CN112018100A - Silicon/perovskite laminated solar cell - Google Patents
Silicon/perovskite laminated solar cell Download PDFInfo
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- CN112018100A CN112018100A CN201910471813.1A CN201910471813A CN112018100A CN 112018100 A CN112018100 A CN 112018100A CN 201910471813 A CN201910471813 A CN 201910471813A CN 112018100 A CN112018100 A CN 112018100A
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L25/00—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof
- H01L25/16—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof the devices being of types provided for in two or more different main groups of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. forming hybrid circuits
- H01L25/167—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof the devices being of types provided for in two or more different main groups of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. forming hybrid circuits comprising optoelectronic devices, e.g. LED, photodiodes
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- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
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Abstract
The invention discloses a silicon/perovskite laminated solar cell and a preparation method thereof, wherein the silicon/perovskite laminated solar cell comprises a silicon cell used as a bottom cell of the silicon/perovskite laminated solar cell; a perovskite cell for use as a top cell of the silicon/perovskite tandem solar cell; and an intermediate transparent conductive layer located between the silicon cell and the perovskite cell. The silicon cell and the perovskite cell of the silicon/perovskite laminated solar cell adopt a parallel structure, the middle transparent conducting layer is used as a positive electrode or a negative electrode, and the front electrode of the top cell and the back electrode of the bottom cell form a corresponding negative electrode or a positive electrode together. In the silicon/perovskite laminated cell with the parallel structure, the photocurrents of the perovskite cell and the silicon cell are independent, so that the photocurrent of the silicon cell can be improved, and the higher photoelectric efficiency compared with a single-junction silicon cell can be obtained.
Description
Technical Field
The invention relates to the technical field of solar cells, in particular to a silicon/perovskite laminated solar cell.
Background
The perovskite solar cell is a novel solar cell, has the advantages of high efficiency, solution-soluble preparation, flexibility, light weight, low cost and the like, and is widely concerned all over the world. The conversion efficiency of perovskite solar cells has approached that of silicon-based solar cells. With the intensive research on silicon-based solar cells, their cell efficiency has also approached their theoretical maximum efficiency. Therefore, improving the photoelectric conversion efficiency of solar cells is becoming a key to the development of the art.
The laminated cell technology is one of effective ways for improving the photoelectric conversion efficiency of the solar cell. As the perovskite material has very strong absorption in the visible light region of 350nm-700nm, silicon absorbs near infrared light of 700-1100 nm. Therefore, a silicon/perovskite tandem structure solar cell composed of perovskite and silicon is increasingly studied and higher efficiency is obtained than a single-junction silicon cell or a perovskite cell.
Prior art silicon/perovskite tandem solar cells are typically constructed in a tandem fashion. The silicon cell is used as a bottom cell, the perovskite is used as a top cell, the silicon cell and the perovskite are connected through a composite layer (or a tunneling layer), and light is incident from the end of the perovskite. The voltage of the final silicon/perovskite tandem cell is the superposition of two sub-junction cells (perovskite and silicon), and the short-circuit current is generally close to the smaller value of the photocurrent generated by the two sub-junction cells.
Therefore, it is generally necessary to optimize the silicon/perovskite tandem stack cell by adjusting the optical band gap (1.6-1.7eV) of the perovskite cell so that the external quantum efficiency integral (photocurrent) of the two sub-junction cells is close to minimize the heat loss, thereby achieving high efficiency. Tandem silicon/perovskite tandem cells have more stringent requirements on the optical bandgap of the perovskite cell.
Furthermore, current perovskite materials have lower stability relative to single crystal silicon. With the attenuation of the performance of the perovskite sub-junction cell, the short-circuit current is reduced, and the balance of the light current in the two sub-junction cells is broken gradually, so that the short-circuit current of the silicon/perovskite laminated cell is reduced, and the service life of the silicon/perovskite solar cell is seriously influenced. The attenuation of the perovskite material can severely affect the performance and lifetime of the tandem cell.
Therefore, there is a need in the art for a new silicon/perovskite tandem cell that overcomes the above-mentioned technical problems with tandem silicon/perovskite tandem cells.
Disclosure of Invention
In order to solve the above technical problems, the present invention provides a silicon/perovskite tandem solar cell having better stability and cell performance than the tandem structure silicon/perovskite solar cell.
The invention provides a silicon/perovskite laminated solar cell, which comprises a silicon cell, a solar cell module and a control module, wherein the silicon cell is used as a bottom cell of the silicon/perovskite laminated solar cell; a perovskite cell for use as a top cell of the tandem solar cell; and an intermediate transparent conductive layer located between the silicon cell and the perovskite cell.
Further, the silicon cell has an extended portion with respect to the perovskite cell, and the intermediate transparent conductive layer covers an upper surface of the extended portion. Preferably, the protruding portion is a crystalline silicon layer of the silicon cell.
Further, a conductive grid line is arranged on or under the middle transparent conductive layer.
Further, the silicon cell is a silicon heterojunction cell.
Further, the perovskite absorption layer material of the perovskite battery has a band gap of 1.1-1.9 eV.
