CN111640867A - Hole transport layer and manufacturing method thereof, perovskite/silicon-based heterojunction laminated solar cell and manufacturing method thereof - Google Patents

Hole transport layer and manufacturing method thereof, perovskite/silicon-based heterojunction laminated solar cell and manufacturing method thereof Download PDF

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CN111640867A
CN111640867A CN202010367037.3A CN202010367037A CN111640867A CN 111640867 A CN111640867 A CN 111640867A CN 202010367037 A CN202010367037 A CN 202010367037A CN 111640867 A CN111640867 A CN 111640867A
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hole transport
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transport layer
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不公告发明人
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Suzhou Liannuo Solar Energy Technology Co ltd
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    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
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    • H10K30/57—Photovoltaic [PV] devices comprising multiple junctions, e.g. tandem PV cells
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Abstract

The invention relates to a hole transport layer and a manufacturing method thereof, a perovskite/silicon-based heterojunction tandem solar cell and a manufacturing method thereof. A method for manufacturing a hole transport layer, the hole transport layer is used for a perovskite/silicon-based heterojunction laminated solar cell, and the method for manufacturing the hole transport layer comprises the following steps: forming a protective layer on the substrate by adopting an atomic layer deposition technology; and forming a metal oxide layer on the protective layer by adopting a magnetron sputtering technology to obtain the hole transport layer. According to the manufacturing method of the hole transport layer for the perovskite/silicon-based heterojunction tandem solar cell, the protective layer is manufactured by adopting the atomic layer deposition technology, and the metal oxide layer is manufactured on the protective layer by adopting the magnetron sputtering technology, so that the low-temperature process can be realized, and the large-scale production can be realized.

Description

Hole transport layer and manufacturing method thereof, perovskite/silicon-based heterojunction laminated solar cell and manufacturing method thereof
Technical Field
The invention relates to the technical field of solar cells, in particular to a hole transport layer and a manufacturing method thereof, a perovskite/silicon-based heterojunction tandem solar cell and a manufacturing method thereof.
Background
The perovskite solar cell has the outstanding advantages of high photoelectric conversion efficiency, low cost, simple manufacture and the like, and becomes the most promising solar cell and a research hotspot. The point cell efficiency of the perovskite solar cell reaches 23.3 percent at present. The band gap of the materials applied to the perovskite solar cell at present is generally larger than 1.5eV, and the band gap of the perovskite absorption layer can be further increased to be more than 1.65eV through doping. The perovskite absorption layer with wide band gap is very favorable for forming a perovskite/Silicon-based heterojunction tandem solar cell with a Silicon crystal solar cell (SHJ). As shown in fig. 1, the conventional perovskite/silicon-based heterojunction stacked solar cell 100 'includes a back conductive grid line 110', a back transparent conductive layer 120', a silicon-based heterojunction cell 130', a tunneling junction 140', a perovskite cell 150', a front transparent conductive layer 160 'and a front conductive grid line 170' which are sequentially stacked. The direction indicated by the arrow in fig. 1 is the direction of illumination. The silicon-based heterojunction cell 130 'includes an amorphous silicon p-layer 131', an amorphous silicon i-layer 132', a crystalline silicon wafer 133', an amorphous silicon i-layer 134', and an amorphous silicon n-layer 135' stacked in this order. The tunnel junction 140' includes an n-layer 141' of a silicon-based thin film tunnel junction and a p-layer 142' of the silicon-based thin film tunnel junction. The perovskite cell 150 'includes a hole transport layer 151', an absorption layer 152', and an electron transport layer 153' stacked in this order.
The photoelectric conversion efficiency of the present perovskite/silicon-based heterojunction tandem solar cell reaches 27.3%, and simultaneously, the stability of the perovskite/silicon-based heterojunction tandem solar cell is superior to that of a perovskite single junction cell. However, the practical efficiency and the theoretical efficiency of the perovskite/silicon-based heterojunction tandem solar cell still have a large difference, and further optimization of the cell structure and optimization of the device design are one of the working key points for improving the efficiency of the perovskite/silicon-based heterojunction tandem solar cell in the future.
The traditional perovskite/silicon-based heterojunction tandem solar cell generally adopts materials such as nickel oxide, Spiro-OMETAD, Spiro-TTB or PTAA and the like as hole transport layer materials of the perovskite top cell. Due to poor stability of organic materials such as Spiro-OMETAD, Spiro-TTB and PTAA, the application of the organic materials to perovskite/SHJ laminated solar cells can result in low service life of the cells. And the service life of the perovskite/SHJ laminated solar cell is remarkably prolonged by adopting inorganic materials such as nickel oxide and the like as a hole transport layer of the perovskite/SHJ laminated solar cell. Taking nickel oxide as an example, the conventional method for manufacturing the hole transport layer of the perovskite/SHJ stacked solar cell by using inorganic materials such as nickel oxide and the like is to spin-coat a nickel oxide nanoparticle suspension or to form nickel oxide by using nickel acetylacetonate, which is a nickel-containing organic material, on a substrate through high-temperature oxidative decomposition. However, the method of spin coating with nickel oxide nanoparticle suspension cannot be applied to large-scale production; the method for forming nickel oxide by adopting nickel-containing organic material nickel acetylacetonate to perform high-temperature oxidative decomposition on the substrate requires a high temperature of more than 500 ℃, so that the production energy consumption is increased, and the SHJ battery is damaged when the SHJ battery is coated with a film.
