CN117202677A - Perovskite solar cell, preparation method thereof, passivation layer and photovoltaic module - Google Patents

Perovskite solar cell, preparation method thereof, passivation layer and photovoltaic module Download PDF

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CN117202677A
CN117202677A CN202210600315.4A CN202210600315A CN117202677A CN 117202677 A CN117202677 A CN 117202677A CN 202210600315 A CN202210600315 A CN 202210600315A CN 117202677 A CN117202677 A CN 117202677A
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layer
molecular weight
average molecular
transport layer
solar cell
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请求不公布姓名
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Beijing Yaoneng Optoelectronic Technology Co ltd
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Priority to PCT/CN2023/096567 priority patent/WO2023227114A1/en
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/40—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
    • H10K30/85—Layers having high electron mobility, e.g. electron-transporting layers or hole-blocking 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
    • H10K30/80—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
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    • 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 application provides a perovskite solar cell and a preparation method thereof, a passivation layer and a photovoltaic module, relates to the technical field of solar cells, and can solve the problems of small resistance and poor passivation effect of devices caused by the fact that a compact transmission layer cannot be well formed by the existing wet process. The perovskite solar cell comprises a perovskite light absorption layer and a transmission layer positioned on one side of the perovskite light absorption layer; the transport layer is made of a high weight average molecular weight material with a weight average molecular weight not lower than a first target value, or, between the transport layer and the perovskite light absorbing layer, there is further provided: and a passivation layer made of a high weight average molecular weight material having a weight average molecular weight not lower than a first target value.

Description

Perovskite solar cell, preparation method thereof, passivation layer and photovoltaic module
Technical Field
The application relates to the technical field of solar cells, in particular to a perovskite solar cell, a preparation method thereof, a passivation layer and a photovoltaic module.
Background
At present, the solar cell industry is rapidly developed, the p-type crystalline silicon solar cell is mainly used in the market, the mass production efficiency exceeds 20%, and the theoretical limit of single-junction silicon efficiency is approached. In order to further reduce the cost of the photovoltaic system, it is necessary to further develop a photovoltaic solar cell having low cost. The perovskite solar cell has the advantages of low cost and the like because the forbidden bandwidth of the perovskite solar cell is adjustable, and the perovskite solar cell can be prepared by using a solution method, so that the perovskite solar cell is not only a potential candidate of a single junction solar cell, but also a potential candidate of a multi-junction solar cell.
For a crystalline silicon-perovskite laminated cell, the surface of an industrial silicon wafer has roughness of a micrometer scale, which presents challenges to the solution process for preparing the perovskite, and becomes a great difficulty in mass production of the crystalline silicon-perovskite laminated cell. If the industrial silicon wafer is directly used without treatment, the roughness is usually not lower than 1 mu m, and the inventor finds that the existing wet process is difficult to form an ultrathin and uniformly covered transmission layer on the industrial silicon wafer, so that the parallel resistance of a perovskite (or perovskite/crystalline silicon laminated cell) battery is easy to be small, and further the short circuit of a device and the poor interface passivation effect are caused. Laboratories typically reduce roughness significantly by chemical mechanical polishing, which adds significantly to the cost of commercial production, while other methods such as vacuum physical deposition are not suitable for large scale mass production.
Disclosure of Invention
The perovskite solar cell, the preparation method thereof, the passivation layer and the photovoltaic module can solve the problems of small device resistance and poor passivation effect caused by the fact that the existing wet process cannot well form a continuously distributed compact transmission layer.
In a first aspect, embodiments of the present application provide a perovskite solar cell comprising a perovskite light absorbing layer, and a transport layer located on one side of the perovskite light absorbing layer; a first high weight average molecular weight material having a value of weight average molecular weight not lower than a first target value;
or a passivation layer is further arranged between the transmission layer and the perovskite light absorption layer, and the material of the passivation layer is a second high-weight-average molecular weight material with the weight-average molecular weight value not lower than a first target value.
Optionally, the first target value is about 80000.
Optionally, the first high weight average molecular weight material and the second high weight average molecular weight material are each independently selected from one or more of the following: PTAA, poly-TPD, P3HT, N2200 and N2300, and modified materials of any of the foregoing.
Optionally, the transport layer is an electron transport layer or a hole transport layer.
Optionally, when the transport layer is an electron transport layer, the first high weight average molecular weight material is selected from one or more of modified or unmodified N2200, modified or unmodified N2300; or,
when the transport layer is a hole transport layer, the first high weight average molecular weight material is selected from one or more of modified or unmodified PTAA, modified or unmodified Poly-TPD, modified or unmodified P3 HT.
Alternatively, the thickness of the transport layer is 3 to 30nm, preferably, the thickness of the transport layer is 4 to 5nm.
Optionally, a passivation layer is further disposed between the transmission layer and the perovskite light absorption layer, and when the material of the passivation layer is a second weight average molecular weight material with a weight average molecular weight value not lower than a first target value, the material of the transmission layer includes SnO x 、TiO x 、ZnO x 、WO x Fullerene and derivatives thereof, cuI, cuSCN, cuO x 、NiO x 、MoS 2 、WS 2 One or more of spiro-TTB, spiro-MeOTAD, PEDOT: PSS.
Optionally, the thickness of the passivation layer made of the second high-weight average molecular weight material is 1-20 nm, and the thickness of the passivation layer is preferably 2nm.