The silicon cell and the perovskite cell of the silicon/perovskite laminated solar cell adopt a parallel structure, the middle transparent conducting layer is used as a positive electrode or a negative electrode, and the front electrode of the top cell and the back electrode of the bottom cell form a corresponding negative electrode or a positive electrode together.
In the silicon/perovskite laminated cell with the parallel structure, the short-circuit current of the laminated solar cell is equal to the sum of the short-circuit current of the perovskite cell and the short-circuit current of the silicon cell, and the open-circuit voltage of the laminated cell is between the open-circuit voltage of the silicon cell and the open-circuit voltage of the perovskite cell and is close to the open-circuit voltage of the one of the perovskite solar cell and the silicon cell with the larger short-circuit current.
A silicon/perovskite tandem solar cell in a parallel configuration does not have as high a bandgap requirement as a tandem configuration for perovskite cells. Therefore, for the tandem solar cell with the parallel structure, the band gap of the perovskite cell does not need to be strictly regulated, so that the preparation of the tandem cell is simpler.
In the silicon/perovskite laminated cell with the parallel structure, the photocurrents of the perovskite cell and the silicon cell are independent, so that the photocurrent of the silicon cell can be improved, and the higher photoelectric efficiency compared with a single-junction silicon cell can be obtained.
In addition, because the photocurrents of the perovskite cell and the silicon cell are independent of each other, the performance attenuation of the perovskite cell has no influence on the silicon cell, so that the influence on the overall silicon/perovskite laminated solar cell is relatively small, and the parallel silicon/perovskite laminated solar cell has better stability than a series laminated solar cell.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by the practice of the invention. The objectives and other advantages of the invention will be realized and attained by the embodiments particularly pointed out in the written description and claims hereof as well as the appended drawings.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the example serve to explain the principles of the invention and not to limit the invention.
FIG. 1 is a schematic view of one embodiment of a silicon/perovskite tandem solar cell of the present invention;
FIG. 2 is a schematic view of another embodiment of a silicon/perovskite tandem solar cell of the present invention;
FIG. 3 is a graph of current density versus voltage for example 1 and comparative examples 2 and 4, measured under standard test conditions.
FIG. 4 is a graph of current density versus voltage for example 3 and comparative examples 3, 4 measured under standard test conditions.
FIG. 5 is a graph of short circuit current versus time curves for example 1 of the present invention and comparative examples 1 and 2.
FIG. 6 is a graph of the conversion efficiency versus time curves for example 1 of the present invention and comparative examples 1 and 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention.
The invention provides a silicon/perovskite tandem solar cell which comprises a silicon cell as a bottom cell, a perovskite cell as a top cell and an intermediate transparent conducting layer positioned between the silicon cell and the perovskite cell.
Intermediate transparent conductive layer:
the invention arranges a middle transparent conducting layer between a silicon battery and a perovskite battery as a common electrode of a bottom battery and a top battery, and the middle transparent conducting layer and a front electrode of the top battery and a back electrode of the bottom battery form a three-end parallel structure.
When the parallel structure silicon/perovskite laminated solar cell works, the short-circuit current of the solar cell is equal to the sum of the short-circuit current of the perovskite cell and the short-circuit current of the silicon cell, and the open-circuit voltage is between the open-circuit voltage of the silicon cell and the open-circuit voltage of the perovskite cell and the open-circuit voltage of the silicon cell, wherein the open-circuit voltage is close to the open-circuit voltage of the perovskite cell and the open-circuit voltage of the.
The thickness of the intermediate transparent conductive layer of the present invention is 50nm to 200nm, preferably 50nm to 150 nm. It can be seen that the intermediate transparent conductive layer of the present invention is very thin and it is difficult to extract it alone as an electrode.
In one embodiment, since the crystalline silicon layer of a tandem solar cell is thicker than all other layers, the present invention provides for the intermediate transparent conductive layer to be extracted from the tandem solar cell by providing the crystalline silicon layer of the silicon cell with an overhang relative to the perovskite cell, and the intermediate transparent conductive layer covering the upper surface of the overhang.
In another embodiment, the entire silicon cell may be provided with an overhang relative to the perovskite cell, and the intermediate transparent conductive layer covers the upper surface of the overhang, thereby extracting the intermediate transparent conductive layer from the tandem solar cell. The whole middle transparent conducting layer of the laminated solar cell is arranged on one plane, so that no crease occurs, and the conductive grid line can be prepared on the middle transparent conducting layer more conveniently (if needed).
The material of the intermediate transparent conductive layer of the present invention is preferably transparent conductive oxide, including but not limited to Indium Tin Oxide (ITO), indium tungsten oxide, aluminum-doped zinc oxide (AZO), boron-doped zinc oxide (zno), fluorine-doped tin oxide (FTO), and the like.
The transparent conductive layer of the present invention can be prepared by any method commonly employed in the art for preparing transparent conductive layers, including but not limited to deposition methods such as chemical vapor deposition, magnetron sputtering deposition, or reactive plasma deposition.
In one embodiment, conductive grid lines are provided above or below the intermediate transparent conductive layer for concentrating the current to enhance the conductive capability of the intermediate transparent conductive layer.