Disclosure of Invention
Based on this, it is necessary to provide a hole transport layer and a manufacturing method thereof, a perovskite/silicon-based heterojunction tandem solar cell and a manufacturing method thereof, which can realize a low-temperature process and can be produced in a large scale.
A method for manufacturing a hole transport layer for a perovskite/silicon-based heterojunction tandem solar cell, the method for manufacturing the hole transport layer comprising the steps of:
forming a protective layer on the substrate by adopting an atomic layer deposition technology; and
and forming a metal oxide layer on the protective layer by adopting a magnetron sputtering technology to obtain a hole transport layer.
According to the manufacturing method of the hole transport layer for the perovskite/silicon-based heterojunction tandem solar cell, the protective layer is manufactured by adopting the atomic layer deposition technology, and the metal oxide layer is manufactured on the protective layer by adopting the magnetron sputtering technology, so that the low-temperature process can be realized, and the large-scale production can be realized.
In one embodiment, in the step of forming the metal oxide layer on the protective layer by using a magnetron sputtering technique, a sputtering gas is argon or a mixed gas of argon and oxygen; in the mixed gas of argon and oxygen, the volume fraction of oxygen is 0.01-30%.
The hole transport layer obtained by the manufacturing method is used for a perovskite/silicon-based heterojunction laminated solar cell and comprises a protective layer and a metal oxide layer which are laminated.
In one embodiment, the material of the protective layer is at least one selected from nickel oxide, lithium cobaltate, copper oxide, vanadium oxide, chromium oxide and molybdenum oxide.
In one embodiment, the thickness of the protective layer is 1nm to 20 nm.
In one embodiment, the material of the metal oxide layer is selected from at least one of nickel oxide, lithium cobaltate, copper oxide, vanadium oxide, chromium oxide and molybdenum oxide.
In one embodiment, the thickness of the metal oxide layer is 1nm to 200 nm.
A perovskite/silicon-based heterojunction tandem solar cell comprises a perovskite cell and a tunneling junction arranged on one side of the perovskite cell, wherein the perovskite cell comprises the hole transport layer or the hole transport layer obtained by the hole transport layer manufacturing method, and a protective layer of the hole transport layer is arranged between the tunneling junction and a metal oxide layer.
In one embodiment, the tunnel junction is a silicon-based thin film tunnel junction.
A manufacturing method of a perovskite/silicon-based heterojunction tandem solar cell comprises the manufacturing method of the hole transport layer.
The perovskite/silicon-based heterojunction tandem solar cell and the manufacturing method thereof can realize low-temperature process and large-scale production.
Drawings
Fig. 1 is a schematic diagram of a conventional perovskite/silicon-based heterojunction tandem solar cell;
FIG. 2 is a flow chart of a method for fabricating a hole transport layer according to an embodiment of the present invention;
fig. 3 is a schematic diagram of a perovskite/silicon-based heterojunction tandem solar cell according to an embodiment of the present invention.
Wherein, 100', perovskite/silicon-based heterojunction tandem solar cells; 110', a back conductive gate line; 120', a back transparent conductive layer; 130', a silicon-based heterojunction cell; 131' and an amorphous silicon p layer; 132', an amorphous silicon i layer; 133', a crystalline silicon wafer; 134', amorphous silicon i layer; 135' and an amorphous silicon n layer; 140', a tunnel junction; 141', n layers of silicon-based thin film tunneling junctions; 142', p layer of silicon-based thin film tunneling junction; 150', a perovskite cell; 151', a hole transport layer; 152', an absorber layer; 153', an electron transport layer; 160', a front transparent conductive layer; 170', front conductive grid lines; 100. a perovskite/silicon-based heterojunction tandem solar cell; 110. a back conductive grid line; 120. a back transparent conductive layer; 130. a silicon-based heterojunction cell; 131. an amorphous silicon p layer; 132. an amorphous silicon i layer; 133. a crystalline silicon wafer; 134. an amorphous silicon i layer; 135. an amorphous silicon n layer; 140. a tunneling junction; 141. n layers of silicon-based thin film tunneling junctions; 142. a p layer of a silicon-based thin film tunneling junction; 150. a perovskite battery; 151. a hole transport layer; 152. an absorbing layer; 153. an electron transport layer; 154. a protective layer; 155. a metal oxide layer; 160. a front transparent conductive layer; 170. and a front conductive grid line.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The invention provides a manufacturing method of a hole transport layer, wherein the hole transport layer is used for a perovskite/silicon-based heterojunction tandem solar cell.