Optionally, the perovskite solar cell comprises a roughened substrate comprising any one of the following: industrial silicon wafers with diamond line cuts or micrometer scale roughness on the surface, conductive glass with transparent conductive electrodes deposited on the surface, and crystalline silicon cells with textured pyramid surfaces.
In a second aspect, another embodiment of the present application also provides a passivation layer for a solar cell, the passivation layer having a material of a first high weight average molecular weight material having a value of a weight average molecular weight not lower than a first target value, the first target value being 80000.
Optionally, the passivation layer simultaneously serves as a transport layer for the solar cell.
In a third aspect, another embodiment of the present application further provides a photovoltaic module, including a perovskite solar cell as described in any one of the above, or including a passivation layer as described in any one of the above.
Optionally, the photovoltaic module includes: perovskite cells, stacked cells of crystalline silicon and perovskite, or all perovskite stacked cells.
In a fourth aspect, another embodiment of the present application further provides a method for preparing a perovskite solar cell, including: a step of preparing a transport layer; in the step of preparing the transport layer, the transport layer is formed using a wet process using a first high weight average molecular weight material having a weight average molecular weight value not lower than a first target value.
Another embodiment of the present application also provides a method for manufacturing a perovskite solar cell, including: a step of preparing a transport layer and a step of preparing a perovskite light absorption layer; between the process of preparing the transport layer and the process of preparing the perovskite light absorbing layer, further comprising:
and forming a passivation layer on the surface of the transmission layer by adopting a wet process by utilizing a second weight average molecular weight material with the weight average molecular weight not lower than a first target value.
Optionally, the transmission layer includes a first transmission layer and a second transmission layer; the second high-weight average molecular weight material comprises a high polymer material A and a high polymer material B;
the preparation method comprises the following steps:
forming a first transmission layer on the rough substrate; the material of the first transmission layer is selected from SnO x 、TiO x 、ZnO x 、WO x Fullerene and derivatives thereof, cuI, cuSCN, cuO x 、NiO x 、MoS 2 、WS 2 One or more of spiro-TTB, spiro-MeOTAD, PEDOT: PSS;
coating a solution containing the high polymer material A on the first transmission layer to form a passivation layer of the first transmission layer; the polymer material A is selected from one or more of modified or unmodified PTAA, modified or unmodified Poly-TPD, modified or unmodified P3HT, modified or unmodified N2200 and modified or unmodified N2300; poly (E)
Forming a perovskite light absorption layer on the passivation layer;
forming a second transport layer over the perovskite light absorbing layer; the material of the second transmission layer is selected from SnO x 、TiO x 、ZnO x 、WO x Fullerene and derivatives thereof, cuI, cuSCN, cuO x 、NiO x 、MoS 2 、WS 2 One or more of spiro-TTB, spiro-MeOTAD, PEDOT: PSS;
coating a solution containing a high polymer material B on the second transmission layer to form a passivation layer of the second transmission layer; the polymer material B is selected from one or more of modified or unmodified PTAA, modified or unmodified Poly-TPD, modified or unmodified P3HT, modified or unmodified N2200 and modified or unmodified N2300.
In a fifth aspect, another embodiment of the present application provides a use of a high weight average molecular weight material having a value of weight average molecular weight not lower than a first target value, the first target value being 80000, as a passivation layer or a transport layer in a solar cell.
In a sixth aspect, embodiments of the present application further provide a passivation layer material of a solar cell, where a value of a weight average molecular weight of the passivation layer material is not lower than a first target value, and the first target value is 80000.
In a seventh aspect, embodiments of the present application also provide a transport layer material of a solar cell, where a value of a weight average molecular weight of the transport layer material is not lower than a first target value, and the first target value is 80000.
According to the perovskite solar cell, the preparation method thereof, the passivation layer and the photovoltaic module, the passivation layer made of the second high-weight-average molecular weight material with high weight-average molecular weight is arranged between the transmission layer and the perovskite light absorption layer, or the transmission layer is directly made of the first high-weight-average molecular weight material with high weight-average molecular weight, the inventor finds that the high-molecular weight (high-weight-average molecular weight) material is easy to spread on a rough surface in a large area to form a continuously distributed compact film layer, so that devices caused by uneven distribution of the transmission layer or the passivation layer thereof can be avoided, and the passivation effect is poor. The weight average molecular weight of the first high-weight average molecular weight material and the second high-weight average molecular weight material is not lower than a first target value, the specific value of the first target value can be determined according to the design requirement of a transmission layer in a specific application scene, and the specific value of the first target value is about 8 ten thousand generally. The design requirement of the transmission layer is thinner, the passivation effect is stronger, the value of the first target value can be larger, and conversely, the value of the first target value can be smaller. The scheme provided by the embodiment of the application can form a thin transmission layer or passivation layer by adopting a wet process, and is very suitable for large-scale industrial production, in particular to the preparation of a perovskite solar cell with a large area.