Silicon cell:
silicon cells for use in the present invention refer to silicon-based solar cells including, but not limited to, emitter cells, PERC back passivated cells, silicon heterojunction cells, PERT cells, IBC cells, MWT cells or Top-con cells, etc. Preferably, the silicon cell of the present invention is a silicon heterojunction cell.
In one embodiment, the silicon cell of the present invention includes a back electrode, an n-type amorphous silicon layer, a first intrinsic amorphous silicon layer, a crystalline silicon layer, a second intrinsic amorphous silicon layer, and a p-type amorphous silicon layer.
The crystalline silicon layer can be a p-type crystalline silicon wafer or an n-type crystalline silicon wafer. The thickness of the silicon wafer is 150 μm to 250 μm.
The n-type amorphous silicon layer and the p-type amorphous silicon layer each have a thickness of 2nm to 200 nm. The first and second intrinsic amorphous silicon layers have a thickness of 2nm to 50 nm.
In one embodiment, there is a transparent conductive layer between the n-type or p-type amorphous silicon layer and the back electrode. The materials and preparation methods of the transparent conductive layer are the same as described above for the intermediate transparent conductive layer section.
Perovskite battery:
the top cell of the silicon/perovskite tandem solar cell of the present invention employs a perovskite cell including, but not limited to, a hole transport layer, a perovskite absorption layer, an electron transport layer, and a front electrode. The perovskite cell structure includes an upright perovskite and an inverted perovskite structure.
Further, the perovskite battery employed in the present invention may further include any other functional layers commonly used in perovskite batteries, such as various modified layers for the purpose of enhancing conversion efficiency and improving performance, and the like.
The hole transport layer refers to a layer for extracting and transporting holes in photogenerated excitons of the perovskite absorption layer, and the material thereof may be any material commonly used in the field of perovskite solar cell technology for preparing a hole transport layer, including but not limited to polyethylenedioxythiophene-poly: styrene sulfonate (PEDOT: PSS), graphite, nickel oxide, cuprous thiocyanate or organic small molecule materials such as poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ] (PTAA), 2',7,7' -tetrakis (di-p-tolylamino) Spiro-9, 9 '-bifluorene (Spiro-TTB), N' -quaterphenylenediamine (TaTm), and the like.
The thickness of the hole transport layer can be adjusted according to the specific practice, and is preferably 5nm to 100 nm.
The hole transport layer of the present invention can be prepared by employing any conventional method for preparing a hole transport layer in the art. For example, nickel oxide can be prepared by magnetron sputtering, reactive plasma deposition, or chemical vapor deposition (including atomic layer deposition, low pressure chemical vapor deposition, metalorganic chemical vapor deposition, and the like); the cuprous sulfocyanide is prepared by vacuum evaporation.
The electron transport layer refers to a layer for extracting and transporting electrons in photogenerated excitons of the perovskite absorption layer, and the material of the electron transport layer can be any material commonly used for preparing the electron transport layer in the technical field of perovskite solar cells, including but not limited to wide-bandgap semiconductors such as SnO2、TiO2ZnO; polymers such as PFN (9, 9-dioctylfluorene-9, 9-bis N, N-dimethylaminopropylfluorene), Polyethyleneimine (PEI), etc.; rich inLexene and its derivatives (PCBM); small molecules such as 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline sulfonic acid disodium salt (BCP), 4, 7-diphenyl-1, 10-phenanthroline (Bpen), lithium fluoride, or the like.
The electron transport layer of the present invention may be a composite of two or more layers of the above materials. The thickness of the electron transport layer is 30nm to 50 nm.
The perovskite absorption layer is ABX3A material of construction wherein:
a is a monovalent cation, including but not limited to Rb+、Na+、K+、Cs+、HN＝CHNH3+(denoted as FA), CH3NH3 +(denoted as MA) or a combination thereof;
b is a divalent cation including but not limited to Sn2+、Pb2+Or a combination thereof;
x is selected from halogen anion, O2-、S2-And combinations thereof. The halide anion of the present invention includes F-、Cl-、Br-And I-。
The thickness of the perovskite absorption layer of the perovskite battery of the invention is preferably from 100nm to 1.5 microns
The perovskite material of the invention can adopt perovskite materials with various band gaps. For example, wide band gap perovskite materials with band gaps of 1.5-1.9eV can be used, including but not limited to CsxFAyMA1-x-yPbIzBr3-zWherein x is more than or equal to 0 and less than or equal to 0.2, y is more than or equal to 0.5 and less than or equal to 0.9, z is more than or equal to 2 and less than or equal to 3, and x + y is more than or equal to 0.5 and less than or equal to 1. Perovskite materials with band gaps of 1.1-1.5eV may also be used, including but not limited to (FASnI)3)x(MAPbI3)1-xWherein x is more than or equal to 0.2 and less than or equal to 0.6. The invention preferably employs narrow bandgap perovskite light absorbing materials.
In a preferred embodiment, a transparent conductive layer is provided between the electron-transport layer or the hole-transport layer and the front electrode. The materials and preparation methods of the transparent conductive layer are the same as described above for the intermediate transparent conductive layer section.
