch may be performed using methods known in the art, the purpose of which is to divide the small module into several sub-cells.
As previously described, in some embodiments, the hole transport layer 103 may include only a single molecule SAM layer 1032. In other embodiments, hole transport layer 103 may include nickel oxide layer 1031 and single molecule SAM layer 1032, i.e., hole transport layer 103 is a NiO x/SAM structure. The NiO x film thickness is 10-15nm, and can be prepared by vacuum method (such as magnetron sputtering method) or solution method (such as slit coating method), and NiO x solution configuration can be referred to in the prior art. The SAM layer may be made of conventional monolayer material H, such as 2PACz ((2- (9H-carbazol-9-yl) ethyl) phosphonic acid), meO-2PACz ([ 2- (3, 6-dimethoxy-9H-carbazol-9-yl) ethyl ] phosphonic acid), PTZ-CPA (2- (4- (10H-phenothiazin-10-yl) phenyl) -1-cyanovinyl) phosphonic acid), me-4PACz ([ 4- (3, 6-dimethyl-9H-carbazol-9-yl) butyl ] phosphoric acid), and the like. The SAM layer may be prepared by a slot coating method, wherein the concentration of the material H in the coating solution is 0.05 to 20mM. Of course, other coating methods may be used.
The material D of the interface modification layer 104 may include one or more of polypyrrole, polyaniline, polyethylene terephthalate, graphene oxide, poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] (PTAA), carbon quantum dots, and carbon nanotubes, but is not limited thereto. The interfacial modification layer 104 can be obtained in two ways, one by blending it with the hole transport material H and the other by coating (depositing) a thin layer directly on top of the hole transport layer. Either method may be obtained by a slit coating method, but other coating methods may be used. The concentration of the material D in the coating solution is 0.1-50 mM. Because the thickness of the interface modification layer 104 is extremely thin, the thickness is difficult to accurately measure, and therefore, different concentrations are adopted to represent the thickness in practical applications.
The perovskite absorber layer 105 may be prepared based on conventional perovskite precursor solutions. The chemical formula of the perovskite is ABX 3. The thickness of the perovskite absorption layer 105 may be controlled to be around 700 nm.
The process of preparing the perovskite absorber layer 105 will be described below using lead-based perovskite as an example. The precursor solution concentration was about 1.3M. In one embodiment (Cs, FA) PbI 3 precursor solution (Cs xFA1-xPbI3, x=0.03) is illustrated.
Preparation of (Cs, FA) PbI 3 precursor solution PbI 2, FAI and CsI are added into an organic solvent, wherein the sum of the mole numbers of CsI and FAI is the same as that of PbI 2, the mole number ratio of CsI to PbI 2 is 0-15%, a small amount of MACl additive is added to promote crystallization and improve the perovskite crystal grain size (a small amount of residue is negligible in the final perovskite film), and the mixture is stirred at normal temperature for 3 hours to obtain a clear and transparent solution.
Other component perovskite precursor solutions may also be obtained by similar methods as described above, including FAPbI3、(CsxMAyFA1-x-yPbI3,x＝0～0.15,y＝0～0.15)、(RbxMAyFA1-x-yPbI3,x＝0～0.15,y＝0～0.15)、(CsxMAyFA1-x-yPbBrmI3-m,x＝0～0.15,y＝0～0.15,m＝0～0.15)、CsPb(I,Br)3, etc.
The perovskite absorption layer 105 may be obtained by a slit coating method. In some specific embodiments, the coating head is spaced from the substrate by 0.25mm, the coating speed is 5mm/s, and the flow rate is 0.1mL/min during the coating process. And placing the obtained perovskite precursor film on a 100 ℃ heat table for heating for 40min, and finally obtaining the perovskite absorption layer 105.
The material of the electron transport layer 106 may include one of C60/SnO 2, C60/BCP, ITO, etc. C60 is mainly obtained by adopting a vacuum evaporation method, the thickness of the C60 is 20-25 nm, BCP is mainly obtained by adopting a vacuum evaporation method, the thickness of the BCP is 7nm, snO 2 is obtained by adopting an atomic layer deposition method, the thickness of the C60 is 15nm, ITO is mainly obtained by adopting a magnetron sputtering method, and the thickness of the C60 is 100nm.
After completion of the perovskite absorption layer 105 and the electron transport layer 106, P2 etching is required. The P2 etch may be performed using methods known in the art for the purpose of achieving a series connection of adjacent subcells.
Finally, the counter electrode 107 is prepared. In some embodiments, a layer of Ag, cu or Ni/Al electrodes is deposited using a thermal evaporation process.