Drawings
Fig. 1 is a schematic structural diagram of a perovskite battery according to an embodiment of the present application;
fig. 2 is a schematic structural diagram of a perovskite battery according to a second embodiment of the present application;
fig. 3 is a schematic structural diagram of a stacked perovskite and crystalline silicon cell according to a third embodiment of the present application;
FIG. 4 is a confocal microscope image of the surface morphology of an industrial wafer (a) and a laboratory-grade wafer (b) according to a third embodiment of the present application;
FIG. 5 is a V of an opaque device employing PTAA (c) and Poly-TPD (d) interface passivation in embodiment III of the application OC Statistics data;
FIG. 6 is a CAFM and AFM image stack of Poly-TPD 15k (e) and Poly-TPD 200k (f) on top of FTO glass in example three of the present application.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more apparent, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Wet forming a uniformly covered transmission layer (e.g. <20 nm) or ultra-thin passivation layer on rough substrate (e.g. <20 nm) surfaces is currently not very good, which causes two major problems: good passivation effect cannot be formed between the perovskite light absorption layer and the existing transmission layer; the transport layer does not form a dense coating on the perovskite light absorbing layer. Thus, perovskite and perovskite/crystalline silicon lamination are easy and have low resistance, and further result in short circuit of devices and low yield. However, too thick a transmission layer or passivation layer is not good, and it affects the conversion efficiency of the solar cell, especially the stacked cell.
Similarly, conductive glass such as FTO glass has transparent electrodes on the surface and photovoltaic grade crystalline silicon cells have textured pyramid surfaces, i.e., these substrates also have roughness that affects the fabrication of the transmission layer, and the same problems exist for the fabrication of perovskite cells.
In carrying out the application to solve the above problems, the inventors of the present application found that: the use of a material having a high molecular weight (e.g., a polymer having a weight average molecular weight of not less than 80,000) can effectively avoid this problem in a wet process. For example, the high molecular weight material can be spread on a rough surface in a large area, and a compact coverage is formed on the perovskite light absorption layer, so that devices caused by uneven material distribution and poor passivation effect of materials in a transmission layer and/or a passivation layer and other layer structures are avoided when the material is prepared by a wet process, and the perovskite light absorption layer is very suitable for large-scale industrial production, in particular for the preparation of large-area perovskite batteries.
High molecular weight materials, particularly high molecular polymers, will have a range of molecular weights, and thus the weight average molecular weight is used herein to describe the size of the molecular weight of the high molecular weight materials as they appear herein. Those skilled in the art will understand that if a high molecular weight material is present that is composed of molecules of a single relative molecular mass, the weight average molecular weight herein will be understood to be the relative molecular mass of the material composed of molecules of that single relative molecular mass; if the high molecular weight material comprises a molecular composition of two or more different relative molecular masses, then the weight average molecular weight herein is understood to be the molecular weight average of the molecules of the two or more different relative molecular masses.
The presence of the first or second high weight average molecular weight material in the description herein is merely representative of a material that is high molecular weight and is not intended to limit that it must be a high molecular polymer.
Based on this, embodiments of the present application provide a perovskite solar cell including a perovskite light absorbing layer, and a transport layer located on one side of the perovskite light absorbing layer; a material of the transport layer is a first high weight average molecular weight material having a weight average molecular weight not lower than a first target value; or alternatively
A passivation layer is further arranged between the transmission layer and the perovskite light absorption layer, and the passivation layer is made of a second high-weight-average molecular weight material with the weight-average molecular weight not lower than a first target value.
Perovskite solar cells herein refer to all mineral solar cells including perovskite absorber layers, including but not limited to single junction perovskite solar cells, perovskite-crystalline silicon tandem solar cells, all perovskite multi-junction solar cells. The battery can solve the problems of poor passivation effect and small resistance of the transmission layer or the passivation layer caused by similar substrate roughness by applying the scheme. The weight average molecular weight herein refers to the average weight average molecular weight, i.e., herein, a first high weight average molecular weight material having a value of the weight average molecular weight not lower than a first target value and a second high weight average molecular weight material having a value of the weight average molecular weight not lower than the first target value should be understood as: when a certain high molecular polymer is selected from the first high weight average molecular weight material and the second high weight average molecular weight material respectively and independently, the relative molecular weight is the weight average molecular weight of the high molecular polymer; when the first high molecular weight material and the second high molecular weight material are respectively and independently selected from a plurality of high molecular polymers, the weight average molecular weight thereof is the average value of the weight average molecular weights of the selected plurality of high molecular polymers.
Illustratively, in some embodiments, the above-mentioned polymer is a polymer material having a weight average molecular weight of not less than 50000, i.e., the first target value may be 5 ten thousand.
According to the embodiment of the application, the passivation layer made of the high-weight average molecular weight material is adopted, or the transmission layer is directly made of the high-weight average molecular weight material, and the high-weight average molecular weight material can be developed on the rough surface in a large area by adopting a wet process to form continuous distribution, so that poor passivation and short circuit paths caused by uneven distribution of the passivation layer or the transmission layer can be solved. The specific weight average molecular weight of the high weight average molecular weight material is not lower than a first target value, so that a film layer continuously covering a rough substrate can be formed by adopting a wet process in specific application, and the design requirement of a passivation layer or a transmission layer can be met.
The first target value is related to a specific material and a rough substrate to be covered, and the embodiment is not specifically limited. The specific value of the passivation layer can be determined according to experiments in specific implementation, so that the transmission layer or the passivation layer can form a film layer which continuously covers a rough substrate, the passivation effect and the device resistance meet requirements, and the thickness of the film layer is in the range of design requirements. The first target value is, for example, approximately 80000. It can be understood by those skilled in the art that 80000 is a general range, and according to the current experimental results, the weight average molecular weight of 80000 or above can achieve a better coverage effect on a conventional rough substrate (an industrial silicon wafer, conductive glass or a crystalline silicon cell with a textured pyramid surface), and can meet the design requirements of a transmission layer or a passivation layer.
In other examples, the first target value is 10 ten thousand or 15 ten thousand.