An electrode:
the silicon/perovskite tandem solar cell provided by the invention comprises a front electrode of a top cell and a back electrode of a bottom cell besides an intermediate transparent conducting layer serving as a common electrode of the top cell and the bottom cell.
The electrodes of the present invention may take the form of conductive grid lines. The material of the conductive grid line can be silver, copper or a composite material of a plurality of different metals, such as titanium/copper, tin/copper and the like. The thickness of the conductive grid lines can be adjusted according to the specific size of the silicon/perovskite tandem solar cell of the present invention, and is preferably 50nm to 200 μm.
The conductive grid line can be prepared by any conventional method in the art for preparing conductive grid lines, including but not limited to screen printing, electroplating and the like.
In one embodiment, a metallic silver grid line is prepared on a transparent conductive layer by screen printing. The silver grid prepared by the screen printing method has the thickness of 5 micrometers to 200 micrometers and the width of 1 micrometer to 200 micrometers.
In another embodiment, a copper grid line is prepared by an electroplating process. Specifically, a thin layer of copper is evaporated or sputtered on a transparent conducting layer through a mask to serve as a front body, and then a layer of copper grid line is electroplated on the front body in a copper salt solution. The thickness of the grid line prepared by the electroplating method is 100nm to 20 microns, wherein the thickness of the front body is 5nm to 100nm, the width is 1 micron to 200 microns, the thickness of the copper grid line is 100nm to 20 microns, and the width is 1 micron to 200 microns.
The following are specific examples of silicon/perovskite tandem solar cell structures of the present invention.
Fig. 1 is a schematic view of an embodiment of a silicon/perovskite tandem solar cell of the present invention.
The silicon/perovskite laminated solar cell sequentially comprises a back conductive grid line 101, a lower transparent conductive layer 102, an n-type amorphous silicon layer 103, a first intrinsic amorphous silicon layer 104, a crystalline silicon layer 105, a second intrinsic amorphous silicon layer 106, a p-type amorphous silicon layer 107, an intermediate transparent conductive layer 108, a hole transport layer 109, a perovskite absorption layer 110, an electron transport layer 111, an upper transparent conductive layer 112 and a front conductive grid line 113 from bottom to top.
The silicon/perovskite tandem solar cell further comprises an overhang 114. In this embodiment, the protruding portion is either side of the crystalline silicon layer 105, and the upper surface of the protruding portion is covered with the intermediate transparent conductive layer 108. The width of the protruding portion may be appropriately adjusted according to the size of the laminate battery to lead out the intermediate transparent conductive layer as an electrode.
The silicon/perovskite laminated solar cell is a p-i-n type perovskite, and the silicon cell adopts p-surface incident light. Electrons of the silicon/perovskite laminated solar cell are collected through the back conductive grid line 101, the lower transparent conductive layer 102, the upper transparent conductive layer 112 and the front conductive grid line 113 to form a negative electrode of the silicon/perovskite laminated solar cell, and holes of the silicon/perovskite laminated solar cell are collected through the common electrode intermediate transparent conductive layer 108 to form a positive electrode of the laminated solar cell.
In another embodiment, the n-type amorphous silicon layer and the p-type amorphous silicon layer in the above silicon/perovskite laminated solar cell are exchanged, and the hole transport layer and the electron transport layer are simultaneously exchanged, so that the silicon/perovskite laminated solar cell with the n-i-p type perovskite and the silicon cell in the n-surface light incidence structure can be obtained. Holes of the laminated solar cell are collected through the back conductive grid line, the lower transparent conductive layer, the upper transparent conductive layer and the front conductive grid line to form a negative electrode of the laminated solar cell, and electrons of the laminated solar cell are collected through the middle transparent conductive layer of the common electrode to form a positive electrode of the laminated solar cell.
Fig. 2 is a schematic view of another embodiment of a silicon/perovskite tandem solar cell of the present invention.
The layer structure of the silicon/perovskite tandem solar cell shown in fig. 2 is similar to that shown in fig. 1, except that the projecting portion 214 includes all layers between the intermediate transparent conductive layer and the crystalline silicon layer (inclusive) in addition to the crystalline silicon layer. With such a structure, the extracted intermediate transparent conductive layer is flat, and it is more convenient to prepare a conductive grid line on the intermediate transparent conductive layer (if necessary). In one embodiment, the silicon/perovskite tandem solar cell comprises a back conductive grid line 201, a lower transparent conductive layer 202, an n-type amorphous silicon layer 203, a first intrinsic amorphous silicon layer 204, a crystalline silicon layer 205, a second intrinsic amorphous silicon layer 206, a p-type amorphous silicon layer 207, an intermediate transparent conductive layer 208, a hole transport layer 209, a perovskite absorption layer 210, an electron transport layer 211, an upper transparent conductive layer 212 and a front conductive grid line 213 from bottom to top in sequence. In another embodiment, the n-type amorphous silicon layer and the p-type amorphous silicon layer in the above silicon/perovskite laminated solar cell are exchanged, and the hole transport layer and the electron transport layer are simultaneously exchanged, so that the silicon/perovskite laminated solar cell with the n-i-p type perovskite and the silicon cell in the n-surface light incidence structure can be obtained. Holes of the laminated solar cell are collected through the back conductive grid line, the lower transparent conductive layer, the upper transparent conductive layer and the front conductive grid line to form a negative electrode of the laminated solar cell, and electrons of the laminated solar cell are collected through the middle transparent conductive layer of the common electrode to form a positive electrode of the laminated solar cell.
