CN112018209B - Perovskite-silicon heterojunction laminated solar cell and manufacturing method thereof - Google Patents
Perovskite-silicon heterojunction laminated solar cell and manufacturing method thereof Download PDFInfo
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- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—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
- H01L31/04—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
- 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 at least one potential-jump barrier or surface barrier
- H01L31/072—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 at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type
- H01L31/0745—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 at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type comprising a AIVBIV heterojunction, e.g. Si/Ge, SiGe/Si or Si/SiC solar cells
- H01L31/0747—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 at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type comprising a AIVBIV heterojunction, e.g. Si/Ge, SiGe/Si or Si/SiC solar cells comprising a heterojunction of crystalline and amorphous materials, e.g. heterojunction with intrinsic thin layer or HIT® solar cells; solar cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/20—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials
- H01L31/202—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials including only elements of Group IV of the Periodic System
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a perovskite-silicon heterojunction tandem solar cell and a manufacturing method thereof, and relates to the technical field of tandem solar cells, so that a pn junction of a silicon heterojunction bottom cell and a mesoporous inorganic hole transport layer coexist. The manufacturing method of the perovskite-silicon heterojunction laminated solar cell comprises the following steps: providing a silicon heterojunction bottom cell; forming a tunneling composite layer on the silicon heterojunction bottom cell; heating the silicon heterojunction bottom battery, simultaneously spraying the inorganic hole-transport nanoparticle suspension on the tunneling composite layer by using a spraying process, and volatilizing a solvent to form a mesoporous inorganic hole-transport layer; a perovskite light absorption layer, an electron transport layer and a transparent conductive layer are formed on the mesoporous inorganic hole transport layer. The manufacturing method provided by the invention is used for manufacturing the laminated solar cell.
Description
Technical Field
The invention relates to the technical field of laminated solar cells, in particular to a perovskite-silicon heterojunction laminated solar cell and a manufacturing method thereof.
Background
In the process of manufacturing the perovskite-silicon heterojunction tandem solar cell, the perovskite cell is a top cell, and the silicon heterojunction cell is a bottom cell. The top cell and the bottom cell may be stacked by tunneling the composite layer.
The hole transport layer in the top cell may be made of an inorganic material or an organic material. In view of the problems that organic materials are easy to be stacked on the tunneling composite layer with the suede structure and have poor stability, inorganic materials become a better choice. In order to solve the problem that the hole extraction of the inorganic hole transport layer is slow, a mesoporous structure is generally formed in the inorganic hole transport layer, so that a mesoporous inorganic hole transport layer is formed. The traditional process for preparing the mesoporous inorganic hole transport layer is a sintering process, but the sintering process can damage the pn junction of the silicon heterojunction bottom cell, so that the performance of the laminated solar cell is influenced.
Disclosure of Invention
The invention aims to provide a perovskite-silicon heterojunction battery and a manufacturing method thereof, and a mesoporous inorganic hole transport layer is manufactured under the condition of ensuring the pn junction performance of a silicon heterojunction bottom battery.
In a first aspect, the present invention provides a method of fabricating a perovskite-silicon heterojunction tandem solar cell. The manufacturing method of the perovskite-silicon heterojunction laminated solar cell comprises the following steps:
providing a silicon heterojunction bottom cell;
forming a tunneling composite layer on the silicon heterojunction bottom cell;
forming a perovskite top battery on the tunneling composite layer; forming a perovskite roof battery includes the steps of:
heating the silicon heterojunction bottom battery, spraying the inorganic hole transport nanoparticle suspension on the tunneling composite layer by using a spraying process, and volatilizing a solvent to form a mesoporous inorganic hole transport layer;
a perovskite light absorption layer, an electron transport layer and a transparent conductive layer are formed on the mesoporous inorganic hole transport layer.