Wherein, optionally, the first high weight average molecular weight material and the second high molecular weight material are each independently selected from PTAA (N, N '-bis-4-butylphenyl-N, N' -diphenyl), poly-TPD (polyanilines), P3HT (Poly-3 hexylthiophene), N2200, and N2300, and modified materials of any of the foregoing.
The material of the transport layer or the passivation layer may include not only PTAA, poly-TPD, P3HT, N2200, and N2300, but also a material obtained by modification based on any one of these materials, or may include a mixture of at least two of these materials and modified materials thereof. Modification of a material refers to modification of the material by various means (including, but not limited to, grafting of functional groups at a branch) in order to achieve superior properties in the material. In particular, the types of polymers that can be used for the passivation or transport layer made of high weight average molecular weight materials include PTAA, poly-TPD, P3HT, N2200, and N2300, as well as modified varieties of these types. For example, modified variety of N2200F-N2200 OS0400-F N2200-F P (NDI-2 FT) P (NDIOD-2 FT) PNDI-2FT, which has the formula:
modified varieties of Poly-TPD are, for example: poly-TPD-C6, poly-TPD-C8; modified varieties of PTAA such as PTAA-2F, PTAA-3F, PTAA-2Me, PTAA-3Me, etc.
The transport layer may be an electron transport layer or a hole transport layer.
Wherein, the thickness of the transmission layer based on the first high weight average molecular weight material is 3-30 nm, such as 3nm, 5nm, 10nm, 13nm, 15nm, 18nm, 20nm, 23nm, 25nm, 28nm, 30nm, which can achieve better experimental effect. Wherein, preferably, the short circuit of the device can be avoided within the range of 3-10 nm, and better film quality and better photoelectric parameters of the device can be achieved. Further preferably, the effect is better when the thickness of the transport layer is 4 to 5nm.
Wherein, when the transport layer is made of conventional material, such as SnO x 、TiO x 、ZnO x 、WO x Fullerene and derivatives thereof, cuI, cuSCN, cuO x 、NiO x 、MoS 2 、WS 2 、spiro-TTB、spiro-MeOTAD、PEDOT:PSS x In one or more of the above, a film layer based on a second high weight average molecular weight material may be used as a passivation layer for the transport layer made of the above conventional material.
When the transmission layer adopts other transmission layer materials which are not disclosed at present, a film layer based on a second high weight average molecular weight material can be used as a passivation layer of the transmission layer made of the traditional material, so that devices are prevented from being excessively small in resistance and passivation effect is ensured.
The second high weight average molecular weight material may be PTAA, poly-TPD, P3HT, N2200 or N2300 having a weight average molecular weight of not less than 8 ten thousand, or a modified polymer of these polymers, or a mixture of at least two of the above modified or unmodified polymers.
In this case, the passivation layer may have a thickness of 1 to 20nm, for example, the passivation layer may have a thickness of 3nm, 5nm, 8nm, 10nm, 13nm, 15nm, 18nm, 20nm. Preferably, the passivation layer has a thickness in the range of 1-15 nm, so that a good passivation effect can be achieved, and the quality of the film layer and the photoelectric parameters of the device are good. Further preferably, the thickness of 2 to 3nm is more effective. In particular embodiments, the passivation layer may have a thickness of 2nm.
The material of the transport layer may comprise a mixture of two or more high weight average molecular weight materials. The first high weight average molecular weight material of the high weight average molecular weight material may be a polymer having a weight average molecular weight of not less than 8 ten thousand. The mixing of a plurality of polymers having a weight average molecular weight of not less than 8 ten thousand can improve the properties of the transport layer. For example, a hole transport layer based on a material with a high weight average molecular weight is prepared from a solution in which PTAA with a weight average molecular weight of 200000 and Poly-TPD with a weight average molecular weight of 80000 to 120000 are mixed as solutes.
PTAA can not well passivate the perovskite surface as a hole transport layer, so that the open-circuit voltage is low, but PTAA is high in hole transport efficiency, and can reduce series groups and improve the filling factor. Conversely, the low hole transport efficiency of Poly-TPD results in a lower device fill factor, but good passivation effect and high open circuit voltage. Thus, mixing PTAA and Poly-TPD in the precursor solution for preparing the transport layer can achieve an increase in open circuit voltage and fill factor.
For easy understanding, the technical scheme of the present application is further described below with reference to specific embodiments and drawings.
Example 1
Referring to fig. 1, there is provided a perovskite solar cell including a rough substrate 10, the cell further including a perovskite light-absorbing layer 14 formed on the rough substrate 10, and an electron transport layer 12 and a hole transport layer 16 located on both sides of the perovskite light-absorbing layer 14; a first passivation layer 13 is further disposed between the electron transport layer 12 and the perovskite light absorbing layer 14, and a material of the first passivation layer 13 is a polymer material a having a weight average molecular weight value not lower than a first target value.
In another implementation of this example, a second passivation layer 15 is disposed between the hole transporting layer 16 and the perovskite light absorbing layer 14, and the material of the second passivation layer 15 is a polymer material B having a weight average molecular weight value not lower than a first target value. The presence or absence of other film layers such as the first passivation layer 13 is not limited.
In other implementations of the present example, the first passivation layer 13 and the second passivation layer 15 are present at the same time, and the first passivation layer 13 and the second passivation layer 15 are each made of a second high weight average molecular weight material having a weight average molecular weight not lower than the first target value. The first target value may be 80000, for example. The specific material of the second high-weight average molecular weight material is not limited, and the second high-weight average molecular weight material can form a passivation layer which is continuously distributed and meets the passivation requirement as long as the weight average molecular weight is large enough.