The technical solution of the invention is further illustrated below by the preparation of a specific silicon/perovskite tandem solar cell:
example 1: preparation of silicon/wide-band-gap perovskite parallel laminated cell
S1, plating an intrinsic amorphous silicon layer on each of two surfaces of a cleaned and textured n-type silicon wafer through plasma enhanced chemical vapor deposition, wherein the thicknesses of the intrinsic amorphous silicon layers are 10nm and 12nm respectively; one side of the n-type silicon wafer is reserved with a part as a region for leading out the middle transparent conducting layer;
s2, depositing a layer of p-type amorphous silicon on the intrinsic amorphous silicon layer with the thickness of 10 nm. Depositing a layer of n-type amorphous silicon on the intrinsic amorphous silicon layer with the thickness of 12nm, wherein the thickness is 15 nm;
s3, preparing indium tin oxide on the n-type amorphous silicon layer through magnetron sputtering, wherein the thickness of the indium tin oxide is 100nm, and preparing indium tin oxide on the p-type amorphous silicon layer through magnetron sputtering, and the thickness of the indium tin oxide is 120 nm;
s4, depositing a layer of nickel oxide on the indium tin oxide layer of the p-type amorphous silicon layer through an electron beam, wherein the thickness of the nickel oxide layer is 50 nm; the nickel oxide layer covers the p-type amorphous silicon layer and also needs to cover a region reserved in advance by the n-type silicon wafer in the step S1;
s5, dissolving lead iodide, cesium iodide and lead bromide (the molar ratio is 4:7:3) in a solvent mixed by DMF/DMSO in a ratio of 9:1 at a concentration of 1.5mmol/ml, fully heating, stirring and dissolving, filtering through a polytetrafluoroethylene filter membrane with the caliber of 0.45 micrometer, spin-coating on the nickel oxide layer in the step S4 at a rotating speed of 4000 revolutions per minute, continuously dropwise adding a FAI (iodoformamidine) solution with a concentration of 0.4mmol/ml after keeping the rotation for 30 seconds, heating at 100 ℃ for 10min after the 1 minute of spin-coating is finished, and completing the preparation of the perovskite film;
s6, sequentially thermally evaporating 40nm PCBM and 5nm 4, 7-diphenyl-1, 10-phenanthroline (Bphen) on the perovskite thin film, and preparing a tin oxide layer with the thickness of 80nm by using atomic layer deposition;
s7, preparing a layer of aluminum-doped zinc oxide with the thickness of 80nm by using reactive plasma deposition;
s8, preparing silver grid lines on the indium tin oxide layers at the two ends by using screen printing, wherein the height of each silver grid line is 30 micrometers, and the width of each silver grid line is 40 micrometers. The distance between the silver grid lines is 3 mm;
and S9, connecting a diode in series on the conducting wire before the back conducting grid line and the front conducting grid line are connected (the maximum reverse working voltage is more than 2V, and the reverse current is less than 0.1mA under 2V), wherein the direction points to the front conducting grid line.
Example 2: preparation of silicon/narrow-band-gap perovskite parallel laminated cell (p-surface incident light)
S1, plating an intrinsic amorphous silicon layer on each of two surfaces of a cleaned and textured n-type silicon wafer through plasma enhanced chemical vapor deposition, wherein the thicknesses of the intrinsic amorphous silicon layers are 10nm and 12nm respectively;
s2, depositing a layer of p-type amorphous silicon on the intrinsic amorphous silicon layer with the thickness of 10 nm. Depositing a layer of n-type amorphous silicon on the intrinsic amorphous silicon layer with the thickness of 12nm, wherein the thickness is 15 nm;
s3, preparing indium tin oxide on the n-type amorphous silicon layer through magnetron sputtering, wherein the thickness of the indium tin oxide is 100nm, and preparing indium tin oxide on the p-type amorphous silicon layer through magnetron sputtering, and the thickness of the indium tin oxide is 120 nm;
s4, depositing a layer of nickel oxide on the indium tin oxide layer of the p-type amorphous silicon layer through an electron beam, wherein the thickness of the nickel oxide layer is 50 nm;
s5, dissolving FAI, cesium iodide, lead iodide and tin iodide (the molar ratio is 3:1:2:2) in a solvent mixed with DMF/DMSO/formic acid in a ratio of 3:1:0.2 at a concentration of 2mmol/ml, fully heating, stirring and dissolving, filtering through a polytetrafluoroethylene filter membrane with the caliber of 0.45 micron, rotationally coating on the nickel oxide layer in the step S4 at a rotating speed of 300 revolutions per minute for 30 seconds, immersing in anisole for 2 seconds, blow-drying with nitrogen gas, and heating at 100 ℃ for 10 minutes to complete the preparation of the perovskite film; when depositing this layer, leaving partial area on any side of nickel oxide layer, so as to lead out the middle transparent conductive layer.