Referring to fig. 2, a method for fabricating a hole transport layer according to an embodiment of the present invention includes the following steps:
and S10, forming a protective layer on the substrate by adopting the atomic layer deposition technology.
The substrate of the present invention refers to any substrate capable of functioning as a carrier protective layer. For example, when the protective layer is formed on the tunnel junction, the substrate includes a back conductive gate line, a back transparent conductive layer, a silicon-based heterojunction cell, and a tunnel junction, which are sequentially stacked. The protective layer plays a role in protecting the substrate positioned below the protective layer, so that the damage of the substrate caused by subsequent magnetron sputtering can be reduced, and the performance of the perovskite/silicon-based heterojunction tandem solar cell is improved.
And S20, forming a metal oxide layer on the protective layer by adopting a magnetron sputtering technology to obtain the hole transport layer.
Further, in the step of forming the metal oxide layer on the protective layer by using a magnetron sputtering technique, the sputtering gas is argon or a mixed gas of argon and oxygen; in the mixed gas of argon and oxygen, the volume fraction of oxygen is 0.01-30%. When the sputtering gas is the mixed gas of argon and oxygen, better crystallization is formed, and the quality of the hole transport layer is improved.
According to the manufacturing method of the hole transport layer for the perovskite/silicon-based heterojunction tandem solar cell, the protective layer is manufactured by adopting the atomic layer deposition technology, and the metal oxide layer is manufactured on the protective layer by adopting the magnetron sputtering technology, so that the low-temperature process can be realized, and the large-scale production can be realized.
The hole transport layer for the perovskite/silicon-based heterojunction tandem solar cell of the embodiment is obtained by adopting the manufacturing method, and comprises a protective layer and a metal oxide layer which are stacked. That is, the protective layer is manufactured by an atomic layer deposition technology, and the metal oxide layer is manufactured by a magnetron sputtering technology.
The protective layer plays a role in protecting the substrate positioned below the protective layer, so that the damage of the substrate caused by subsequent magnetron sputtering can be reduced, and the performance of the perovskite/silicon-based heterojunction tandem solar cell is improved.
Further, the material of the protective layer is selected from at least one of nickel oxide, lithium cobaltate, copper oxide, vanadium oxide, chromium oxide and molybdenum oxide.
Further, the thickness of the protective layer is 1nm to 20 nm. Alternatively, the protective layer may have a thickness of 1nm, 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, 11nm, 12nm, 13nm, 14nm, 15nm, 16nm, 17nm, 18nm, 19nm, or 20 nm. Of course, the thickness of the protective layer may be any integer value or non-integer value between 1nm and 20 nm. More preferably, the thickness of the protective layer is 5nm to 10 nm.
Further, the material of the metal oxide layer is selected from at least one of nickel oxide, lithium cobaltate, copper oxide, vanadium oxide, chromium oxide and molybdenum oxide. The material of the metal oxide layer is not limited thereto, and other materials that can be used for preparing the heterojunction solar energy lamination are all suitable for the invention.
Further, the thickness of the metal oxide layer is 1nm to 200 nm. Alternatively, the metal oxide layer may have a thickness of 1nm, 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 110nm, 120nm, 130nm, 140nm, 150nm, 160nm, 170nm, 180nm, 190nm, or 200 nm. Of course, the thickness of the metal oxide layer may be any integer value or non-integer value between 1nm and 20 nm. More preferably, the metal oxide layer has a thickness of 10nm to 50 nm.
The hole transport layer for the perovskite/silicon-based heterojunction tandem solar cell can realize a low-temperature process and can be produced in a large scale.
The perovskite/silicon-based heterojunction tandem solar cell comprises a perovskite cell and a tunneling junction positioned on one side of the perovskite cell, wherein the perovskite cell comprises the hole transport layer or the hole transport layer obtained by adopting the hole transport layer manufacturing method, and a protective layer of the hole transport layer is positioned between the tunneling junction and a metal oxide layer.
Furthermore, the tunneling junction is a silicon-based thin film tunneling junction. At this time, the energy of the deposited particles in the magnetron sputtering deposition is too large, which may damage the silicon-based thin film tunneling junction on the silicon-based heterojunction bottom cell as the substrate, and further affect the performance of the perovskite/silicon-based heterojunction tandem cell. Therefore, before magnetron sputtering, an atomic layer deposition technology is used for preparing a thin protective layer on the tunneling junction of the silicon-based heterojunction bottom cell, so that the damage of magnetron sputtering to the tunneling junction can be reduced, and the performance of the perovskite/silicon-based heterojunction laminated solar cell is improved.