The materials of the electron transport layer of this embodiment include those made of: snO (SnO) x 、TiO x And Zno x One or more of the following; the material of the hole transport layer comprises NiO x One or more of CuI, cuSCN, and PTAA.
The material of the electron transport layer may further comprise ZrO 2 Fullerene and its derivative, tiSnO X And SnZnO X One or more of the following; the hole transport layer material may also include PTAA, poly-TPD, P3HT, V 2 O 5 、MoO x 、PEDOT:PSS、WO x 、Spiro-OMeTAD、Cu 2 O, spiro-TTB, m-MTDATA and TAPC.
The material of the perovskite light absorbing layer 14 is not particularly limited in this embodiment. The perovskite light absorbing layer generally has ABX 3 Crystal bodyStructure wherein a and B are cations and X is an anion. Wherein A may be a monovalent cation including, but not limited to, one or more cations of lithium, sodium, potassium, cesium, rubidium, amine groups, or amidino groups; b can be divalent cations including, but not limited to, one or more cations of lead, tin, tungsten, copper, zinc, gallium, selenium, rhodium, germanium, arsenic, palladium, silver, gold, indium, antimony, mercury, iridium, thallium, bismuth; x may be a monovalent anion including, but not limited to, one or more anions of iodine, bromine, chlorine, or astatine. Illustratively, the perovskite light absorbing layer may be a methylammonium lead trihalide CH 3 NH 3 PbX 3 Where X is a halide ion, such as iodide, bromide or chloride, having an optical bandgap between-1.2 and 2.3eV (depending on the halide content).
Further, the perovskite solar cell may further include an upper electrode 17 and a lower electrode 11.
Example two
Referring to fig. 2, there is provided a perovskite solar cell including a rough substrate 10, a perovskite light-absorbing layer 14 formed on the rough substrate 10, and an electron transport layer 12 and a hole transport layer 16 located on both sides of the perovskite light-absorbing layer 14; the material of at least one layer structure of the electron transport layer 12 and the hole transport layer 16 includes a first high-weight average molecular weight material having a weight average molecular weight not lower than a first target value. The first target value may be 80000, for example. The perovskite solar cell further comprises an upper electrode 17 and a lower electrode 11.
As an implementation manner of this embodiment, the material of the electron transport layer of the perovskite battery is N2200 or a modified material of N2200 or a mixed material of the two, and the weight average molecular weight of the modified materials of N2200 and N2200 is not lower than the first target value, so that the solution of the modified material of N2200 or N2200 can form a continuously distributed film layer on the rough substrate 10, thereby solving the problem that an ultrathin and uniformly covered electron transport layer is difficult to form on the rough substrate by a wet process, and further improving the problem that the perovskite battery has low resistance and causes a short circuit of a device. Further, the thickness of the electron transport layer formed by the high-weight average molecular weight material is preferably 4-5 nm, and the interface passivation effect contacted with perovskite is relatively good on the basis of realizing the function of the electron transport layer, and no passivation layer is required to be additionally added. The ultra-thin electron transport layer can be formed by a wet process (such as a solution spin-on film forming method) suitable for industrialization. In other embodiments, the material of the electron transport layer of the perovskite battery is N2300, or a modified material of N2300, or a mixture of both, and the weight average molecular weight of the modified materials of N2300 and N2300 is not lower than the first target value, so that an ultra-thin and uniform electron transport layer covering the rough substrate 10 can be formed on the rough substrate 10.
As an implementation of the present example, the material of the hole transport layer of the perovskite battery includes a first high weight average molecular weight material, wherein the first high weight average molecular weight material may be one or more of PTAA, poly-TPD, P3HT and a modified material of any of the above. The weight average molecular weight of the first high weight average molecular weight material is not lower than the first target value, so that a continuously distributed film can be formed on the rough substrate 10, the problem that an ultrathin and uniformly covered hole transport layer is difficult to form on the rough substrate by a wet process is solved, and the problem that a device is short-circuited due to low resistance of a perovskite battery can be further improved. Further, the thickness of the hole transport layer formed by the first high-weight average molecular weight material is preferably 4-5 nm, so that the interface passivation effect of the perovskite contact is relatively good on the basis of ensuring the function of the hole transport layer, and no passivation layer is required to be additionally added. The ultrathin hole transport layer of the embodiment can be manufactured by adopting a wet process (such as a mode of manufacturing a solution spin-coating film) suitable for industrialization.
It will be appreciated by those skilled in the art that materials with high weight average molecular weight capable of functioning as a transport layer (electron transport layer/hole transport layer) achieve the technical effects described in this embodiment, and therefore are not limited to the above-mentioned materials, but are intended to be covered by the present application.
Example III
The present embodiment provides a perovskite and crystalline silicon laminate cell. Referring to fig. 3, a layer of NiO is formed on the surface of a crystalline silicon solar cell as an underlying cell x As perovskite cellsHole transport layer due to NiO x The interface defect between the perovskite and the perovskite is too much, and in the embodiment, 5nm Poly-TPD is used as a passivation layer to passivate the transmission layer and improve the voltage of the perovskite top cell. Because the surface of the crystalline silicon battery is provided with diamond line cuts, the surface is very rough, a conventional polymer with small weight average molecular weight cannot effectively passivate a perovskite layer, and the embodiment uses the Poly-TPD with high weight average molecular weight not lower than 80000 in a wet process to form a passivation layer, so that the uniformity, the repeatability and the voltage of the device are greatly improved.