S6, sequentially carrying out thermal evaporation on 40nm PCBM and 5nm Bphen on the perovskite thin film, and preparing a tin oxide layer with the thickness of 80nm by using atomic layer deposition;
s7, preparing a layer of aluminum-doped zinc oxide with the thickness of 80nm by using reactive plasma deposition;
s8, preparing silver grid lines on the indium tin oxide layers at the two ends by using screen printing, wherein the height of each silver grid line is 30 micrometers, and the width of each silver grid line is 40 micrometers. The distance between the silver grid lines is 3 mm.
Example 3: preparation of silicon/narrow-band-gap perovskite parallel laminated cell (n-surface incident light)
S1, plating an intrinsic amorphous silicon layer on each of two surfaces of a cleaned and textured n-type silicon wafer through plasma enhanced chemical vapor deposition, wherein the thicknesses of the intrinsic amorphous silicon layers are 10nm and 12nm respectively;
s2, depositing a layer of p-type amorphous silicon on the intrinsic amorphous silicon layer with the thickness of 10 nm. Depositing a layer of n-type amorphous silicon on the intrinsic amorphous silicon layer with the thickness of 12nm, wherein the thickness is 15 nm;
s3, preparing indium tin oxide on the p-type amorphous silicon layer by magnetron sputtering, wherein the thickness of the indium tin oxide is 100nm, and preparing indium tin oxide on the n-type amorphous silicon layer by magnetron sputtering, and the thickness of the indium tin oxide is 120 nm;
s4, depositing a layer of tin oxide on the indium tin oxide layer of the n-type amorphous silicon layer through an electron beam, wherein the thickness of the tin oxide layer is 40 nm;
s5, dissolving FAI, cesium iodide, lead iodide and tin iodide (the molar ratio is 3:1:2:2) in a solvent mixed by DMF/DMSO/formic acid in a ratio of 3:1:0.2 at a concentration of 2mmol/ml, fully heating, stirring and dissolving, filtering through a polytetrafluoroethylene filter membrane with the caliber of 0.45 micron, rotationally coating on the tin oxide layer in the step S4 at a rotating speed of 300 revolutions per minute for 30 seconds, immersing in anisole for 2 seconds, blow-drying with nitrogen gas, and heating at 100 ℃ for 10 minutes to complete the preparation of the perovskite film;
s6, sequentially spin-coating 40nm of PTAA and evaporating 50nm of molybdenum oxide on the perovskite thin film;
s7, preparing a layer of aluminum-doped zinc oxide with the thickness of 80nm by using reactive plasma deposition;
s8, preparing silver grid lines on the indium tin oxide layers at the two ends by using screen printing, wherein the height of each silver grid line is 30 micrometers, and the width of each silver grid line is 40 micrometers. The distance between the silver grid lines is 3 mm.
Comparative example 1: preparation of silicon/perovskite series laminated cell
S1, plating an intrinsic amorphous silicon layer on each of two surfaces of a cleaned and textured n-type silicon wafer through plasma enhanced chemical vapor deposition, wherein the thicknesses of the intrinsic amorphous silicon layers are 8nm and 10nm respectively;
s2, depositing a layer of p-type amorphous silicon on the intrinsic amorphous silicon layer with the thickness of 8nm, wherein the thickness is 15 nm. Depositing a layer of n-type amorphous silicon on the 10nm thick intrinsic amorphous silicon layer, wherein the thickness is 20 nm;
s3, manufacturing an n-type nano silicon layer on the n-type amorphous silicon through plasma enhanced chemical vapor deposition, wherein the thickness of the n-type nano silicon layer is 20nm, and continuously depositing a layer of p-type nano silicon with the thickness of 20 nm; preparing indium tin oxide on the p-type amorphous silicon layer by magnetron sputtering, wherein the thickness is 100 nm;
s4, depositing a layer of Spiro-TTB on the indium tin oxide layer of the n-type amorphous silicon layer through thermal evaporation, wherein the thickness of the Spiro-TTB is 80 nm;
s5, dissolving lead iodide, cesium iodide and lead bromide (the molar ratio is 4:7:3) in a solvent mixed by DMF/DMSO in a ratio of 9:1 at a concentration of 1.5mmol/ml, fully heating, stirring and dissolving, filtering through a polytetrafluoroethylene filter membrane with the caliber of 0.45 micrometer, spin-coating on the Spiro-TTB layer in the step S4 at a rotating speed of 4000 revolutions per minute, continuously dropwise adding a FAI solution with the concentration of 0.4mmol/ml after keeping the rotation for 30 seconds, heating at 100 ℃ for 10min after the spin-coating is finished for 1 min, and completing the preparation of the perovskite film;
s6, sequentially carrying out thermal evaporation on 40nm fullerene and 5nm BCP on the perovskite thin film, and preparing a tin oxide layer with the thickness of 80nm by using atomic layer deposition;
s7, preparing a layer of indium tin oxide with the thickness of 80nm by using reactive plasma deposition;
s8, preparing silver grid lines on the indium tin oxide layers at the two ends by using screen printing, wherein the height of each silver grid line is 20 micrometers, and the width of each silver grid line is 50 micrometers. The distance between the silver grid lines is 2 mm.