Referring to fig. 3, the perovskite/silicon-based heterojunction stacked solar cell 100 according to an embodiment of the present invention includes a back conductive grid line 110, a back transparent conductive layer 120, a silicon-based heterojunction cell 130, a tunneling junction 140, a perovskite cell 150, a front transparent conductive layer 160, and a front conductive grid line 170, which are sequentially stacked. The direction indicated by the arrow in fig. 3 is the direction of illumination. The silicon-based heterojunction cell 130 comprises an amorphous silicon p layer 131, an amorphous silicon i layer 132, a crystalline silicon wafer 133, an amorphous silicon i layer 134 and an amorphous silicon n layer 135 which are sequentially stacked. The tunnel junction 140 includes an n layer 141 of a silicon-based thin film tunnel junction and a p layer 142 of the silicon-based thin film tunnel junction. The perovskite cell 150 includes a hole transport layer 151, an absorption layer 152, and an electron transport layer 153, which are stacked in this order. The hole transport layer 151 includes a protective layer 154 and a metal oxide layer 155 stacked therein.
The back conductive grid line 110 is generally a silver grid, and is manufactured by screen printing. The back transparent conductive layer 120 is typically Indium Tin Oxide (ITO) and is fabricated by magnetron sputtering deposition to a thickness of about 80 nm. The amorphous silicon p-layer 131 is fabricated by Plasma Enhanced Chemical Vapor Deposition (PECVD) and is typically 10nm thick. The amorphous silicon i-layer 132 is typically 10nm thick and is fabricated by Plasma Enhanced Chemical Vapor Deposition (PECVD). The crystalline silicon wafer 133 is an n-type silicon wafer or a p-type silicon wafer, and generally has a thickness of 150 to 250 micrometers. The amorphous silicon i-layer 134 is typically 10nm thick. Fabricated by Plasma Enhanced Chemical Vapor Deposition (PECVD). The amorphous silicon n-layer 135 is typically 10nm thick. Fabricated by Plasma Enhanced Chemical Vapor Deposition (PECVD). The cathode of the silicon-based heterojunction cell 130 is in contact with the tunneling junction, and the anode is in contact with the back transparent conductive layer 120.
The protective layer 154 of the hole transport layer 151 of the present embodiment is formed by an atomic layer deposition technique. The metal oxide layer 155 of the hole transport layer 151 is formed by a magnetron sputtering technique.
Wherein, the material of the absorption layer 152 of the perovskite battery 150 is FA1-xCsxPbI3Typically 0.1 thereof<x is less than or equal to 1. Wherein, the material of the electron transport layer 153 of the perovskite battery 150 is SnO2、TiO2ZnO, is generally produced by Atomic Layer Deposition (ALD), and has a thickness of 50 nm.
The perovskite/silicon-based heterojunction tandem solar cell can realize a low-temperature process and can be produced in a large scale.
The method for manufacturing the perovskite/silicon-based heterojunction tandem solar cell comprises the method for manufacturing the hole transport layer.
The manufacturing method of the perovskite/silicon-based heterojunction tandem solar cell can realize a low-temperature process and can realize large-scale production.
The hole transport layer and the method for manufacturing the hole transport layer, the perovskite/silicon-based heterojunction tandem solar cell and the method for manufacturing the perovskite/silicon-based heterojunction tandem solar cell of the present invention are further described below with reference to specific embodiments.
Example 1
And plating an intrinsic amorphous silicon layer on each of two surfaces of the 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 15nm respectively.
And then depositing a layer of p-type amorphous silicon on the intrinsic amorphous silicon layer with the thickness of 15nm, wherein the thickness of the p-type amorphous silicon layer is 10 nm. And depositing a layer of n-type amorphous silicon on the intrinsic amorphous silicon layer with the thickness of 10nm, wherein the thickness of the n-type amorphous silicon layer is 15 nm.
And preparing a back transparent conducting layer on the p-type amorphous silicon layer by magnetron sputtering, wherein the material is Indium Tin Oxide (ITO) and the thickness is 60 nm.
And preparing a silicon-based film on the n-type amorphous silicon layer by Plasma Enhanced Chemical Vapor Deposition (PECVD) to be used as a tunneling junction of the laminated cell, wherein the thickness of the silicon-based film is 20 nm.
And then preparing a vanadium oxide protective layer on a 20nm silicon-based thin film tunneling junction through atomic layer deposition. The deposition precursor material is vanadium tetra (methylethylamine) (TEMAV) and the oxidant is water. The deposition temperature was 200 ℃ and the thickness of the deposited film was 3 nm.
And then preparing a metal oxide layer of a hole transport layer of the perovskite solar cell on a vanadium oxide protective layer with the thickness of 3nm through magnetron sputtering. Vanadium pentoxide is used as a target material for preparation. The sputtering gas is argon, and oxygen with the flow of argon of 10 percent is introduced at the same time; the sputtering power supply is a radio frequency power supply, and the power supply frequency is 2 MHz; the sputtering power density is 2W/square centimeter; the process pressure is 1 pascal; the thickness of the deposited film was 20 nm.
Followed by deposition of a perovskite absorption layer on the hole transport layer. The material of the absorbing layer is FA0.9MA0.1PbI3(ii) a The deposition method is vacuum co-evaporation. The evaporation raw materials are FAI, MAI and PbI2 respectively; the FAI evaporation temperature was 200 ℃, the MAI evaporation temperature was 120 ℃ and the PbI2 evaporation temperature was 400 ℃. The temperature of the substrate material was 30 ℃. The thickness of the perovskite absorption layer is 400 nm.