After the electrode 107 is completed, P3 etching is performed to complete the preparation of the flexible perovskite solar cell small module. The P3 etch may be performed using methods known in the art.
According to the flexible perovskite solar cell small module, the interface modification layer is introduced to improve the contact performance of the buried bottom interface, relieve stress, and also help to improve the quality of perovskite thin film crystals, regulate and control interface energy level matching, so that the conversion efficiency and stability of the perovskite solar cell are remarkably improved. In addition, the interface modification layer and the perovskite solar cell small module have the advantages of raw materials and preparation cost, and the preparation process is simple, easy to operate, suitable for large-area preparation and easy for large-scale production.
The buried interface modification layer, the preparation method thereof and the flexible perovskite solar cell small module using the buried interface modification layer are described above, and the embodiments of the invention are described below by specific examples. Other advantages and effects of the present invention will be readily apparent to those skilled in the art from the present disclosure. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
Examples 1 to 8
The hole transport layer 103 was prepared on a flexible ITO/PET substrate with 2PACz as material H, the H concentration was fixed at 1.8mM. The polypyrrole is used as a material D to prepare the interface modification layer 104, and the concentration range of D is 0.1-50 mM. Materials H and D were prepared as a mixed ethanol solution and deposited on a flexible substrate by slot coating, and the resulting wet film was heated at 100℃for 15 minutes. On this basis, a flexible trans-perovskite solar cell (for example, a module having an area of 12.4cm 2) was prepared. Other thin film materials in the cell are based on common materials commonly used in the art, wherein the transparent substrate 101 is PET, the conductive layer 102 is ITO, the perovskite absorber layer 105 is Cs 0.03FA0.97PbI3, the electron transport layer 106 is C60/SnO 2, and the counter electrode 107 is a Cu electrode.
Table 1 lists the specific experimental parameters of the flexible perovskite solar cell small modules prepared in examples 1-8.
TABLE 1
Wherein Jsc is short circuit current density, voc is open circuit voltage, FF is fill factor, and off is battery conversion efficiency.
Examples 9 to 16
NiO x/2 PACz was deposited as hole transport layer 103 on a flexible ITO/PET substrate in sequence, with NiO x thickness of 10nm and 2PACz concentration fixed at 1.8mM. Polypyrrole is used as an interface modification layer 104, and the concentration of D is 0.1-50 mM. An ethanol solution of the two materials mixed was deposited on a flexible substrate by a slot coating method, and the resulting wet film was heated at 100 ℃ for 15 minutes. On this basis, a flexible trans-perovskite solar cell (for example, a 12.4cm2 module) was prepared. Other thin film materials in the cell are based on common materials commonly used in the art, wherein the transparent substrate 101 is PET, the conductive layer 102 is ITO, the perovskite absorber layer 105 is Cs 0.03FA0.97PbI3, the electron transport layer 106 is C60/SnO 2, and the counter electrode 107 is a Cu electrode.
Table 2 shows the specific experimental parameters of the flexible perovskite solar cell modules prepared in examples 9-16.
TABLE 2
Examples 17 to 24
NiO x/2 PACz is sequentially deposited or 2PACz is directly deposited on the flexible ITO/PET substrate to serve as a hole transport layer 103, wherein the thickness of NiO x is 10nm, and the concentration of 2PACz is 0.05-20 mM. Polypyrrole was used as the interface modification layer 104 at a concentration of 0.50mM. An ethanol solution of the two materials mixed was deposited on a flexible substrate by a slot coating method, and the resulting wet film was heated at 100 ℃ for 15 minutes. On this basis, a flexible trans-perovskite solar cell (exemplified by a 12.4cm 2 small module) was prepared. Other thin film materials in the cell are based on common materials commonly used in the art, where the transparent substrate 101 is PET, the conductive layer 102 is ITO, the perovskite absorber layer 105 is Cs 0.03FA0.97PbI3, the electron transport layer 106 is C60/SnO 2, and the counter electrode 107 is a Cu electrode.
Table 3 sets forth specific experimental parameters for the flexible perovskite solar cell modules prepared in examples 17-24.
TABLE 3 Table 3
Examples 25 to 29
On a flexible ITO/PET substrate, 2PACz was used as the hole transport layer 103 at a concentration of 1.8mM. The interface modification layer 104 uses a different modification material at a concentration of 0.50mM. The two materials were mixed and deposited on a flexible substrate by slot coating, and the resulting wet film was heated at 100 ℃ for 15 minutes. On this basis, a flexible trans-perovskite solar cell (exemplified by a 12.4cm 2 small module) was prepared. Other thin film materials in the cell are based on common materials commonly used in the art, wherein the transparent substrate 101 is PET, the conductive layer 102 is ITO, the perovskite absorber layer 105 is Cs 0.03FA0.97PbI3, the electron transport layer 106 is C60/SnO 2, and the counter electrode 107 is a Cu electrode.
