CN116600580B - Solar cell, preparation method thereof and solar cell module - Google Patents

Solar cell, preparation method thereof and solar cell module Download PDF

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CN116600580B
CN116600580B CN202310861115.9A CN202310861115A CN116600580B CN 116600580 B CN116600580 B CN 116600580B CN 202310861115 A CN202310861115 A CN 202310861115A CN 116600580 B CN116600580 B CN 116600580B
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layer
photoelectric conversion
electrode
conductive ceramic
conversion layer
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CN116600580A (en
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段野
吴颐良
郭清秀
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Beijing Yaoneng Technology Co ltd
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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80Constructional details
    • H10K30/81Electrodes
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/40Organic 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
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50Photovoltaic [PV] devices
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/60Forming conductive regions or layers, e.g. electrodes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/549Organic PV cells

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  • Electromagnetism (AREA)
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Abstract

The application provides a solar cell, a preparation method thereof and a solar cell module, relates to the technical field of solar cells, and can solve the problem of degradation of cell efficiency caused by chemical reaction between metal of a metal electrode and a material of a photoelectric conversion layer. The solar cell provided by the application comprises a photoelectric conversion layer and a back electrode positioned on one side of the photoelectric conversion layer, wherein the photoelectric conversion layer comprises at least one light absorption layer, and the back electrode is a conductive ceramic electrode, or a conductive ceramic layer is formed on a part of the back electrode, which is close to the light absorption layer.

Description

Solar cell, preparation method thereof and solar cell module
Technical Field
The application relates to the technical field of solar cells, in particular to a solar cell, a preparation method thereof and a solar cell module.
Background
The organic-inorganic hybrid perovskite has excellent characteristics of large absorption coefficient, small exciton binding energy, long carrier diffusion length, high carrier mobility and the like, and is widely paid attention to as an ideal photovoltaic absorption material. Perovskite solar cells were reported for the first time since 2009, with a rapid increase in perovskite solar cell power conversion efficiency from the initial 3.8% to 25.7% comparable to commercial single crystal silicon solar cells.
The solar cell generally adopts a metal electrode, but for the perovskite solar cell, halogen in a perovskite light absorption layer can diffuse to the metal electrode, and the metal electrode can be oxidized by the halogen, so that the contact resistance of the electrode is increased; meanwhile, the metal elements of the metal electrode migrate to the perovskite light absorption layer and also affect the stability of the perovskite light absorption layer.
If the metal electrode is replaced with ITO (indium tin oxide, a commonly used transparent conductive material) to enhance cell stability, but a larger film thickness is generally required to meet the conductivity requirement, a thicker ITO film consumes a large amount of indium, which is too costly for solar cells.
Disclosure of Invention
The application aims to provide a solar cell, a preparation method and a module thereof, which can at least partially solve the problem of cell efficiency degradation caused by chemical reaction between a metal electrode and a light absorption layer material, and have lower cost.
The embodiment of the application adopts the following technical scheme:
a solar cell, comprising: the photoelectric conversion device comprises a photoelectric conversion layer and a back electrode positioned on one side of the photoelectric conversion layer, wherein the back electrode is a conductive ceramic electrode, or a conductive ceramic layer is formed on a part of the back electrode, which is close to the photoelectric conversion layer.
Optionally, the back electrode includes a conductive ceramic layer and a metal electrode layer, and the metal electrode layer is disposed on a side of the conductive ceramic layer away from the photoelectric conversion layer.
Optionally, the distribution areas of the metal electrode layer are in one-to-one correspondence with the distribution areas of the conductive ceramic layer, and neither of the distribution areas of the metal electrode layer and the distribution areas of the conductive ceramic layer is beyond the distribution range of the conductive ceramic layer.
Optionally, the solar cell further comprises: a substrate and a transparent conductive layer covering the substrate; the transparent conductive layer is provided with a P1 wire slot for dividing the transparent conductive layer;
the photoelectric conversion layer is positioned on the transparent conductive layer, a P2 wire slot for dividing the photoelectric conversion layer is arranged on the photoelectric conversion layer, and the P2 wire slot is positioned on one side of the P1 wire slot;
the back electrode is positioned on the photoelectric conversion layer, the back electrode is also provided with an electrode extension part, the electrode extension part is connected to the transparent conductive layer through the P2 wire slot, the electrode extension part is a part of the conductive ceramic electrode, or a conductive ceramic layer is formed on a part of the electrode extension part, which is close to the photoelectric conversion layer;
the back electrode is provided with a P3 wire slot, the P3 wire slot is positioned on one side, far away from the P1 wire slot, of the P2 wire slot, and the P3 wire slot is used for dividing the back electrode.
Optionally, the materials of the conductive ceramic electrode and the conductive ceramic layer each include at least one of: tiN, tiC, tiCN, tiSiN, alTiN, zrN, taN and HfN.