Depositing an electron transport layer on the deposited perovskite absorption layer, wherein the material is tin oxide SnO2The deposition method is Atomic Layer Deposition (ALD). The film thickness was 30 nm.
And depositing a front transparent conductive layer on the deposited hole transport layer, wherein the material is Indium Tin Oxide (ITO). The deposition method is Reactive Plasma Deposition (RPD). The deposited film thickness was 80 nm.
And preparing silver grid lines on the deposited front electrode transparent conductive layer by screen printing, wherein the height of the silver grid lines is 20 micrometers, the width of the silver grid lines is 50 micrometers, and the distance between the silver grid lines is 2 millimeters.
And preparing silver grid lines on the deposited back electrode transparent conductive layer by screen printing, wherein the height of the silver grid lines is 20 micrometers, the width of the silver grid lines is 50 micrometers, and the distance between the silver grid lines is 1.5 millimeters.
And finishing the preparation of the whole laminated solar cell, wherein the silver grid line on one side of the perovskite solar cell is the cathode of the cell, and the silver grid line on the side of the SHJ cell is the anode of the cell.
Example 2
And plating an intrinsic amorphous silicon layer on each of two surfaces of the cleaned and textured n-type silicon wafer through plasma enhanced chemical vapor deposition, wherein the thickness of each intrinsic amorphous silicon layer is 10 nm.
And then depositing a layer of p-type amorphous silicon and a layer of n-type amorphous silicon on the intrinsic amorphous silicon layers on the two surfaces respectively, wherein the thickness of the p-type amorphous silicon is 20nm, the doping concentration of boron is 0.5%, the thickness of the n-type amorphous silicon is 15nm, and the doping concentration of phosphorus is 0.4%.
And preparing a back transparent conductive layer on the p-type amorphous silicon layer by magnetron sputtering, wherein the material is aluminum-doped zinc oxide (AZO) and the thickness is 200 nm.
And preparing a nano silicon film as a tunneling junction of the laminated cell on the n-type amorphous silicon layer by Plasma Enhanced Chemical Vapor Deposition (PECVD), wherein the thickness of the nano silicon film is 30 nm.
And then preparing a nickel oxide protective layer on the nano silicon film tunnel junction with the thickness of 30nm by atomic layer deposition. The deposition precursor material was nickel bis (N, N' -diisopropylacetamidinyl) (Ni (iPr-MeAMD)2) The oxidant is ozone. The deposition temperature was 200 ℃ and the thickness of the deposited film was 5 nm.
And then preparing a metal oxide layer of a hole transport layer of the perovskite solar cell on a nickel oxide protective layer with the thickness of 5nm by magnetron sputtering. The preparation method adopts lithium cobaltate (LiCoO)2) As a target material. The sputtering gas is argon; the sputtering power supply is a radio frequency power supply, and the power supply frequency is 20 kilohertz; the sputtering power density is 2W/square centimeter; the process pressure is 1 pascal; the thickness of the deposited film was 30 nm.
And then preparing a hole transport layer of the perovskite solar cell on the silicon-based thin film tunneling junction through magnetron sputtering. The hole transport layer is prepared by adopting nickel oxide as a target material. The sputtering gas was argon, and oxygen gas at a flow rate of 1% argon was introduced. The sputtering power supply is an alternating current power supply, and the power frequency is 20 kilohertz; the sputtering pressure is 3 pascal; the sputtering power density was 1 watt/cm. The thickness of the deposited film was 15 nm.
A perovskite absorber layer is deposited on the hole transport layer nickel oxide. The material of the absorbing layer is FA0.7MA0.3PbI3(ii) a The deposition method is vacuum co-evaporation. The evaporation raw materials are FAI, MAI and PbI2 respectively; the FAI evaporation temperature was 200 ℃, the MAI evaporation temperature was 140 ℃ and the PbI2 evaporation temperature was 400 ℃. The temperature of the substrate material was 30 ℃. The thickness of the perovskite absorption layer is 400 nm.
Depositing an electron transport layer on the deposited perovskite absorption layer, wherein the material is fullerene (C)60) The deposition method is vacuum evaporation, and the evaporation temperature of the raw material is420 ℃, the substrate temperature is 30 ℃, and the film thickness is 10 nm.
And depositing a front transparent conductive layer on the deposited hole transport layer, wherein the material is indium tungsten oxide (IWO). The deposition method is Reactive Plasma Deposition (RPD), and the thickness of the deposited film is 80 nm.
And preparing silver grid lines on the deposited front electrode transparent conductive layer by screen printing, wherein the height of the silver grid lines is 15 micrometers, the width of the silver grid lines is 60 micrometers, and the distance between the silver grid lines is 2 millimeters.
And preparing silver grid lines on the deposited back electrode transparent conductive layer by screen printing, wherein the height of the silver grid lines is 15 micrometers, the width of the silver grid lines is 50 micrometers, and the distance between the silver grid lines is 1.5 millimeters.