Comparative example 2: preparation of single-junction wide-band-gap perovskite cell
S1, using glass/FTO with the thickness of 2mm as a substrate/transparent electrode, carrying out ultraviolet/ozone treatment on the surface of the glass/FTO, depositing a layer of TaTm and 2,3,5, 6-tetrafluoro-7, 7,8, 8-tetracyanoquinodimethane (F4-TCNNQ) (the doping proportion is 12 mass percent) on an indium tin oxide layer of a p-type amorphous silicon layer by vacuum thermal co-evaporation, wherein the thickness is 30nm, and continuously depositing a layer of undoped TaTm with the thickness of 10 nm;
s2, dissolving lead iodide, cesium iodide and lead bromide (the molar ratio is 4:7:3) in a solvent mixed by DMF/DMSO in a ratio of 9:1 at a concentration of 1.5mmol/ml, fully heating, stirring and dissolving, filtering through a polytetrafluoroethylene filter membrane with the caliber of 0.45 micrometer, spin-coating on the TaTm layer in the step S1 at a rotating speed of 4000 revolutions per minute, continuously dropwise adding a FAI solution with a concentration of 0.4mmol/ml after keeping the rotation for 30 seconds, and heating at 100 ℃ for 10min after the spin-coating is finished for 1 minute to finish the preparation of the perovskite film;
s3, thermally evaporating 40nm PCBM, 5nm BCP and 1nm lithium fluoride on the perovskite thin film in sequence;
s4, preparing a layer of aluminum-doped zinc oxide with the thickness of 80nm by using reactive plasma deposition.
Comparative example 3: preparation of single-junction narrow-band-gap perovskite cells
S1, using glass/FTO with the thickness of 2mm as a substrate/transparent electrode, carrying out ultraviolet/ozone treatment on the surface of the substrate/transparent electrode, and depositing a layer of nickel oxide on an indium tin oxide layer on the p-type amorphous silicon layer side by using an electron beam, wherein the thickness is 50 nm;
s2, dissolving FAI, cesium iodide, lead iodide and tin iodide (the molar ratio is 3:1:2:2) in a solvent mixed with DMF/DMSO/formic acid in a ratio of 3:1:0.2 at a concentration of 2mmol/ml, fully heating, stirring and dissolving, filtering through a polytetrafluoroethylene filter membrane with the caliber of 0.45 micron, rotationally coating on the nickel oxide layer in the step S1 at a rotating speed of 300 revolutions per minute for 30 seconds, immersing in anisole for 2 seconds, blow-drying with nitrogen gas, and heating at 100 ℃ for 10 minutes to complete the preparation of the perovskite film;
s3, thermally evaporating 40nm PCBM, 5nm BCP and 1nm lithium fluoride on the perovskite thin film in sequence;
s4, preparing a layer of aluminum-doped zinc oxide with the thickness of 80nm by using reactive plasma deposition.
Comparative example 4: preparation of single silicon cell
S1, plating an intrinsic amorphous silicon layer on each of two surfaces of a cleaned and textured n-type silicon wafer through plasma enhanced chemical vapor deposition, wherein the thicknesses of the intrinsic amorphous silicon layers are 8nm and 10nm respectively;
s2, depositing a layer of p-type amorphous silicon on the intrinsic amorphous silicon layer with the thickness of 8nm, wherein the thickness is 15 nm. Depositing a layer of n-type amorphous silicon on the 10nm thick intrinsic amorphous silicon layer, wherein the thickness is 20 nm;
s3, preparing indium tin oxide on the n-type amorphous silicon layer by magnetron sputtering, wherein the thickness of the indium tin oxide is 80nm, and preparing indium tin oxide on the p-type amorphous silicon layer by magnetron sputtering, and the thickness of the indium tin oxide is 120 nm;
s8, preparing silver grid lines on the indium tin oxide layers at the two ends by using screen printing, wherein the height of each silver grid line is 20 micrometers, and the width of each silver grid line is 50 micrometers. The distance between the silver grid lines is 2 mm.
And (3) testing the battery performance:
and (3) testing procedures: adopting IEC 61646-testing standard of design and sizing (GB/T18911-2002) of film type photovoltaic modules for ground,
and (3) testing conditions are as follows: test spectrum AM1.5 (actual distance of light passing through atmosphere is 1.5 times of vertical thickness of atmosphere, incident angle is 48.2 degree), test temperature is 25 degree centigrade, and test light intensity is 1000W/m2。
Short-circuit current densities (J) were respectively tested under the above conditionssc) Open circuit voltage (V)oc) A conversion efficiency (PCE) and a Fill Factor (FF), resulting in a current density-voltage graph.
FIG. 3 is a graph of current density versus voltage for example 1 and comparative examples 2 and 4, measured under standard test conditions.
FIG. 4 is a graph of current density versus voltage for example 3 and comparative examples 3, 4 measured under standard test conditions.