When the technical scheme is adopted, inorganic hole-transport nanoparticle suspension is sprayed on the heated silicon heterojunction bottom battery. At this time, the temperature of the silicon heterojunction bottom cell is transferred to the inorganic hole transport nanoparticle suspension, so that the solvent of the suspension is volatilized, and the solute (i.e. the inorganic hole transport nanoparticles) of the suspension is deposited on the tunneling composite layer on the silicon heterojunction bottom cell to form the mesoporous inorganic hole transport layer. Based on the method, the heating temperature of the silicon heterojunction bottom cell can be controlled to be lower than the tolerance temperature of the pn junction, so that the pn junction of the bottom cell is prevented from being damaged in the process of manufacturing the dielectric hole type inorganic hole transport layer. Therefore, the manufacturing method of the perovskite-silicon heterojunction tandem solar cell provided by the invention can ensure that the dielectric hole type inorganic hole transport layer and the silicon heterojunction bottom cell coexist under the condition of ensuring the performance of the dielectric hole type inorganic hole transport layer and the silicon heterojunction bottom cell, thereby improving the filling factor and the photoelectric conversion efficiency of the perovskite-silicon heterojunction tandem solar cell.
In addition, due to the characteristics of mesopores of the mesoporous inorganic hole transport layer, the mesoporous inorganic hole transport layer can have more contact areas with the perovskite light absorption layer, so that the hole extraction efficiency is improved, the electrical property of the perovskite top cell is improved, and the electrical property of the tandem solar cell is further improved.
In some possible implementations, the solvent of the inorganic hole transporting nanoparticle suspension has a boiling point lower than 100 ℃ and is heated at a temperature of 100 ℃ to 180 ℃. In this case, the solvent has a low boiling point and is relatively easily volatilized. Meanwhile, the highest heating temperature of the silicon heterojunction bottom battery is 180 ℃, and the highest heating temperature is still less than 200 ℃ of the tolerance temperature of the pn junction, so that the damage of the pn junction in the process of heating the silicon heterojunction bottom battery can be avoided, and the performance of the silicon heterojunction bottom battery can be further ensured.
In some possible implementations, the temperature of the heating is 150 ℃ to 180 ℃. At the moment, the damage of heating the silicon heterojunction bottom battery to the pn junction can be avoided, the volatilization of a solvent can be accelerated at a higher temperature, the film forming speed of the mesoporous inorganic hole transport layer is improved, and meanwhile, the heating time of the silicon heterojunction bottom battery can be reduced, so that the damage probability of the pn junction is reduced. In addition, the solvent is volatilized quickly and efficiently, so that the water content of the inorganic hole transport nanoparticles is smaller, the quality of the formed mesoporous inorganic hole transport layer is improved, and the hole transport performance is improved.
In some possible implementations, the solvent is water or alcohol. The water and the alcohol are used as solvents, so that the solvent is easy to volatilize, is nontoxic and pollution-free, and can ensure the production safety of the laminated solar cell.
In some possible implementations, the inorganic hole transporting nanoparticle suspension contains nanoparticles with a particle size of 20nm to 80nm. Considering that the size of the suede surface on the silicon heterojunction bottom battery is usually 0.3-5 μm, the particle size of the nano particles of 20-80 nm is far smaller than the size of the suede surface. When the solvent of the suspension is volatilized, the nano-particles with smaller particle sizes can be attached to the tunneling composite layer on the silicon heterojunction bottom cell. At the moment, the mesoporous inorganic hole transport layer can be formed on the silicon heterojunction bottom cell along with the shape, and further the hole transport performance can be improved while the textured light trapping structure is reserved.
In some possible implementations, the material of the nanoparticles contained in the inorganic hole transporting nanoparticle suspension is MoO x 、NiO y 、Cu 2 O、CuGaO 2 One or more of (a) or (b),wherein x =1 to 3, y =1 to 1.5.
In some possible implementations, after forming the tunneling composite layer and before forming the mesoporous inorganic hole transport layer, the method further includes: and forming a compact hole transport layer on the tunneling composite layer.