And finishing the preparation of the whole laminated solar cell, wherein the silver grid line on the perovskite side is the anode of the cell, and the silver grid line on the SHJ cell side is the cathode of the cell.
Example 3
And plating an intrinsic amorphous silicon layer on each of two surfaces of the 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.
Then a layer of p-type amorphous silicon with a thickness of 10nm is deposited on the intrinsic amorphous silicon layer with a thickness of 12 nm. An n-type amorphous silicon layer with a thickness of 15nm is deposited on the 10nm thick intrinsic amorphous silicon layer.
And preparing a back transparent conducting layer on the p-type amorphous silicon layer by magnetron sputtering, wherein the material is Indium Tin Oxide (ITO) and the thickness is 120 nm.
And preparing a nano silicon film as a tunneling junction of the laminated cell on the n-type amorphous silicon layer by Plasma Enhanced Chemical Vapor Deposition (PECVD), wherein the thickness of the nano silicon film is 30 nm.
And then preparing a cobalt oxide protective layer on the nano silicon film tunneling junction with the thickness of 30nm by atomic layer deposition. Depositing a precursor material as cobaltocene (CoCp)2) The oxidant is water. The deposition temperature was 150 ℃ and the thickness of the deposited film was 5 nm.
And then preparing a metal oxide layer of a hole transport layer of the perovskite solar cell on the cobalt oxide protective layer with the thickness of 5nm through magnetron sputtering. The preparation adopts nickel oxide as a target material. The sputtering gas is argon; the sputtering power supply is a radio frequency power supply, and the power supply frequency is 20 kilohertz; the sputtering power density is 2W/square centimeter; the process pressure is 1 pascal; the thickness of the deposited film was 30 nm.
Followed by deposition of a perovskite absorption layer on the hole transport layer. The material of the absorbing layer is FA0.9MA0.1PbI3(ii) a The deposition method is vacuum co-evaporation. The evaporation raw materials are FAI, MAI and PbI2 respectively; the FAI evaporation temperature is 200 ℃, the MAI evaporation temperature is 120 ℃, the PbI2 evaporation temperature is 400 ℃, the temperature of the substrate material is 30 ℃, and the thickness of the perovskite absorption layer is 400 nm.
Depositing an electron transport layer on the deposited perovskite absorption layer, wherein the material is tin oxide SnO2The deposition method is Atomic Layer Deposition (ALD) and the film thickness is 30 nm.
And depositing a front transparent conductive layer on the deposited hole transport layer, wherein the material is Indium Tin Oxide (ITO). The deposition method is Reactive Plasma Deposition (RPD), and the thickness of the deposited film is 80 nm.
And preparing silver grid lines on the deposited front electrode transparent conductive layer by screen printing, wherein the height of the silver grid lines is 20 micrometers, the width of the silver grid lines is 50 micrometers, and the distance between the silver grid lines is 2 millimeters.
And preparing silver grid lines on the deposited back electrode transparent conductive layer by screen printing, wherein the height of the silver grid lines is 20 micrometers, the width of the silver grid lines is 50 micrometers, and the distance between the silver grid lines is 1.5 millimeters.
And finishing the preparation of the whole laminated solar cell, wherein the silver grid line on one side of the perovskite solar cell is the cathode of the cell, and the silver grid line on the side of the SHJ cell is the anode of the cell.
Comparative example 1
And plating an intrinsic amorphous silicon layer on each of two surfaces of the 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.
Then a layer of p-type amorphous silicon with a thickness of 10nm is deposited on the intrinsic amorphous silicon layer with a thickness of 12 nm. An n-type amorphous silicon layer with a thickness of 15nm is deposited on the 10nm thick intrinsic amorphous silicon layer.
And preparing a back transparent conducting layer on the p-type amorphous silicon layer by magnetron sputtering, wherein the material is Indium Tin Oxide (ITO) and the thickness is 120 nm.
And preparing a nano silicon film as a tunneling junction of the laminated cell on the n-type amorphous silicon layer by Plasma Enhanced Chemical Vapor Deposition (PECVD), wherein the thickness of the nano silicon film is 30 nm.
And then preparing a hole transport layer of the perovskite solar cell on a nano silicon thin film tunnel junction with the thickness of 30nm by a spray thermal decomposition method. The specific method comprises the following steps: the silicon cell for preparing the tunnel junction is heated to 500 ℃, and prepared nickel acetylacetonate with the concentration of 5% is sprayed on the silicon cell substrate by a spraying mode. The nickel acetylacetonate reacts with oxygen in the air under the action of high temperature to generate nickel oxide which is used as a hole transport layer of the perovskite solar cell and has the thickness of 15 nm.
Followed by deposition of a perovskite absorption layer on the hole transport layer. The material of the absorbing layer is FA0.9MA0.1PbI3(ii) a The deposition method is vacuum co-evaporation. The evaporation raw materials are FAI, MAI and PbI2 respectively; the FAI evaporation temperature is 200 ℃, the MAI evaporation temperature is 120 ℃, the PbI2 evaporation temperature is 400 ℃, the temperature of the substrate material is 30 ℃, and the thickness of the perovskite absorption layer is 400 nm.