The photoelectric conversion layer further includes: and/or an electron transport layer, wherein the P2 wire groove and the P3 wire groove simultaneously divide the hole transport layer and/or the electron transport layer.
Optionally, the thickness of the conductive ceramic electrode is greater than 0.5 μm. Preferably, the thickness of the conductive ceramic electrode is 0.8-2.5 μm.
Preferably, the thickness of the conductive ceramic layer is 0.1-0.5 μm. The thickness of the conductive ceramic layer is preferably 0.1 to 0.3 μm.
Optionally, the substrate is a glass substrate or a flexible transparent substrate; the photoelectric conversion layer includes a perovskite light absorption layer.
Optionally, the photoelectric conversion layer includes a plurality of light absorbing layers, and a tunneling layer located between any two adjacent light absorbing layers.
Optionally, the photoelectric conversion layer includes: a wide bandgap perovskite light absorbing layer having a bandgap greater than 1.6ev, a narrow bandgap light absorbing layer having a bandgap less than 1.6ev, and a tunneling layer between the wide bandgap perovskite light absorbing layer and the narrow bandgap light absorbing layer.
A cell assembly comprising the solar cell of any one of the above.
A method of fabricating a solar cell, comprising the steps of:
providing a substrate: the substrate is provided with a transparent conductive layer;
p1 scribing: dividing the transparent conductive layer through a battery scribing process to form a P1 wire slot exposing the substrate;
and (3) manufacturing a photoelectric conversion layer: manufacturing the photoelectric conversion layer on the surface of the transparent conductive layer;
p2 scribing: dividing the photoelectric conversion layer at one side of the P1 wire groove through a battery scribing process to form a P2 wire groove exposing the transparent conductive layer;
back electrode deposition: depositing an electrode material on the surface of the photoelectric conversion layer to obtain the back electrode;
p3 scribing: forming a P3 wire groove on one side, far away from the P1 wire groove, of the P2 wire groove through a battery scribing process, wherein the P3 wire groove at least divides the back electrode; wherein,
the back electrode is a conductive ceramic electrode, or a conductive ceramic layer is formed on a portion of the back electrode, which is close to the photoelectric conversion layer.
Optionally, depositing an electrode material on the surface of the photoelectric conversion layer to obtain the back electrode includes:
and generating a patterned conductive ceramic layer by using a patterned mask plate through a reactive magnetron sputtering or cathodic arc deposition method, wherein the conductive ceramic layer is also distributed in the P2 wire grooves and is electrically connected with the transparent conductive layer.
Optionally, when the patterned conductive ceramic layer is generated, alignment marks are synchronously formed on the surface of the battery; after the patterned conductive ceramic layer is generated, the method further comprises:
and printing the metal electrode layer on the conductive ceramic layer by adopting a screen printing machine through the reserved alignment mark in the last step, wherein the metal electrode layer does not exceed the distribution range of the corresponding conductive ceramic layer.
According to the solar cell, the back electrode is the conductive ceramic electrode, or the conductive ceramic layer is formed on the part, close to the photoelectric conversion layer, of the back electrode, compared with metal, the conductive ceramic is more stable in chemical property, is not easy to react with a light absorption material (such as halogen simple substance or ions of a perovskite light absorption layer) of the photoelectric conversion layer, is compact in film layer, can prevent ions of the photoelectric conversion layer from migrating outwards, and can also prevent external metal and ions of the external metal from migrating to the photoelectric conversion layer, so that the problem of degradation of cell efficiency caused by chemical reaction between the metal electrode and the photoelectric conversion layer material can be solved.
Drawings
Fig. 1 is a schematic structural diagram of a solar cell according to embodiment 1 of the present application;
fig. 2 is a schematic structural diagram of another solar cell according to embodiment 2 of the present application;
fig. 3 is a schematic structural diagram of another stacked solar cell according to embodiment 3 of the present application;
fig. 4 is a schematic flow chart of a solar cell according to embodiment 5 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.
An embodiment of the present application provides a solar cell including: a photoelectric conversion layer and a back electrode positioned at a backlight side of the photoelectric conversion layer, wherein the photoelectric conversion layer comprises at least one light absorption layer; the back electrode is a conductive ceramic electrode, or a conductive ceramic layer is formed on a part of the back electrode, which is close to the light absorption layer.
The photoelectric conversion layer at least comprises a light absorption layer (such as a perovskite light absorption layer, a copper indium gallium selenide light absorption layer and the like), and auxiliary functional layers can be arranged in addition, and the implementation effect of the scheme of the application is not affected by the functional layers, so that the application is not limited by the presence or absence of the auxiliary functional layers. For example, the photoelectric conversion layer may include a hole transport layer and an electron transport layer, may include only one of the hole transport layer and the electron transport layer, or may not include both of them. Further, the photoelectric conversion layer may or may not further include an interface modification layer or a buffer layer.