When the technical scheme is adopted, the compact hole transport layer can be in full contact with the tunneling composite layer due to the compact characteristic of the compact hole transport layer, and the compact hole transport layer also has the effect of extracting holes, so that the hole transport effect can be improved by adding the compact hole transport layer. And after the compact hole transport layer is added, the energy levels of the tunneling composite layer, the compact hole transport layer, the mesoporous inorganic hole transport layer and the perovskite light absorption layer are gradually reduced, so that the hole transport barrier can be reduced, and the loss of electrical performance is reduced.
In some possible implementations, the spray process is an ultrasonic spray process or a two-fluid spray process.
In some possible implementation manners, when the spraying process is an ultrasonic spraying process, in the ultrasonic spraying process, the ultrasonic power is 0.5W-6W, the liquid inlet speed is 0.1 mL/s-0.4 mL/s, the pressure of the driving gas source is 2 kPa-6 kPa, the distance between the nozzle and the compact hole transport layer is 22 cm-28 cm, and the moving speed of the nozzle is 8 cm/s-13 cm/s.
When the technical scheme is adopted, the ultrasonic spraying process utilizes ultrasonic oscillation to atomize the suspension, and the formed liquid particles are fine and uniform, so that the thickness of the film layer of the prepared mesoporous inorganic hole transport layer is more uniform. In addition, extra atomization pressure is not needed in the suspension atomization process, so that the liquid particles can be prevented from rebounding and splashing, the material utilization rate can be improved, and the processing cost can be reduced.
In some possible implementation manners, when the spraying process is a two-fluid spraying process, in the two-fluid spraying process, the air pressure of the nozzle is 1 bar-3 bar, the distance between the nozzle and the compact hole transport layer is 22 cm-28 cm, and the moving speed of the nozzle is 8 cm/s-13 cm/s.
When the technical scheme is adopted, the two-fluid spraying process is mature, the operation is convenient and fast, and the equipment is low in price, so that the manufacturing difficulty and the processing cost of the laminated solar cell can be reduced.
In a second aspect, the invention further provides a tandem solar cell manufactured by the method for manufacturing the perovskite-silicon heterojunction tandem solar cell.
The beneficial effects of the tandem solar cell provided by the second aspect may refer to the beneficial effects of the method for manufacturing a perovskite-silicon heterojunction tandem solar cell described in the first aspect or any possible implementation manner of the first aspect, and are not described herein again.
Drawings
The accompanying drawings, which 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 description serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 to 12 are schematic diagrams illustrating states of various stages of a process flow for manufacturing a perovskite-silicon heterojunction tandem solar cell according to an embodiment of the present invention;
fig. 13 is a schematic structural diagram of a perovskite-silicon heterojunction tandem solar cell provided by an embodiment of the invention.
Reference numerals:
101-n type crystalline silicon wafer, 102-first passivation layer, 103-second passivation layer, 104-n type amorphous silicon layer, 105-p type amorphous silicon layer, 106-first transparent conducting layer, 107-tunneling composite layer, 108-compact type hole transport layer, 109-mesoporous type inorganic hole transport layer, 110-perovskite light absorption layer, 111-electron transport layer, 112-second transparent conducting layer and 113-electrode.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects of the present invention more clearly understood, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
It will be understood that when an element is referred to as being "secured to" or "disposed on" another element, it can be directly on the other element or be indirectly on the other element. When an element is referred to as being "connected to" another element, it can be directly connected to the other element or be indirectly connected to the other element.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or to implicitly indicate the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise. The meaning of "a number" is one or more unless specifically limited otherwise.
In the description of the present invention, it should be understood that the terms "upper", "lower", "front", "rear", "left", "right", and the like indicate orientations or positional relationships based on orientations or positional relationships shown in the drawings, which are merely for convenience of description and simplification of description, and do not indicate or imply that the device or element referred to must have a particular orientation, be constructed in a particular orientation, and operate, and thus, should not be construed as limiting the present invention.
With the development of photovoltaic technology, the laminated cell is proved to be capable of effectively improving the utilization rate of sunlight. In a typical dual stack cell, the top cell is typically a wider bandgap solar cell, the bottom cell is typically a smaller bandgap solar cell, and the top and bottom cells are connected in series by a tunneling recombination layer.