Table 4 shows the specific experimental parameters of the flexible perovskite solar cell modules prepared in examples 25 to 29.
TABLE 4 Table 4
Examples 30 to 31
On a flexible ITO/PET substrate, different SAMs were used as hole transport layers 103 at a concentration of 1.8mM. The interface modification layer 104 employs carbon quantum dots at a concentration of 0.50mM. The two materials were mixed and deposited on a flexible substrate by slot coating, and the resulting wet film was heated at 100 ℃ for 15 minutes. On this basis, a flexible trans-perovskite solar cell (exemplified by a 12.4cm 2 small module) was prepared. Other thin film materials in the cell are based on common materials commonly used in the art, wherein the transparent substrate 101 is PET, the conductive layer 102 is ITO, the perovskite absorber layer 105 is Cs 0.03FA0.97PbI3, the electron transport layer 106 is C60/SnO 2, and the counter electrode 107 is a Cu electrode.
Table 5 lists the specific experimental parameters of the flexible perovskite solar cell small modules prepared in examples 28, 30 and 31.
TABLE 5
Examples 32 to 36
On a flexible ITO/PET substrate, 2PACz was used as the hole transport layer 103 at a concentration of 1.8mM. The interface modification layer 104 employs carbon quantum dots at a concentration of 0.50mM. The two materials were mixed and deposited on a flexible substrate by slot coating, and the resulting wet film was heated at 100 ℃ for 15 minutes. On this basis, a flexible trans-perovskite solar cell (exemplified by a 12.4cm 2 small module) was prepared. Other thin film materials in the cell are based on common materials commonly used in the art, wherein the transparent substrate 101 is PET, the conductive layer 102 is ITO, the perovskite absorbing layer 105 is a perovskite absorbing layer of different composition, the electron transporting layer 106 is C60/SnO 2, and the counter electrode 107 is a Cu electrode.
Table 6 shows the specific experimental parameters of the flexible perovskite solar cell modules prepared in examples 32 to 36.
TABLE 6
In summary, it can be seen from examples 1-36 that the flexible perovskite solar cell small module based on the buried interface modification layer of the present invention can obtain higher photoelectric conversion efficiency compared to examples 1 and 9 where the interface modification layer 104 is not formed. Meanwhile, the preparation process is simple, the cost is low, and the commercialization requirements can be met.
In the description provided herein, numerous specific details are set forth. However, it is understood that embodiments of the invention may be practiced without these specific details. In some instances, well-known methods, structures and techniques have not been shown in detail in order not to obscure an understanding of this description.
By now it should be appreciated by those skilled in the art that while a number of exemplary embodiments of the invention have been shown and described herein in detail, many other variations or modifications of the invention consistent with the principles of the invention may be directly ascertained or inferred from the present disclosure without departing from the spirit and scope of the invention. Accordingly, the scope of the present invention should be understood and deemed to cover all such other variations or modifications.

Claims (10)

1.一种埋底界面修饰层的制备方法，包括：1. A method for preparing a buried interface modification layer, comprising: 将自组装空穴传输材料与界面修饰材料在溶剂中混合得到界面修饰混合溶液，并将所述界面修饰混合溶液涂敷在柔性导电基底上或覆盖有氧化镍的柔性导电基底上获得湿膜；或者Mixing a self-assembled hole transport material and an interface modification material in a solvent to obtain an interface modification mixed solution, and coating the interface modification mixed solution on a flexible conductive substrate or a flexible conductive substrate covered with nickel oxide to obtain a wet film; or 利用溶剂分别配制所述自组装空穴传输材料的溶液和所述界面修饰材料的溶液，并将所述自组装空穴传输材料的溶液和所述界面修饰材料的溶液依次涂敷在柔性导电基底上或覆盖有氧化镍的柔性导电基底上获得湿膜；The solution of the self-assembled hole transport material and the solution of the interface modification material are prepared by using a solvent respectively, and the solution of the self-assembled hole transport material and the solution of the interface modification material are sequentially coated on a flexible conductive substrate or a flexible conductive substrate covered with nickel oxide to obtain a wet film; 将所述湿膜通过低温加热或抽真空方法进行干燥，得到经修饰的空穴传输层作为埋底界面修饰层。