The solar cell of the application may be a single junction, double junction stack or multi-junction stack solar cell, and in the case of a multi-junction stack solar cell, the photoelectric conversion layer may comprise a plurality of light absorbing layers, and may further comprise a tunneling layer between any two adjacent light absorbing layers. The double junction tandem solar cell may be, for example, a perovskite/crystalline silicon tandem cell, and the multi-junction tandem solar cell may be, for example, a full perovskite tandem cell. The solar cell is a full perovskite laminated cell, and the photoelectric conversion layer at least comprises two perovskite light absorption layers and a tunneling layer positioned between the two perovskite light absorption layers.
In the application, the back electrode can be made of conductive ceramic material (most of metals in the prior art), and the conductive ceramic does not react with the light absorption layer (such as halogen ions of perovskite light absorption layer) of the photoelectric conversion layer, and the film layer is compact, so that the outward migration of ions of the light absorption layer and the migration of external metal ions (such as metal ions of a grid line) to the light absorption layer can be prevented, and the problem of degradation of battery efficiency caused by chemical reaction between the metal electrode and the light absorption layer material can be solved. The method has simple process and high yield.
In other embodiments, the back electrode may be made of a metal material, but the electrode with a conductive ceramic layer formed near the perovskite light absorption layer can still play a role in blocking the outward migration of ions in the light absorption layer and the migration of external metal ions to the light absorption layer, and can solve the problem of degradation of battery efficiency caused by chemical reaction between the metal electrode and the light absorption layer material. In the scheme, the back electrode main body still adopts high-conductivity metal, so that the thickness of the back electrode can be controlled to be almost the same as that of the existing metal back electrode.
Illustratively, in one embodiment, the back electrode includes a conductive ceramic layer and a metal electrode layer, and the metal electrode layer is disposed on a side of the conductive ceramic layer remote from the light absorbing layer. The specific distribution range of the thickness of the conductive ceramic layer is based on the fact that the simple substance and ions of the light absorption layer can be blocked from reacting with the metal electrode layer, and the design requirement is met.
The conductive ceramic electrode or the conductive ceramic layer in the back electrode is made of a conductive ceramic material, and the conductive ceramic material has the following characteristics: the material has certain compactness after film formation, can play a role in blocking ion migration, and does not react with the light absorption layer material and the escaping ions; in addition, the conductivity of the conductive ceramic material should also satisfy the following conditions: the conductive requirement index of the back electrode can be met within the maximum thickness range allowed by the back electrode.
Illustratively, the material of the conductive ceramic layer in the conductive ceramic electrode or the back electrode comprises at least one of: tiN, tiC, tiCN, tiSiN, alTiN, zrN, taN and HfN. In addition, the above materials may be mixed materials obtained by doping.
It will be appreciated by those skilled in the art that the "ceramic" in the conductive ceramic described in this embodiment is only used to emphasize the inertness of the material and the compactness after film formation, and can act as a barrier to ion migration, and is not used to limit it to some specific materials, such as silicate materials.
When the whole back electrode is made of conductive ceramic material, the thickness of the conductive ceramic electrode is larger than 0.5 mu m, and the thickness is preferably 0.8-2.5 mu m. The conductive ceramic electrode may be a TiN film having a thickness of not less than 0.8 μm, for example, 0.8, 1, 1.2, 1.5, 1.7, 1.8, 1.9, 2.0, 2.2, 2.4, 2.5 μm.
When the back electrode adopts a composite layer scheme of a conductive ceramic layer and a metal electrode layer, the thickness of the conductive ceramic layer is 0.1-0.5 mu m, and preferably 0.1-0.3 mu m. The thickness of the metal electrode layer may be determined based on the thickness of the conductive ceramic layer and the overall conductivity requirements. Illustratively, tiN is used as the conductive ceramic layer, and a thickness of 0.2 μm is sufficient to act as a barrier layer, and a copper electrode layer about 150nm thick is further laminated thereon to form the back electrode.
Example 1
Large area thin film solar cells require individual small cell interconnections divided into small areas, typically by three basic interconnections (formed by a scribe process called P1, P2 and P3). Wherein, the P1 scribing process removes the transparent conductive layer in the groove, the P2 scribing process removes the photoelectric conversion layer, and the P3 scribing process removes the metal electrode. However, this solution has a major problem for the perovskite battery, since after the photoelectric conversion layer (in the perovskite battery, the perovskite light absorption layer) is removed by the P2 scribing process, the metal electrode fills the P2 wire slot as an internal wire for realizing the serial connection of the battery cells when the metal electrode layer is deposited, but this simultaneously makes the metal electrode directly contact with the perovskite light absorption layer, and the metal electrode can chemically react with the perovskite, so that on one hand, the conductivity of the metal electrode is affected; on the other hand, ions in the metal electrode enter the perovskite light absorption layer to influence the photoelectric conversion performance of the perovskite light absorption layer. The scheme of the application can also solve the problem that perovskite in the P2 wire slot is in direct contact with the metal electrode. The present application will be further described with reference to specific examples.