Organic-inorganic hybrid perovskite solar cells are of wide interest worldwide as novel high-efficiency, low-cost solar cells. In short years, the photoelectric conversion efficiency of single-junction small-area perovskite cells rapidly rises from 3.8% in 2009 to more than 25%, and the photoelectric conversion efficiency of perovskite-silicon heterojunction laminated cells also reaches more than 29%. Compared with the traditional thin-film solar cell (copper indium gallium selenide, cadmium telluride and the like), the perovskite solar cell has the advantages of high conversion efficiency, simple preparation process, low cost and the like, so that the perovskite solar cell becomes a thin-film solar cell technology with the most industrialization prospect. By adjusting the component proportion of the precursor solution of the perovskite light absorption layer, the spectral response cut-off wavelength of the perovskite solar cell can be regulated and controlled, so that the perovskite solar cell becomes an ideal top cell of the laminated cell.
The silicon heterojunction solar cell technology has the advantages of simple process (texturing cleaning → amorphous silicon deposition → TCO deposition → silver electrode printing), low preparation temperature (less than 220 ℃), high conversion efficiency (more than 25%), symmetrical structure (capable of generating power on two sides) and the like, and is considered as a new generation cell technology after passivation of an emitter and a back local contact cell (PERC cell). The silicon heterojunction solar cell is one of the best bottom cell choices due to the advantages of high absorptivity to infrared bands, strong weak light effect and capability of matching with p-i-n.
The perovskite-silicon heterojunction laminated solar cell formed by the perovskite solar cell (top cell) and the silicon heterojunction solar cell (bottom cell) can realize the distribution and absorption of solar spectrum, and is expected to obtain the conversion efficiency of more than 30%.
In order to reduce reflection of incident light, increase an effective optical path of the incident light in the cell absorption layer, and improve photoelectric conversion efficiency of the solar cell, each functional layer of the solar cell is usually configured to be a textured structure. The silicon heterojunction bottom cell is a typical solar cell with a textured structure, and the silicon heterojunction bottom cell with the structure enables a perovskite top cell formed on the silicon heterojunction bottom cell in a conformal manner to also have the textured structure.
The hole transport layer in the perovskite top cell may be in direct contact with the silicon heterojunction bottom cell. The material of the hole transport layer may be an inorganic material or an organic material.
When the hole transport layer is manufactured using organic materials such as 2,2', 7' -tetrabromo-9, 9' -spirodi-or tri (4-iodobenzene) amine (Sprio-OMeTAD), tetra (di-p-tolylamino) spiro-9, 9' -bifluorene (Sprio-TTB), 2', 7' -tetra (diphenylamino) -9,9' -spirobifluorene (Sprio-TAD), 1,3,4, 6-O-tetraacetyl-2-O-trifluoromethanesulfonyl- β -D-mannopyranose (TATM), etc., if the hole transport layer is manufactured using an evaporation process, the organic material located at the valley position of the textured structure easily slips to the valley position due to unstable properties of the organic material, resulting in baldness at the valley position, causing accumulation of the organic material at the valley position, and easily causing a problem of internal leakage of the battery. In order to solve the problem that a hole transport layer made of an organic material has poor compatibility with a textured structure, the surface of a silicon heterojunction solar cell is generally polished. The problem that organic materials are accumulated at the valley bottom position of the textured structure can be solved by polishing the surface, but the light trapping structure is lost, so that the photoelectric conversion efficiency of the perovskite-silicon heterojunction tandem solar cell is influenced.
When the inorganic metal oxide is used for manufacturing the hole transport layer, the inorganic metal oxide has stable property, and the problem of electric leakage in the hole transport layer of the organic material can be solved. However, the hole transport layer made of the inorganic metal oxide has a low hole extraction speed, which leads to a low filling factor and a low photoelectric conversion efficiency of the perovskite-type top cell, thereby affecting the photoelectric conversion efficiency of the perovskite-silicon heterojunction tandem solar cell. On a conventional single-junction perovskite battery, in order to solve the problem that a hole transmission layer made of an inorganic material is slow in hole extraction speed, a mesoporous inorganic hole transmission layer is added on a compact inorganic hole transmission layer, so that the contact area between the inorganic hole transmission layer and a perovskite light absorption layer is increased, and the hole extraction speed is improved.