The crystalline silicon solar cell used as the bottom cell is a TOPCon structure cell. Perovskite batteries as top batteries also include SnO x Layer C 60 A layer, and a transparent electrode IZO.
Experimental data:
as shown in fig. 4, which is a confocal microscope image of the surface morphology of the industrial wafer (a) and the laboratory-grade wafer (b), it can be seen from the figure that the x-axis and the y-axis are different in proportion to the z-axis, and the industrial wafer surface has a micrometer-scale roughness.
FIG. 5 is a V of an opaque device using PTAA (c) and Poly-TPD (d) interface passivation OC And (5) statistics data. The corresponding samples of fig. 5 are all stacked cells of the structure shown in fig. 3 prepared using industrial wafer based crystalline silicon cells. In the experiment of fig. 5, the first step: sputtering NiO with the thickness of 10nm x The film layer acts as a Hole Transport Layer (HTL) to minimize the possibility of pinholes that may lead to shunt paths. The sputtered film forms a dense conformal film on the roughened silicon surface. To reduce recombination losses, further, we were on NiO x And a thin PTAA (N, N '-bis-4-butylphenyl-N, N' -diphenyl) or a Poly-benzidine (Poly-TPD) layer interposed between the perovskite thin film to passivate the interface between the NiOx and the perovskite thin film. PTAA in the experimental sample has a weight average molecular weight of 9K to 325K and Poly-TPD has a weight average molecular weight of 15K to 200K. Experimental results as shown in fig. 5 c and d, both polymers showed significant V on the opaque device OC Reinforcing%>100mV)。
From FIGS. 5 c and d, we have found that PTAA and PTAA having higher weight average molecular weights (Mw)Opaque devices of Poly-TPD showed significantly better V OC Consistency. For the roughened surface of the tandem cell, the low weight average molecular weight polymer tends to form beads, but the high weight average molecular weight polymer tends to form fibers in solution, which may be why the high weight average molecular weight polymer has better coverage on the roughened surface.
Example IV
The present embodiment provides a perovskite battery using FTO transparent conductive glass. The FTO conductive glass is fluorine doped SnO 2 Transparent conductive glass (SnO 2: F), abbreviated as FTO. PTAA is used as a hole transport layer on the surface of the FTO transparent conductive glass, and the ultrathin transport layer is difficult to completely cover the surface of the substrate due to rough surface of the FTO. Conventional small weight average molecular weight polymers do not form an effective passivation. In the embodiment, PTAA with the weight average molecular weight not lower than 80000 is used as a solute of a precursor solution of the hole transport layer, and a wet process is used for preparing an ultrathin transport layer of the perovskite battery, so that the uniformity, the repeatability and the voltage of the device are greatly improved.
FIG. 6 is a CAFM and AFM image stack of Poly-TPD 15k (e) and Poly-TPD 200k (f) on top of FTO glass. We performed Conductive Atomic Force Microscopy (CAFM) and Atomic Force Microscopy (AFM) tests on a thin polymer layer coated on top of an FTO substrate. In fig. 6 e and f, we superimpose the CAFM results on the AFM morphology results. White patches on the image are where the CAFM measurement shows high current (i.e., high conductivity). In fig. 6 e shows significantly more and larger areas of high current than f. Since the electrical conductivity of the polymer film is significantly lower than that of FTO glass substrates, this suggests that high weight average molecular weight (Mw) polymers can provide better surface coverage on rough surfaces.
The embodiments described above provide solutions that relate to a transmission layer or passivation layer of a perovskite solar cell on a roughened substrate, which may include any one of the following: an industrial silicon wafer with diamond line cuts on the surface or with micro-scale roughness, conductive glass with diamond line cuts on the surface, and a crystalline silicon cell with a suede pyramid surface.
In addition, it should be noted that, although the solution proposed in this solution is directed to preparing perovskite on micron-sized roughened substrates, non-roughened substrates may be applied, still having the effect of easily forming ultra-thin passivation layers or ultra-thin transport layers.
Example five
Embodiments of the present application also provide a passivation layer for a solar cell, the passivation layer being made of a second high weight average molecular weight material having a weight average molecular weight not lower than a first target value, the first target value being about 80000. In this embodiment, the passivation layer is made of a second high-weight average molecular weight material with a weight average molecular weight not lower than the first target value, so that film formation is easy, and a dense film with a thickness not exceeding 20nm can be formed by a wet process, such as coating film formation or spin coating film formation, so as to achieve the passivation effect.
In other embodiments, the film layer formed of the second high weight average molecular weight material having a weight average molecular weight of not less than 80000 serves as both the electron transporting layer and the hole transporting layer. The electron transport layer or the hole transport layer made of the first high-weight average molecular weight material can be continuously distributed on a rough substrate in a large area, and a large-area ultrathin transport layer (smaller than 20 nm) is easy to form by a wet process without passivation.
Example six
The embodiment of the application also provides a photovoltaic module, which comprises the perovskite solar cell or the passivation layer. The photovoltaic module may be a perovskite cell, a stack of crystalline silicon and perovskite cells, or a combination of one or more of the foregoing.
The photovoltaic module provided in this embodiment may be formed by a wet process suitable for industrial mass production, because the film layer formed of the high-weight average molecular weight material having the weight average molecular weight not lower than the first target value, for example 80000, is used as the transmission layer or the passivation layer of the transmission layer.