Depositing an electron transport layer on the deposited perovskite absorption layer, wherein the material is tin oxide SnO2The deposition method is Atomic Layer Deposition (ALD). The film thickness was 30 nm.
And depositing a front transparent conductive layer on the deposited hole transport layer, wherein the material is Indium Tin Oxide (ITO). The deposition method is Reactive Plasma Deposition (RPD). The deposited film thickness was 80 nm.
And preparing silver grid lines on the deposited front electrode transparent conductive layer by screen printing, wherein the height of the silver grid lines is 20 micrometers, the width of the silver grid lines is 50 micrometers, and the distance between the silver grid lines is 2 millimeters.
And preparing silver grid lines on the deposited back electrode transparent conductive layer by screen printing, wherein the height of the silver grid lines is 20 micrometers, the width of the silver grid lines is 50 micrometers, and the distance between the silver grid lines is 1.5 millimeters.
And finishing the preparation of the whole laminated solar cell, wherein the silver grid line on one side of the perovskite solar cell is the cathode of the cell, and the silver grid line on the side of the SHJ cell is the anode of the cell.
Comparative example 2
And plating an intrinsic amorphous silicon layer on each of two surfaces of the 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.
Then a layer of p-type amorphous silicon with a thickness of 10nm is deposited on the intrinsic amorphous silicon layer with a thickness of 12 nm. An n-type amorphous silicon layer with a thickness of 15nm is deposited on the 10nm thick intrinsic amorphous silicon layer.
And preparing a back transparent conducting layer on the p-type amorphous silicon layer by magnetron sputtering, wherein the material is Indium Tin Oxide (ITO) and the thickness is 120 nm.
And preparing a nano silicon film as a tunneling junction of the laminated cell on the n-type amorphous silicon layer by Plasma Enhanced Chemical Vapor Deposition (PECVD), wherein the thickness of the nano silicon film is 30 nm.
And then preparing a hole transport layer of the perovskite solar cell on a nano silicon thin film tunneling junction of 30nm through magnetron sputtering. The preparation method comprises the following steps: nickel oxide is used as a target material, and sputtering gas is mixed gas of argon and oxygen, wherein the volume fraction of the oxygen is 10% of the volume of the argon; the sputtering power supply is a radio frequency power supply, and the power supply frequency is 2 MHz; the sputtering power density is 2W/square centimeter; the process pressure is 1 pascal; the film was deposited to obtain a hole transport layer with a thickness of 20 nm.
Followed by deposition of a perovskite absorption layer on the hole transport layer. The material of the absorbing layer is FA0.9MA0.1PbI3(ii) a The deposition method is vacuum co-evaporation. The evaporation raw materials are FAI, MAI and PbI2 respectively; the FAI evaporation temperature is 200 ℃, the MAI evaporation temperature is 120 ℃, the PbI2 evaporation temperature is 400 ℃, the temperature of the substrate material is 30 ℃, and the thickness of the perovskite absorption layer is 400 nm.
Depositing an electron transport layer on the deposited perovskite absorption layer, wherein the material is tin oxide SnO2The deposition method is Atomic Layer Deposition (ALD). The film thickness was 30 nm.
And depositing a front transparent conductive layer on the deposited hole transport layer, wherein the material is Indium Tin Oxide (ITO). The deposition method is Reactive Plasma Deposition (RPD). The deposited film thickness was 80 nm.
And preparing silver grid lines on the deposited front electrode transparent conductive layer by screen printing, wherein the height of the silver grid lines is 20 micrometers, the width of the silver grid lines is 50 micrometers, and the distance between the silver grid lines is 2 millimeters.
And preparing silver grid lines on the deposited back electrode transparent conductive layer by screen printing, wherein the height of the silver grid lines is 20 micrometers, the width of the silver grid lines is 50 micrometers, and the distance between the silver grid lines is 1.5 millimeters.
And finishing the preparation of the whole laminated solar cell, wherein the silver grid line on one side of the perovskite solar cell is the cathode of the cell, and the silver grid line on the side of the SHJ cell is the anode of the cell.
Comparative example 3
And plating an intrinsic amorphous silicon layer on each of two surfaces of the 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.
Then a layer of p-type amorphous silicon with a thickness of 10nm is deposited on the intrinsic amorphous silicon layer with a thickness of 12 nm. An n-type amorphous silicon layer with a thickness of 15nm is deposited on the 10nm thick intrinsic amorphous silicon layer.
And preparing a back transparent conducting layer on the p-type amorphous silicon layer by magnetron sputtering, wherein the material is Indium Tin Oxide (ITO) and the thickness is 120 nm.
And preparing a nano silicon film as a tunneling junction of the laminated cell on the n-type amorphous silicon layer by Plasma Enhanced Chemical Vapor Deposition (PECVD), wherein the thickness of the nano silicon film is 30 nm.