The traditional process for preparing the mesoporous inorganic hole transport layer is a sintering process. When the sintering process is adopted to manufacture the mesoporous inorganic hole transport layer, the process temperature is up to more than 400 ℃. At the moment, the mesoporous inorganic hole transport layer is sintered on the silicon heterojunction bottom cell, and the pn junction of the silicon heterojunction bottom cell can be damaged at a higher process temperature, so that the performance of the laminated solar cell is seriously influenced, and the application of the mesoporous inorganic hole transport layer on the perovskite-silicon heterojunction laminated solar cell is limited.
In order to solve the technical problem and enable the mesoporous inorganic hole transport layer to be compatible with a silicon heterojunction bottom cell of a perovskite-silicon heterojunction tandem solar cell, the embodiment of the invention provides a manufacturing method of the perovskite-silicon heterojunction tandem solar cell.
Fig. 1 to 12 are schematic diagrams illustrating various stages of a method for fabricating a perovskite-silicon heterojunction tandem solar cell according to an embodiment of the present invention. As shown in fig. 1 to 12, a method for manufacturing a perovskite-silicon heterojunction tandem solar cell provided in an embodiment of the present invention includes:
as shown in fig. 1 to 5, a silicon heterojunction bottom cell is provided. Taking an n-type silicon heterojunction bottom cell as an example, the manufacturing method thereof can be as follows.
As shown in FIG. 1, an n-type crystalline silicon wafer 101 is provided. In practical applications, the n-type crystalline silicon wafer 101 may be a commercial grade M6 silicon wafer having a resistivity of 1 Ω. Cm to 10 Ω. Cm and a thickness of 50 μ M to 200 μ M.
The n-type crystal silicon wafer 101 is sequentially subjected to polishing, texturing and cleaning to form the n-type crystal silicon wafer 101 with a textured surface. The n-type crystalline silicon wafer 101 serves as a light absorption layer of a silicon heterojunction bottom cell and converts photons into photogenerated carriers (electron-hole pairs).
As shown in fig. 2, intrinsic amorphous silicon passivation layers are deposited on both sides of an n-type crystalline silicon wafer 101 to form a first passivation layer 102 on the front side of the n-type crystalline silicon wafer 101 and a second passivation layer 103 on the back side of the n-type crystalline silicon wafer 101. The first passivation layer 102 and the second passivation layer 103 mainly function to passivate dangling bonds on the surface of the n-type crystalline silicon wafer 101.
In practical applications, the intrinsic amorphous silicon passivation layer may be fabricated by a Plasma Enhanced Chemical Vapor Deposition (PECVD) process. The thickness of the first passivation layer 102 and the second passivation layer 103 may each be 5nm to 10nm.
As shown in fig. 3, an n-type amorphous silicon layer 104 is deposited on the first passivation layer 102 to form a front field structure. In practical applications, the n-type amorphous silicon layer 104 may be formed by a PECVD process. The thickness of the n-type amorphous silicon layer 104 may be 5nm-15nm.
As shown in fig. 4, a p-type amorphous silicon layer 105 is deposited on the second passivation layer 103 to form a back emitter. In practical applications, the p-type amorphous silicon layer 105 may be fabricated by a PECVD process. The p-type amorphous silicon layer 105 may have a thickness of 5nm to 15nm.
As shown in fig. 5, a first transparent conductive layer 106 is formed on the p-type amorphous silicon layer 105. The first transparent conductive layer 106 mainly functions to collect photogenerated carriers and transfer the photogenerated carriers to the back metal electrode. Specifically, the material of the first transparent conductive layer 106 may be Indium Tin Oxide (ITO), tungsten-doped indium oxide (In) 2 O 3 W, abbreviated as IWO), indium Zinc Oxide (IZO), titanium-doped indium oxide thin film (ITIO), and the like.