Example seven
The embodiment of the application also provides a preparation method of the perovskite solar cell, which comprises the following steps: a step of preparing a transport layer; in the step of preparing the transport layer, the transport layer is formed using a wet process using a first high weight average molecular weight material having a weight average molecular weight value not lower than a first target value. The first target value is 80000, for example.
The embodiment of the application also provides a preparation method of the perovskite solar cell, which comprises the following steps: the process for preparing the transmission layer and the process for preparing the perovskite light absorption layer further comprise, between the process for preparing the transmission layer and the process for preparing the perovskite light absorption layer:
forming a passivation layer on the surface of the transmission layer by using a wet process by using a second high-weight-average molecular weight material with a weight-average molecular weight not lower than a first target value; the first target value is 80000, for example.
The embodiment of the application also provides a preparation method of the perovskite solar cell, wherein the transmission layer comprises a first transmission layer and a second transmission layer; the second high-weight average molecular weight material comprises a high polymer material A and a high polymer material B; the preparation method comprises the following steps:
forming a first transmission layer on a roughened substrate using one or more of the following materials: snO (SnO) x 、TiO x 、ZnO x 、WO x Fullerene and derivatives thereof, cuI, cuSCN, cuO x 、NiO x 、MoS 2 、WS 2 The spiro-TTB, spiro-MeOTAD and PEDOT are PSS; if the first transport layer is an electron transport layer, the material of the first transport layer may be selected from SnO x 、TiO x 、Zno x One or more of fullerenes and derivatives; if the first transport layer is a hole transport layer, the material of the second transport layer may be selected from WO therein x 、CuI、CuSCN、CuO x 、NiO x 、MoS 2 、WS 2 One or more of spiro-TTB, spiro-MeOTAD, PEDOT: PSS.
Preparing a polymer solution from a high polymer material A, and coating the polymer solution containing the high polymer material A on the first transmission layer to form a passivation layer of the first transmission layer; the polymer material A is selected from one or more of modified or unmodified PTAA, modified or unmodified Poly-TPD, modified or unmodified P3HT, modified or unmodified N2200 and modified or unmodified N2300;
forming a perovskite light absorption layer on the passivation layer;
forming a second transport layer over the perovskite light absorbing layer; the material of the second transmission layer is selected from SnO x 、TiO x 、ZnO x 、WO x Fullerene and derivatives thereof, cuI, cuSCN, cuO x 、NiO x 、MoS 2 、WS 2 One or more of spiro-TTB, spiro-MeOTAD, PEDOT: PSS;
preparing a polymer solution from a high polymer material B, and coating the polymer solution containing the high polymer material B on the second transmission layer, wherein the high polymer material B is one or more selected from modified or unmodified PTAA, modified or unmodified Poly-TPD, modified or unmodified P3HT, modified or unmodified N2200 and modified or unmodified N2300; one of the first transport layer and the second transport layer is an electron transport layer, and the other is a hole transport layer.
In addition, the embodiment of the application also provides a preparation method of the serial perovskite crystalline silicon solar cell, which comprises the following steps:
texturing the surface of the p-type silicon wafer;
carrying out local or full boron expansion heavily doping on the back surface of the silicon;
forming pn junction by expanding phosphor on the front surface of the battery;
preparing a bottom electrode open pore passivation layer on the back surface of the silicon;
opening holes in the passivation layer on the back surface of the silicon;
preparing a bottom electrode on the back surface of the silicon;
preparing an emitter passivation layer on the front surface of silicon;
preparing a tunneling layer on the silicon emission passivation layer;
preparing a hole transport layer comprising a first high weight average molecular weight material on the tunneling layer;
preparing a perovskite light absorbing layer on the hole transporting layer containing the first high weight average molecular weight material;
preparing an electron transport layer comprising a first high weight average molecular weight material on the perovskite light absorbing layer;
depositing a top electrode buffer layer over the electron transport layer comprising the first high weight average molecular weight material;
preparing a transparent electrode on the top electrode buffer layer;
and preparing a metal grid line electrode on the transparent electrode.
The embodiment of the application also provides the application of the high-weight average molecular weight material with the weight average molecular weight not lower than 80000 as a passivation layer or a transmission layer in the solar cell, so that the passivation layer or the transmission layer with the wavelength of less than 20nm can be formed by a wet process during the preparation of the solar cell, and the open-circuit voltage of the cell can be improved.
The embodiment of the application also provides a passivation layer material of the solar cell, wherein the value of the weight average molecular weight of the passivation layer material is not lower than a first target value, and the first target value is 80000.
The embodiment of the application also provides a transmission layer material of the solar cell, wherein the value of the weight average molecular weight of the transmission layer material is not lower than a first target value, and the first target value is 80000.
Further, the transport layer material may be a mixture of two high weight average molecular weight materials. The high weight average molecular weight material may be a polymer. For example, the material of the hole transport layer includes PTAA having a weight average molecular weight of 200000 and Poly-TPD having a weight average molecular weight of 80000 to 120000.
PTAA can not well passivate the perovskite surface as a hole transport layer, so that the open-circuit voltage is low, but PTAA is high in hole transport efficiency, and can reduce series groups and improve the filling factor. Conversely, the low hole transport efficiency of Poly-TPD results in a lower device fill factor, but good passivation effect and high open circuit voltage. Mixing PTAA and Poly-TPD in the precursor solution can achieve an increase in open circuit voltage and fill factor.