And spin-coating a suspension of nickel oxide nanoparticles on a 30nm nano-silicon thin film tunnel junction, and baking at 200 ℃ for 30 minutes to form a nickel oxide thin film, wherein the thickness of the thin film is generally 20nm, so as to obtain a hole transport layer of the perovskite solar cell.
Followed by deposition of a perovskite absorption layer on the hole transport layer. The material of the absorbing layer is FA0.9MA0.1PbI3(ii) a The deposition method is vacuum co-evaporation. The evaporation raw materials are FAI, MAI and PbI2 respectively; the FAI evaporation temperature is 200 ℃, the MAI evaporation temperature is 120 ℃, the PbI2 evaporation temperature is 400 ℃, the temperature of the substrate material is 30 ℃, and the thickness of the perovskite absorption layer is 400 nm.
Depositing an electron transport layer on the deposited perovskite absorption layer, wherein the material is tin oxide SnO2The deposition method isAtomic Layer Deposition (ALD). The film thickness was 30 nm.
And depositing a front transparent conductive layer on the deposited hole transport layer, wherein the material is Indium Tin Oxide (ITO). The deposition method is Reactive Plasma Deposition (RPD). The deposited film thickness was 80 nm.
And preparing silver grid lines on the deposited front electrode transparent conductive layer by screen printing, wherein the height of the silver grid lines is 20 micrometers, the width of the silver grid lines is 50 micrometers, and the distance between the silver grid lines is 2 millimeters.
And preparing silver grid lines on the deposited back electrode transparent conductive layer by screen printing, wherein the height of the silver grid lines is 20 micrometers, the width of the silver grid lines is 50 micrometers, and the distance between the silver grid lines is 1.5 millimeters.
And finishing the preparation of the whole laminated solar cell, wherein the silver grid line on one side of the perovskite solar cell is the cathode of the cell, and the silver grid line on the side of the SHJ cell is the anode of the cell.
And (3) performance testing:
the performance of the tandem solar cells of examples 1 to 3 and comparative examples 1 to 3 was tested to obtain the data in table 1.
TABLE 1 test data for the tandem solar cells of examples 1-3 and comparative examples 1-3
Figure BDA0002477013220000161
Comparing the tandem solar cells of examples 1 to 3 with the tandem solar cells of comparative examples 1 to 3, it can be seen that the efficiency, the open-circuit voltage, the short-circuit current density, and the fill factor of the tandem solar cells of examples 1 to 3 are higher than those of the tandem solar cells of comparative examples 1 to 3. This shows that the tandem solar cells of examples 1-3 have good performance and can be produced at low temperature and on a large scale.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. A method for manufacturing a hole transport layer for a perovskite/silicon-based heterojunction tandem solar cell, the method comprising the steps of:
forming a protective layer on the substrate by adopting an atomic layer deposition technology; and
and forming a metal oxide layer on the protective layer by adopting a magnetron sputtering technology to obtain a hole transport layer.
2. The method for manufacturing a hole transport layer according to claim 1, wherein in the step of forming a metal oxide layer on the protective layer by using a magnetron sputtering technique, a sputtering gas is argon gas or a mixed gas of argon gas and oxygen gas; in the mixed gas of argon and oxygen, the volume fraction of oxygen is 0.01-30%.
3. The hole transport layer obtained by the manufacturing method 1 or 2 is used for a perovskite/silicon-based heterojunction laminated solar cell, and is characterized by comprising a protective layer and a metal oxide layer which are laminated.
4. The hole transport layer according to claim 3, wherein the material of the protective layer is at least one selected from the group consisting of nickel oxide, lithium cobaltate, copper oxide, vanadium oxide, chromium oxide, and molybdenum oxide.
5. The hole transport layer according to claim 3 or 4, wherein the protective layer has a thickness of 1nm to 20 nm.
6. The hole transport layer of claim 3, wherein the material of the metal oxide layer is at least one selected from the group consisting of nickel oxide, lithium cobaltate, copper oxide, vanadium oxide, chromium oxide, and molybdenum oxide.
7. The hole transport layer according to claim 3 or 6, wherein the metal oxide layer has a thickness of 1nm to 200 nm.
8. A perovskite/silicon-based heterojunction tandem solar cell, which comprises a perovskite cell and a tunneling junction arranged on one side of the perovskite cell, wherein the perovskite cell comprises the hole transport layer as defined in any one of claims 3 to 7 or the hole transport layer obtained by the method for manufacturing the hole transport layer as defined in 1 or 2, and a protective layer of the hole transport layer is arranged between the tunneling junction and the metal oxide layer.
9. The perovskite/silicon-based heterojunction tandem solar cell of claim 8, wherein the tunneling junction is a silicon-based thin film tunneling junction.
10. A manufacturing method of a perovskite/silicon-based heterojunction tandem solar cell is characterized by comprising the manufacturing method of the hole transport layer 1 or 2.
CN202010367037.3A 2020-04-30 2020-04-30 Hole transport layer and manufacturing method thereof, perovskite/silicon-based heterojunction laminated solar cell and manufacturing method thereof Pending CN111640867A (en)

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