In practical applications, the first transparent conductive layer 106 may be formed by a magnetron sputtering process. The thickness of the first transparent conductive layer 106 may be 70nm to 120nm.
The silicon heterojunction bottom cell is manufactured through the process steps shown in the figures 1 to 5. Because the crystalline silicon substrate has a textured structure, the functional layers of the first passivation layer 102, the second passivation layer 103, the n-type amorphous silicon layer 104, the p-type amorphous silicon layer 105 and the first transparent conductive layer 106 which are formed on the crystalline silicon substrate in a conformal manner also have textured structures.
As shown in fig. 6, a tunneling composite layer 107 is formed on the n-type amorphous silicon layer 104 to achieve tunneling composite collection of photogenerated carriers. The thickness of the tunneling composite layer 107 may be 10nm to 100nm.
The tunneling composite layer 107 may be a tunneling composite layer 107 made of transparent metal oxides such as tin-doped indium oxide (ITO), zinc-doped indium oxide (IZO), tungsten-doped indium oxide (IWO), titanium-doped indium oxide (ITIO), fluorine-doped tin oxide (FTO), and aluminum-doped zinc oxide (AZO). In practical application, the tunneling composite layer 107 can be manufactured by a magnetron sputtering process, and is simple in process, low in manufacturing cost and suitable for commercial production.
Of course, the tunneling composite layer 107 may also be a tunneling composite layer 107 made of heavily doped silicon opposite to the pn junction of the bottom cell. For example, a tunneling layer consisting essentially of a n-type doped microcrystalline silicon layer and a p-type doped microcrystalline silicon layer, wherein the p-type doped microcrystalline silicon layer is adjacent to a perovskite cell as described below and the n-type doped microcrystalline silicon layer is adjacent to a silicon heterojunction bottom cell. Specifically, the n-type doped microcrystalline silicon layer may be a phosphorus-doped microcrystalline silicon layer, and the p-type doped microcrystalline silicon layer may be a boron-doped microcrystalline silicon layer. In practical applications, the tunneling layer can be fabricated by a PECVD process. At this time, equipment and production costs are high.
Forming a perovskite cell on tunneling composite layer 107 specifically includes the steps of:
as shown in fig. 7, dense hole transport layer 108 is formed on tunnel composite layer 107. The material of the compact hole transport layer 108 may be MoO x 、NiO y 、Cu 2 O、CuGaO 2 And the like, and is not limited thereto. The thickness of the compact hole transport layer 108 may be 5nm to 50nm.
The compact hole transport layer can be in full contact with the tunneling composite layer due to the compact characteristic of the compact hole transport layer, and the compact hole transport layer also has the effect of extracting holes, so that the hole transport effect can be improved by adding the compact hole transport layer. And after the compact hole transport layer is added, the energy levels of the tunneling composite layer, the compact hole transport layer, the mesoporous inorganic hole transport layer and the perovskite light absorption layer are gradually reduced, so that the hole transport barrier can be reduced, and the loss of electrical performance is reduced.
Illustratively, when the material of the tunneling composite layer 107 is ITO (valence band energy level of-4.8eV) The material of the compact hole transport layer 108 is NiO y (valence band energy level of-5.26eV), the material of the following mesoporous inorganic hole transporting layer 109 is also NiO y (valence band energy level of-5.5eV) The perovskite light absorption layer 110 is made of FAPbIBr (valence band energy level: fapbbr)- 5.7eV) During the process, the energy level is gradually reduced from the tunneling composite layer 107 to the compact type hole transport layer 108, the mesoporous type inorganic hole transport layer 109 and the perovskite light absorption layer 110, and the energy level difference between adjacent film layers is small, so that the hole transport is facilitated.
In practical applications, the compact hole transport layer 108 can be fabricated by a magnetron sputtering process.