An embodiment of the present application provides a perovskite solar cell, as shown in fig. 1, including:
a substrate 10 covered with a transparent conductive layer 11; the transparent conductive layer 11 is provided with a P1 wire slot for dividing the transparent conductive layer;
a photoelectric conversion layer including a perovskite light absorption layer 12, an electron transport layer 14, and a hole transport layer 15; the photoelectric conversion layer is positioned on the transparent conductive layer 11, and a P2 wire groove for dividing the photoelectric conversion layer is arranged on the photoelectric conversion layer, and the P2 wire groove is positioned on one side of the P1 wire groove; and
the back electrode 13, the back electrode 13 is located on the photoelectric conversion layer, the back electrode 13 further has an electrode extension 130, and the electrode extension 130 is connected to the transparent conductive layer 11 through the P2 wire slot; the back electrode 13 is provided with a P3 wire groove, the P3 wire groove is positioned on one side of the P2 wire groove far away from the P1 wire groove, and the P3 wire groove divides the back electrode 13 and the perovskite light absorption layer 12, the hole transmission layer 15 and the electron transmission layer 14.
Only the states of the P1, P2 and P3 trunking under ideal process conditions are described in the application, and those skilled in the art can understand that under-etching or over-etching conditions are easy to exist in the implementation, and under the premise that the conditions have little influence on the battery performance, under-etching or over-etching is also allowed to exist. Thus, the present application does not exclude such cases of incomplete etching or over-etching.
Illustratively, in some embodiments, the P3 wireway only segments the back electrode 13. In particular, the P3 wire chase only needs to divide the back electrode, and the transmission layer or other functional layer immediately below the back electrode may or may not be etched.
The substrate 10 in the present embodiment may be, for example, a glass substrate or a flexible transparent substrate.
The whole back electrode is made of conductive ceramic, namely the material of the back electrode 13 is conductive ceramic, and the P2 wire groove is also filled with conductive ceramic to separate the perovskite light absorption layer 12, namely the electrode extension 130 is made of conductive ceramic.
The conductive ceramic layer of the back electrode 13 may be, for example, at least one of a TiN film, a TiC film, a TiCN film, a TiSiN film, an AlTiN film, a ZrN film, a TaN film, a HfN film, or a composite layer composed of a plurality of the above.
The conductive ceramic layer of the embodiment is distributed in the electrode area and the P2 wire groove to form a conductive ceramic back electrode and an electrode extension part made of conductive ceramic.
The perovskite light absorbing layer 12 material may diffuse outward, such as perovskite cations, methyl ether, halogen ions, or simple substances such as iodine and bromine, to the metal electrode, react with the metal electrode, and cause an increase in contact resistance at the interface; in addition, the metal of the metal electrode can diffuse into the perovskite light absorption layer and enter the perovskite light absorption layer, so that the stability and the battery efficiency of the battery are affected. The back electrode is made of conductive ceramic material instead of metal, and the ceramic material is inert and compact in film layer, so that ion diffusion can be prevented, and the problem of degradation of battery efficiency caused by chemical reaction between metal of the metal electrode and material of the photoelectric conversion layer is solved.
In the application, the back electrode is made of conductive ceramic material instead of metal, the electrode material is deposited on the surface of the photoelectric conversion layer after the P2 is scribed to obtain the back electrode 13, and meanwhile, the conductive ceramic material is deposited on the P2 wire slot, so that the direct contact between the perovskite light absorption layer 12 at the P2 wire slot and the metal electrode is avoided, and the problem of degradation of battery efficiency caused by chemical reaction between the metal electrode at the P2 wire slot and the perovskite is solved. In addition, the conductive ceramic film layer is compact, so that escaping ions in the perovskite light absorption layer 12 can be prevented from migrating outwards, and the influence on the photoelectric performance of the perovskite light absorption layer 12 due to ion escaping in the perovskite light absorption layer 12 is avoided; and meanwhile, the migration of external metal ions to the perovskite light absorption layer 12 can be blocked, and the influence of the metal ions on the battery performance caused by the metal ions entering the perovskite light absorption layer 12 is avoided.