The wet film is dried by low temperature heating or vacuuming to obtain a modified hole transport layer as a buried interface modification layer. 2.根据权利要求1所述的埋底界面修饰层的制备方法，其中，2. The method for preparing the buried interface modification layer according to claim 1, wherein: 所述界面修饰材料包括聚吡咯、聚苯胺、聚对苯二甲酸乙二醇酯、氧化石墨烯、聚[双(4-苯基)(2,4,6-三甲基苯基)胺](PTAA)、碳量子点、碳纳米管中的一种或多种。The interface modification material includes one or more of polypyrrole, polyaniline, polyethylene terephthalate, graphene oxide, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), carbon quantum dots, and carbon nanotubes. 3.根据权利要求1所述的埋底界面修饰层的制备方法，其中，3. The method for preparing the buried interface modification layer according to claim 1, wherein: 在所述界面修饰混合溶液或所述自组装空穴传输材料的溶液中所述自组装空穴传输材料的浓度为0.05～20mM范围内的值；The concentration of the self-assembled hole transport material in the interface modification mixed solution or the solution of the self-assembled hole transport material is a value within the range of 0.05 to 20 mM; 在所述界面修饰混合溶液或所述界面修饰材料的溶液中所述界面修饰材料的浓度为0.1～50mM范围内的值。The concentration of the interface modification material in the interface modification mixed solution or the interface modification material solution is in the range of 0.1 to 50 mM. 4.根据权利要求3所述的埋底界面修饰层的制备方法，其中，4. The method for preparing the buried interface modification layer according to claim 3, wherein: 所述涂敷的方式为刮涂法或狭缝涂布法，The coating method is a blade coating method or a slit coating method. 所述涂敷的条件为：总涂敷溶液量100～200μl，涂布速度5mm·s-1，涂布次数1次。The coating conditions are as follows: the total coating solution volume is 100-200 μl, the coating speed is 5 mm·s -1 , and the coating frequency is 1 time. 5.根据权利要求1所述的埋底界面修饰层的制备方法，其中，5. The method for preparing the buried interface modification layer according to claim 1, wherein: 所述低温加热的条件为：80～100℃热台加热5～20min；The low temperature heating conditions are: heating on a hot plate at 80-100°C for 5-20 minutes; 所述抽真空的条件为：在80～100Pa真空下保持5～10min。The vacuuming condition is: maintaining a vacuum of 80-100 Pa for 5-10 minutes. 6.根据权利要求1所述的埋底界面修饰层的制备方法，其中，6. The method for preparing the buried interface modification layer according to claim 1, wherein: 所述自组装空穴传输材料包括(2-(9H-咔唑-9-基)乙基)膦酸(2PACz)、[2-(3,6-二甲氧基-9H-咔唑-9-基)乙基]膦酸(MeO-2PACz)、(2-(4-(10H-吩噻嗪-10-基)苯基)-1-氰乙烯基)膦酸(PTZ-CPA)、[4-(3,6-二甲基-9H-咔唑-9-基)丁基]磷酸(Me-4PACz)中的一种或多种。The self-assembled hole transport material includes one or more of (2-(9H-carbazole-9-yl)ethyl)phosphonic acid (2PACz), [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid (MeO-2PACz), (2-(4-(10H-phenothiazine-10-yl)phenyl)-1-cyanovinyl)phosphonic acid (PTZ-CPA), and [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid (Me-4PACz). 7.一种埋底界面修饰层，其是通过权利要求1-6中任一项所述的方法制得的。7. A buried interface modification layer, which is prepared by the method according to any one of claims 1 to 6. 8.根据权利要求7所述的埋底界面修饰层，其中，所述埋底界面修饰层的面积为1～1000cm2。8 . The buried interface modification layer according to claim 7 , wherein the area of the buried interface modification layer is 1 to 1000 cm 2 . 9.一种柔性钙钛矿太阳能电池小模组，包括自下而上顺序堆叠的柔性透明基底、导电层、埋底界面修饰层、钙钛矿吸收层、电子传输层以及对电极，其中，所述埋底界面修饰层为根据权利要求7或8所述的埋底界面修饰层。9. A flexible perovskite solar cell small module, comprising a flexible transparent substrate, a conductive layer, a buried interface modification layer, a perovskite absorption layer, an electron transport layer and a counter electrode stacked in sequence from bottom to top, wherein the buried interface modification layer is the buried interface modification layer according to claim 7 or 8. 10.根据权利要求9所述的柔性钙钛矿太阳能电池小模组，其中，所述柔性钙钛矿太阳能电池为反式钙钛矿太阳能电池。10. The flexible perovskite solar cell small module according to claim 9, wherein the flexible perovskite solar cell is an inverted perovskite solar cell.
CN202411210831.1A 2024-08-30 2024-08-30 Buried interface modification layer and its preparation, flexible perovskite solar cell small module Pending CN119095453A (en)

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