The foregoing is merely illustrative of the present application, and the present application is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the scope of the present application should be included in the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.

Claims (15)

1. A perovskite solar cell comprising a perovskite light absorbing layer, and a transport layer located on one side of the perovskite light absorbing layer, characterized in that the transport layer is made of a first high weight average molecular weight material having a weight average molecular weight value not lower than a first target value; or,
a passivation layer is further arranged between the transmission layer and the perovskite light absorption layer, and the material of the passivation layer is a second high-weight-average molecular weight material with the weight-average molecular weight value not lower than a first target value.
2. The perovskite solar cell of claim 1, wherein the first target value is 80000.
3. The perovskite solar cell of claim 1, wherein the first high weight average molecular weight material and the second high molecular weight material are each independently selected from one or more of the following:
PTAA, poly-TPD, P3HT, N2200 and N2300, and modified materials of any of the foregoing.
4. A perovskite solar cell according to any one of claims 1 to 3, wherein when the transport layer is an electron transport layer, the first high molecular weight material is selected from one or more of modified or unmodified N2200, modified or unmodified N2300; or,
when the transport layer is a hole transport layer, the first high weight average molecular weight material is selected from one or more of modified or unmodified PTAA, modified or unmodified Poly-TPD, and modified or unmodified P3 HT.
5. The perovskite solar cell according to claim 4, wherein,
the thickness of the transmission layer is 3-30 nm;
the thickness of the transport layer is preferably 4 to 5nm.
6. A perovskite solar cell according to any one of claims 1 to 3, wherein a passivation layer is further provided between the transport layer and the perovskite light absorbing layer, and wherein when the material of the passivation layer is a second weight average molecular weight material having a weight average molecular weight value not lower than a first target value, the material of the transport layer comprises: snO (SnO) x 、TiO x 、ZnO x 、WO x Fullerene and derivatives thereof, cuI, cuSCN, cuO x 、NiO x 、MoS 2 、WS 2 One or more of spiro-TTB, spiro-MeOTAD, PEDOT: PSS.
7. The perovskite solar cell of claim 6, wherein the passivation layer of the second high weight average molecular weight material has a thickness of 1-20 nm, preferably 2nm.
8. A perovskite solar cell according to any one of claims 1 to 3, wherein the perovskite solar cell comprises a roughened substrate comprising any one of the following:
industrial silicon wafers with diamond line cuts or micrometer scale roughness on the surface, conductive glass with transparent conductive electrodes deposited on the surface, and crystalline silicon cells with textured pyramid surfaces.
9. A passivation layer for a solar cell, characterized in that a material of the passivation layer is a first high molecular weight material having a weight average molecular weight not lower than a first target value, the first target value being 80000.
10. The passivation layer of claim 9, wherein the passivation layer simultaneously acts as a transport layer for the solar cell.
11. A photovoltaic module comprising a perovskite solar cell according to any one of claims 1 to 8, or comprising a passivation layer according to claim 9 or 10.
12. A method of fabricating a perovskite solar cell, comprising: a step of preparing a transport layer; wherein in the step of preparing the transport layer, the transport layer is formed by a wet process using a first high weight average molecular weight material having a weight average molecular weight value not lower than a first target value.
13. A method of fabricating a perovskite solar cell, comprising: the process for preparing a transmission layer and the process for preparing a perovskite light-absorbing layer are characterized in that the process for preparing a transmission layer and the process for preparing a perovskite light-absorbing layer are further included:
and forming a passivation layer on the surface of the transmission layer by adopting a wet process by utilizing a second high-weight-average molecular weight material with the weight-average molecular weight not lower than a first target value.
14. The method of manufacturing according to claim 13, wherein the transport layer comprises a first transport layer and a second transport layer; the second high-weight average molecular weight material comprises a high polymer material A and a high polymer material B;
the preparation method comprises the following steps:
forming a first transmission layer on a rough substrate; the material of the first transmission layer is selected from SnO x 、TiO x 、ZnO x 、WO x Fullerene and derivatives thereof, cuI, cuSCN, cuO x 、NiO x 、MoS 2 、WS 2 One or more of spiro-TTB, spiro-MeOTAD, PEDOT: PSS;
coating a solution containing the high polymer material A on the first transmission layer to form a passivation layer of the first transmission layer; the polymer material A is selected from one or more of modified or unmodified PTAA, modified or unmodified Poly-TPD, modified or unmodified P3HT, modified or unmodified N2200 and modified or unmodified N2300;
poly forms a perovskite light absorbing layer on the passivation layer;
forming a second transport layer on the perovskite light absorption layer, wherein the material of the second transport layer is selected from SnO x 、TiO x 、ZnO x 、WO x Fullerene and derivatives thereof, cuI, cuSCN, cuO x 、NiO x 、MoS 2 、WS 2 One or more of spiro-TTB, spiro-MeOTAD, PEDOT: PSS;
coating a solution containing a high polymer material B on the second transmission layer to form a passivation layer of the second transmission layer; the polymer material B is selected from one or more of modified or unmodified PTAA, modified or unmodified Poly-TPD, modified or unmodified P3HT, modified or unmodified N2200 and modified or unmodified N2300.
15. Use of a high molecular weight material having a weight average molecular weight not lower than a first target value, said first target value being 80000, as a passivation layer or transport layer in a solar cell.
CN202210600315.4A 2022-05-27 2022-05-27 Perovskite solar cell, preparation method thereof, passivation layer and photovoltaic module Pending CN117202677A (en)

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