The perovskite light absorbing layer 12 in this embodiment may be a wide band gap perovskite (band gap greater than 1.6 ev) or a narrow band perovskite (band gap less than 1.6 ev). Wide band gap perovskites include, but are not limited to FACsPbIBrCl, FAMACsPbIBrCl, FACsDMAPbIBrCl, csDMAPbIBrCl and facspbeibr; narrow-band perovskite including but not limited to FAPbI 3 FAMACsPbIBr, FACsDMAPbIBr, csDMAPbIBr, FACsPbI, FAMACsPbI, FACsDMAPbI, csDMAPbI, FACsPbSnI, FAMACsPbSnI and FACsDMAPbSnI and CsDMAPbSnI.
Preferably, the photoelectric conversion layer comprises a perovskite light absorption layer with a band gap width of 1.4-1.6 eV.
The perovskite cell may have a formal structure or a trans structure. When the perovskite cell is of a formal structure, the electron transport layer 14 is located between the transparent electrode layer 11 and the perovskite light-absorbing layer 12, and the hole transport layer 15 is located between the back electrode 13 and the perovskite light-absorbing layer 12. When the perovskite cell is of a trans-structure, the hole transport layer 15 is located between the transparent electrode layer 11 and the perovskite light-absorbing layer 12, and the electron transport layer 14 is located between the back electrode 13 and the perovskite light-absorbing layer 12.
The hole transport layer 15 may be any suitable material for perovskite solar cells, such as PTAA, PEDOT: PSS, spiro-OMeTAD, poly-TPD, cuSCN, cu 2 O、CuI、NiO x 、P3HT、MoOx、V 2 O 5 Any one of 2PACz, 4PACz, meO-4PACz, spiro-TTB, F4-TCNQ, F6-TCNNQ, m-MTDATA, meO-2PACz and TAPC can also be other hole transport layer materials, and the application is not limited thereto; the material of the electron transport layer 14 may be any material suitable for perovskite solar cells, such as PCBM, tiO 2 、ZnO、SnO 2 At least one of H-PDI, F-PDI, C60 and ICBA can be other electron transport layer materials, and is not limited in the application.
In other embodiments, there may or may not be other functional layers between the transparent electrode (or back electrode) and the hole transport layer that may improve the perovskite solar cell; other functional layers which can improve the perovskite solar cell can be arranged between the hole transport layer and the perovskite light absorption layer or not; other functional layers which can improve the perovskite solar cell can be arranged between the perovskite light absorption layer and the electron transport layer or not; there may or may not be other functional layers between the electron transport layer and the transparent electrode (or back electrode) that may improve the perovskite solar cell. The functional layer may be, for example, a buffer layer or an interface modification layer.
The thickness of the conductive ceramic layer as the back electrode is not less than 0.8 μm. The conductive ceramic layer acts as a back electrode and a thicker film layer is required to ensure sufficient conductivity. In addition, the titanium ore light absorbing layer 12 is generally thicker and the P2 wire slots are also deeper, so the conductive ceramic layer cannot be too thin. Too thin a conductive ceramic layer may not form a continuous electrode extension in the P2 wire chase or form an electrode with excessive resistance. Generally, the thickness of the conductive ceramic layer is about 1.5-2.5 μm, which can well meet the design requirement of the battery electrode.
Illustratively, tiN is used as the back electrode, typically about 2 μm thick, regardless of other factors.
In some embodiments, the P2 trunking may be formed in cross-section in a structure with a narrow bottom and a wide top.
Example 2
As shown in fig. 2, compared with the perovskite solar cell provided in embodiment 1, the perovskite solar cell of this embodiment is different only in that the back electrode of the perovskite solar cell is not integrally made of conductive ceramics, but includes a conductive ceramic layer 131 and a metal electrode layer 132, the metal electrode layer 132 is disposed on one side of the conductive ceramic layer 131 far from the photoelectric conversion layer 12, and the distribution area of the metal electrode layer 132 corresponds to the distribution area of the conductive ceramic layer 131 one by one, and does not exceed the distribution range of the conductive ceramic layer 131.
In some embodiments, the metal electrode layer 132 has a substantially uniform pattern with the conductive ceramic layer 131.
In other embodiments, the metal electrode layer 132 is distributed only in the electrode region of the conductive ceramic layer 131, and the electrode extension 130 may not have the metal electrode layer 132. The electrode extension 130 is formed of only conductive ceramics.
The presence of the metal electrode layer 132 may increase the current collection capability of the back electrode, reducing the contact resistance of the electrode. Meanwhile, the conductive ceramic layer 131 is distributed between the metal electrode layer 132 and the perovskite light absorption layer 12, and the conductive ceramic layer 131 can serve as a blocking layer to block escape ions or simple substances in the perovskite light absorption layer from migrating to the metal electrode layer 132 and reacting with metal ions in the metal electrode to influence the conductivity of the back electrode; the conductive ceramic layer also can block migration of metal ions in the metal electrode layer 132 to the perovskite light absorption layer, so that the metal ions in the metal electrode layer 132 are prevented from entering the perovskite light absorption layer to affect the performance of the battery.