The performance parameters of the examples measured under the above test conditions are shown in table 1:
table 1: performance parameters of each cell measured under standard test conditions
According to fig. 3, 4 and table 1, the photoelectric conversion efficiency, voltage and current of the parallel tandem solar cell are improved compared to the single silicon cell; compared with a series laminated cell, the photoelectric conversion efficiency is improved. And (3) analyzing the stability of the battery:
efficiency-time curve of the cell: the cells of the examples of the invention and comparative examples (not encapsulated) were subjected to intermittent illumination (short circuit, 6 hour illumination-18 hour dark cycle) under an inert gas atmosphere and the performance of the cells was tested (every 96 hours) to obtain an efficiency-time curve.
FIG. 5 is a graph of short circuit current versus time curves for example 1 of the present invention and comparative examples 1 and 2.
After 2400 hours of testing, the short-circuit current attenuation of the silicon/perovskite parallel laminated battery of the example 1 is only 9 percent; the short-circuit current attenuation of the silicon/perovskite series laminated cell of the comparative example 1 reaches 22 percent; the short circuit current decay of the wide band gap perovskite single junction cell of comparative example 2 reached 21%.
FIG. 6 is a graph of the efficiency versus time curves of example 1 of the present invention and comparative examples 1 and 2.
The photoelectric conversion efficiency decay of the silicon/perovskite parallel laminated cell of example 1 is only 12%; the attenuation of the photoelectric conversion efficiency of the perovskite/silicon tandem laminated cell of the comparative example 1 reaches 27 percent; the perovskite single-junction cell of comparative example 2 decayed to 28% in photoelectric conversion efficiency.
As can be seen from fig. 5 and 6, the photoelectric conversion efficiency and the decay rate of the short-circuit current of the parallel tandem solar cell of the present invention are much lower than those of the tandem solar cell and the single-junction perovskite solar cell.
This is mainly due to the fact that in a tandem stack cell, the short circuit current is typically close to the smaller of the photocurrents generated by the two sub-junction cells. As the perovskite sub-junction cell decays (silicon cell has substantially no decay), the photo-generated current gradually decreases, resulting in a decrease in the photo-generated current of the entire series structure cell. And the short-circuit current density and the cell efficiency decay speed with time of the single-junction perovskite solar cell are basically consistent with those of a perovskite/silicon tandem laminated cell.
Therefore, the decay rate of the current density and conversion efficiency of the silicon/perovskite parallel tandem solar cell of the invention with time is lower than that of the silicon/perovskite series tandem solar cell and the single-junction perovskite solar cell, thereby having better stability and longer service life.
It is to be understood that the terms first, second, third, fourth, and the like in the description of the embodiments of the invention are used for distinguishing between the descriptions and not for indicating or implying relative importance or order.
Although the embodiments of the present invention have been described above, the above description is only for the convenience of understanding the present invention, and is not intended to limit the present invention. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A silicon/perovskite tandem solar cell, characterized in that it comprises:
a silicon cell used as a bottom cell of the silicon/perovskite tandem solar cell;
a perovskite cell for use as a top cell of the silicon/perovskite tandem solar cell; and
an intermediate transparent conductive layer located between the silicon cell and the perovskite cell, serving as a common electrode for the silicon cell and the perovskite cell.
2. The silicon/perovskite tandem solar cell of claim 1, wherein the silicon cell has an overhang portion with respect to the perovskite cell, the intermediate transparent conductive layer covering an upper surface of the overhang portion.
3. The silicon/perovskite tandem solar cell according to claim 2, wherein the overhanging portion is a crystalline silicon layer of the silicon cell.
4. The silicon/perovskite tandem solar cell according to any one of claims 1 to 3, wherein the upper or lower surface of the intermediate transparent conductive layer is provided with a conductive grid line.
5. The silicon/perovskite tandem solar cell according to claims 1 to 3, wherein the silicon cell is a silicon heterojunction cell.
6. The silicon/perovskite tandem solar cell of claim 5, wherein the silicon cell comprises a back electrode, an n-type amorphous silicon layer, a first intrinsic amorphous silicon layer, a crystalline silicon layer, a second intrinsic amorphous silicon layer, and a p-type amorphous silicon layer.
7. A silicon/perovskite tandem solar cell according to any of claims 1 to 3, wherein the perovskite cell comprises a hole transport layer, a perovskite absorption layer, an electron transport layer and a front electrode.
8. The silicon/perovskite tandem solar cell according to claim 7, wherein the perovskite absorber layer material has a band gap of 1.1-1.9 eV.
9. The silicon/perovskite tandem solar cell according to claim 7, wherein the perovskite absorber layer material has a band gap of 1.1-1.5 eV.
10. The silicon/perovskite tandem solar cell according to claim 7, wherein the perovskite absorption layer is:
CsxFAyMA1-x-yPbIzBr3-zwherein x is more than or equal to 0 and less than or equal to 0.2, y is more than or equal to 0.5 and less than or equal to 0.9, z is more than or equal to 2 and less than or equal to 3, and x + y is more than or equal to 0.5 and less than or equal to 1; or
(FASnI3)x(MAPbI3)1-xWherein x is more than or equal to 0.2 and less than or equal to 0.6.
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| CN112864262A (en) * | 2021-01-20 | 2021-05-28 | 西安电子科技大学 | Perovskite-silicon two-end series battery based on mechanical pressing and preparation method |
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