Illustratively, the back electrode includes a 0.2 μm TiN film layer, and a copper metal layer disposed on the back surface of the TiN film layer at about 150 nm.
Example 3
The difference from the perovskite solar cell provided in embodiment 1 or 2 is only that the photoelectric conversion layer of the perovskite solar cell of this embodiment includes, in addition to the perovskite light-absorbing layer, other light-absorbing layers, and a tunneling layer and a transport layer between the perovskite light-absorbing layer and the other light-absorbing layers. The band gaps of the other light absorbing layers are matched to the perovskite light absorbing layer band gaps such that the absorption spectrum of both covers the dominant energy spectral range of the solar spectrum.
Illustratively, as shown in fig. 3, the photoelectric conversion layer includes: a hole transporting layer 15, an electron transporting layer 14, a wide bandgap perovskite light absorbing layer 121, a narrow bandgap perovskite light absorbing layer 123, and an intermediate layer 122 between the wide bandgap perovskite light absorbing layer 121 and the narrow bandgap light absorbing layer 123; the intermediate layer 122 includes a transport layer and a tunneling layer, and the intermediate layer 122 may include a PEDOT: PSS layer (hole transport layer), an Au metal layer and a tin oxide layer (these two layers are referred to as a composite layer or a tunneling structure), and a C60 layer (electron transport layer), for example.
The narrow bandgap light absorbing layer 123 may also be replaced with a light absorbing layer formed of other materials, such as a crystalline silicon thin film light absorbing layer.
The back electrode of the embodiment adopts a conductive ceramic material, and the conductive ceramic layer formed by the P2 wire grooves separates the light absorption layers (such as a wide band gap perovskite layer and a narrow band gap perovskite layer) in the photoelectric conversion layer, so that the contact of mobile ions of the light absorption layers with the metal electrode can be avoided, the problem of degradation of battery efficiency caused by chemical reaction between the metal electrode and the light absorption layer material is solved, and the stability of the battery is improved. Meanwhile, compared with ITO which needs to consume a large amount of indium material, the cost can be reduced by selecting the conductive ceramic material as the back electrode.
Further, in other embodiments, as shown in fig. 2, the back electrode of the present embodiment may further include a conductive ceramic layer 131 and a metal electrode layer 132, where the metal electrode layer 132 is disposed on a side of the conductive ceramic layer 131 away from the photoelectric conversion layer 12, and the distribution areas of the metal electrode layer 132 are in one-to-one correspondence with the distribution areas of the conductive ceramic layer 131, and neither of them exceeds the distribution range of the conductive ceramic layer 131.
The presence of the metal electrode layer 132 may increase the current collection capability of the back electrode, reducing the contact resistance of the electrode. Meanwhile, the conductive ceramic can prevent escaping ions in the perovskite light absorption layer from migrating to the metal electrode layer 132, and can also prevent ions in the metal electrode layer 132 from migrating to the perovskite light absorption layer, so that the ions in the metal electrode layer 132 are prevented from entering the perovskite light absorption layer to influence the performance of the battery.
Example 4
The embodiment also provides a battery assembly including the solar cell described in any one of the embodiments above.
Example 5
As shown in fig. 4, this embodiment also provides a method for manufacturing a solar cell, including the following steps:
step 101, providing a substrate: the substrate is provided with a transparent conductive layer;
step 102, scribing P1: dividing the transparent conductive layer through a battery scribing process to form a P1 wire slot exposing the substrate;
step 103, manufacturing a photoelectric conversion layer: manufacturing the photoelectric conversion layer on the surface of the transparent conductive layer;
step 104, P2 scribing: dividing the photoelectric conversion layer at one side of the P1 wire groove through a battery scribing process to form a P2 wire groove exposing the transparent conductive layer;
step 105, depositing a back electrode: depositing an electrode material on the surface of the photoelectric conversion layer to obtain the back electrode, wherein the photoelectric conversion layer comprises a perovskite light absorption layer, the back electrode is a conductive ceramic electrode, or a conductive ceramic layer is formed on a part, close to the perovskite light absorption layer, of the back electrode;
step 106, scribing P3: and forming a P3 wire groove exposing the transparent conductive layer on one side of the P2 wire groove far away from the P1 wire groove through a battery scribing process, wherein the P3 wire groove divides the back electrode and the photoelectric conversion layer.
According to the preparation method of the solar cell, the back electrode is made of the conductive ceramic material, or the conductive ceramic layer formed by the conductive ceramic material is formed at the part, close to the light absorption layer, of the back electrode, the conductive ceramic material does not react with the light absorption layer material, the film layer is compact, and ions of the light absorption layer can be prevented from migrating outwards; meanwhile, the migration of external metal ions to the light absorption layer can be blocked, so that the problem of degradation of battery efficiency caused by chemical reaction between the metal electrode and the light absorption layer can be solved.
In this embodiment, the back electrode or the conductive ceramic layer is made of a conductive ceramic material, for example, at least one of TiN, tiC, tiCN, tiSiN, alTiN, zrN, taN, hfN, or a composite material composed of a plurality of materials therein, so that conductive ceramic in direct contact with the perovskite light-absorbing layer is formed in the P2 wire slot, and metal ions which are easy to react with the light-absorbing layer are not present in the conductive ceramic material, thereby solving the problem of efficiency degradation mentioned in the background art.
Depositing an electrode material on the surface of the photoelectric conversion layer in step 105 to obtain the back electrode may specifically be: and generating a patterned conductive ceramic layer by using a patterned mask plate through a reactive magnetron sputtering or cathodic arc deposition method, wherein the conductive ceramic layer is also distributed in the P2 wire grooves and is electrically connected with the transparent conductive layer.
The conductive ceramic electrode may be formed directly in step 105, or the conductive ceramic layer may be formed as a barrier layer in step 105, followed by further formation of a metal electrode layer. The conductive ceramic layer and the metal electrode layer together form the back electrode of the solar cell.
Specifically, when the patterned conductive ceramic layer is generated in step 105, alignment marks are also synchronously formed on the surface of the battery; after the patterned conductive ceramic layer is generated, the method further comprises:
and 106, printing a metal electrode on the conductive ceramic layer by adopting a screen printer through the reserved alignment mark in the last step, wherein the distribution range of the corresponding conductive ceramic layer is not exceeded.
When the whole back electrode adopts the scheme of conducting ceramic material, the thickness of the formed conducting ceramic electrode is larger than 0.5 mu m, and the thickness is preferably 0.8-2.5 mu m. The conductive ceramic electrode may be a TiN film having a thickness of not less than 0.8 μm, for example, 0.8, 1, 1.2, 1.5, 1.7, 1.8, 1.9, 2.0, 2.2, 2.4, 2.5 μm.
When the composite layer of the conductive ceramic layer and the metal electrode layer is used as the back electrode, the thickness of the conductive ceramic layer is 0.1-0.5 μm, preferably 0.1-0.3 μm. The thickness of the metal electrode layer may be determined based on the thickness of the conductive ceramic layer and the overall conductivity requirements. Illustratively, a conductive ceramic layer TiN is sufficient as a barrier layer having a thickness of 0.2 μm, and a copper electrode layer having a thickness of about 150nm is further laminated on the conductive ceramic layer.
Referring to fig. 1, the photoelectric conversion layer may further include: the hole transport layer 15 and the electron transport layer 14 are respectively located at two sides of the perovskite light absorption layer 12, and the P2 wire groove and the P3 wire groove also divide the hole transport layer 15 and the electron transport layer 14. In addition, the photoelectric conversion layer may further include a buffer layer and a perovskite interface modification layer.
In other embodiments, the photoelectric conversion layer may further include a plurality of light absorbing layers with different bandgaps, that is, the perovskite cell refers to a multi-junction stacked cell including a perovskite light absorbing layer. The photoelectric conversion layer may include a wide band gap perovskite light absorption layer, a hole transport layer and an electron transport layer positioned on both sides of the wide band gap perovskite light absorption layer in this order from the light incident side; a tunneling layer; and a narrow band gap perovskite light absorbing layer or a crystalline silicon light absorbing layer, a hole transporting layer and an electron transporting layer located on both sides of the narrow band gap perovskite light absorbing layer (or the crystalline silicon light absorbing layer).
According to the perovskite solar cell preparation method, the back electrode preparation material comprises the conductive ceramic material, so that the conductive ceramic layer is filled in the P2 wire groove, the perovskite light absorption layer is separated by the conductive ceramic layer in the P2 wire groove, the perovskite light absorption layer is prevented from being contacted with the metal electrode, and the problem of degradation of cell efficiency caused by chemical reaction between the metal electrode and the perovskite is solved.
The technical features mentioned in the present application can be used in any combination without conflict. For reasons of brevity, this will not be described in any way herein.
The material and film thickness of the conductive ceramic layer are not particularly limited so long as electrode extensions sufficient to interconnect adjacent battery cells can be formed.
The application provides a scheme aiming at perovskite solar cells, but practical application is not limited to the scheme, and all similar scenes in which the performance of the solar cells is affected due to the reaction of electrode materials and light absorption layers can be applied.
It will be apparent to those skilled in the art that the examples are merely to aid in understanding the application and should not be construed as limiting the application in any way. The specific techniques or conditions are not identified in the examples, and the reagents or apparatus used, which are conventional products available commercially, are carried out according to conventional techniques or conditions in the art or according to the specifications of the product, and the manufacturer is not identified.
The present application is not limited to the above embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present application are intended to be included in the scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.

Claims (11)

1. A solar cell, comprising: a photoelectric conversion layer and a back electrode positioned on the backlight side of the photoelectric conversion layer, characterized in that,
the photoelectric conversion layer comprises at least one perovskite light absorption layer; the back electrode is a conductive ceramic electrode,
the conductive ceramic electrode is a compact film layer prepared by a reaction magnetron sputtering or cathodic arc deposition method and is used for blocking outward migration of halogen simple substances or ions of the photoelectric conversion layer and also blocking migration of external metals and ions thereof to the photoelectric conversion layer;
wherein the thickness of the conductive ceramic electrode is not less than 0.8 μm; the conductive ceramic electrode is in direct contact with the perovskite light absorption layer in a P2 wire groove penetrating through the photoelectric conversion layer.
2. The solar cell of claim 1, further comprising: a substrate and a transparent conductive layer covering the substrate; the transparent conductive layer is provided with a P1 wire slot for dividing the transparent conductive layer;
the photoelectric conversion layer is positioned on the transparent conductive layer, the P2 wire groove is used for dividing the photoelectric conversion layer, and the P2 wire groove is positioned on one side of the P1 wire groove;
the back electrode is positioned on the photoelectric conversion layer and is also provided with an electrode extension part, the electrode extension part is connected to the transparent conductive layer through the P2 wire slot, and the electrode extension part is a part of the conductive ceramic electrode;
the back electrode is provided with a P3 wire slot, the P3 wire slot is positioned on one side, far away from the P1 wire slot, of the P2 wire slot, and the P3 wire slot is used for dividing the back electrode.
3. The solar cell according to any of claims 1-2, wherein the materials of the conductive ceramic electrodes each comprise at least one of:
TiN, tiC, tiCN, tiSiN, alTiN, zrN, taN and HfN.
4. The solar cell according to claim 2, wherein the photoelectric conversion layer further comprises: and/or an electron transport layer, wherein the P2 wire groove and the P3 wire groove are used for dividing the hole transport layer and/or the electron transport layer.
5. The solar cell according to claim 1, wherein the thickness of the conductive ceramic electrode is 0.8-2.5 μm.
6. The solar cell according to claim 2, wherein the substrate is a glass substrate or a flexible transparent substrate.
7. The solar cell of claim 1, wherein the photoelectric conversion layer comprises a plurality of light absorbing layers, and a tunneling layer between any two adjacent light absorbing layers.
8. The solar cell according to claim 1, wherein the photoelectric conversion layer includes: a wide bandgap light absorbing layer having a bandgap greater than 1.6ev, a narrow bandgap light absorbing layer having a bandgap less than 1.6ev, and a tunneling layer between the wide bandgap light absorbing layer and the narrow bandgap light absorbing layer.
9. A battery assembly comprising the solar cell of any one of claims 1-8.
10. A method of making a battery comprising the steps of:
providing a substrate: the substrate is provided with a transparent conductive layer;
p1 scribing: dividing the transparent conductive layer through a battery scribing process to form a P1 wire slot exposing the substrate;
and (3) manufacturing a photoelectric conversion layer: manufacturing the photoelectric conversion layer on the surface of the transparent conductive layer, wherein the photoelectric conversion layer comprises at least one perovskite light absorption layer;
p2 scribing: dividing the photoelectric conversion layer at one side of the P1 wire groove through a battery scribing process to form a P2 wire groove exposing the transparent conductive layer;
depositing a back electrode: depositing an electrode material on the surface of the photoelectric conversion layer to obtain the back electrode;
p3 scribing: forming a P3 wire groove exposing the transparent conductive layer on one side of the P2 wire groove far away from the P1 wire groove through a battery scribing process, wherein the P3 wire groove divides the back electrode and the photoelectric conversion layer; wherein,
the back electrode is a conductive ceramic electrode; the conductive ceramic electrode is a compact film layer prepared by a reaction magnetron sputtering or cathodic arc deposition method and is used for blocking outward migration of halogen simple substances or ions of the photoelectric conversion layer and also blocking migration of external metals and ions thereof to the photoelectric conversion layer; wherein the thickness of the conductive ceramic electrode is not less than 0.8 μm; the conductive ceramic electrode is in direct contact with the perovskite light absorption layer in a P2 wire groove penetrating through the photoelectric conversion layer.
11. The method of manufacturing according to claim 10, wherein said depositing an electrode material on the surface of said photoelectric conversion layer to obtain said back electrode comprises:
and generating a patterned conductive ceramic layer by using a patterned mask plate through a reactive magnetron sputtering or cathodic arc deposition method, wherein the conductive ceramic layer is also distributed in the P2 wire grooves and is electrically connected with the transparent conductive layer.
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