As shown in fig. 8, a mesoporous inorganic hole transport layer 109 is formed on the dense hole transport layer 108. The mesoporous inorganic hole transport layer 109 may be MoO x 、NiO y 、Cu 2 O、CuGaO 2 And not limited thereto.
The method for manufacturing the mesoporous inorganic hole transport layer 109 may be: and heating the silicon heterojunction bottom cell at a temperature lower than the tolerance temperature of the pn junction of the silicon heterojunction bottom cell, and spraying the inorganic hole-transport nanoparticle suspension on the compact hole-transport layer 108 above the silicon heterojunction bottom cell by using a spraying process. At this time, under heating, the temperature of the silicon heterojunction bottom cell is transferred to the inorganic hole transporting nanoparticle suspension, so that the solvent of the inorganic hole transporting nanoparticle suspension is volatilized, and the solute (inorganic hole transporting nanoparticles) of the inorganic hole transporting nanoparticle suspension is deposited on the dense hole transporting layer 108, forming the mesoporous inorganic hole transporting layer 109. Based on the above, the heating temperature of the bottom cell of the silicon heterojunction can be controlled to be lower than the tolerance temperature of the pn junction, so that the pn junction of the bottom cell is prevented from being damaged in the process of manufacturing the via-type inorganic hole transport layer 109. Therefore, the manufacturing method of the embodiment of the invention can ensure that the mesoporous inorganic hole transport layer 109 and the silicon heterojunction coexist under the condition of ensuring the performance of the two, thereby improving the filling factor and the photoelectric conversion efficiency of the perovskite-silicon heterojunction tandem solar cell.
In addition, due to the characteristics of mesopores of the mesoporous inorganic hole transport layer 109, the mesoporous inorganic hole transport layer 109 can have more contact areas with the perovskite light absorption layer 110, so that the hole extraction efficiency can be improved, the electrical property of the perovskite top cell can be improved, and the electrical property of the tandem solar cell can be further improved. The mesoporous inorganic hole transport layer 109 is made of an inorganic material and has a stable molecular structure. When the inorganic material is sprayed on the compact hole transport layer 108 by using a spraying process, the inorganic material can be uniformly deposited on the textured surface, certain stability is kept, and the problem that the organic material is accumulated at the valley bottom of the textured structure is avoided, so that the problem of internal electric leakage can be avoided, and the filling factor and the photoelectric conversion efficiency of the laminated solar cell are further improved. The inorganic material is not easily influenced by temperature, illumination and the like, and has better stability compared with an organic material, so that the tandem solar cell has better stability, and the service life of the tandem solar cell is prolonged.
In the process of spraying the inorganic hole-transporting nanoparticle suspension on the compact hole-transporting layer 108, a solvent of the inorganic hole-transporting nanoparticle suspension is used as a carrier for transporting the inorganic hole-transporting nanoparticles, the inorganic hole-transporting nanoparticles are transported to the surface of the compact hole-transporting layer under the power transportation of the spraying equipment, and then the solvent is volatilized, and the inorganic hole-transporting nanoparticles are attached to the surface of the compact hole-transporting layer 108. After the solvent of the inorganic hole transporting nanoparticle suspension sprayed on the compact hole transporting layer 108 is volatilized, that is, after the inorganic hole transporting nanoparticles are attached, the next spraying operation can be performed, so as to form the mesoporous inorganic hole transporting layer 109 with a set thickness.
The solute of the inorganic hole transporting nanoparticle suspension, i.e. the inorganic hole transporting nanoparticles, is the main constituent material for forming the mesoporous inorganic hole transporting layer 109, i.e. the material of the mesoporous inorganic hole transporting layer 109, which may be MoO x 、NiO y 、Cu 2 O、CuGaO 2 And the like.
In order to form a uniform mesoporous structure with a moderate size in the mesoporous inorganic hole transport layer 109, the particle size of the nanoparticles contained in the inorganic hole transport nanoparticle suspension may be 20nm to 80nm. Whereas the size of the textured surface on the compact hole transport layer 108 is typically 0.3 μm to 5 μm, the size of the nanoparticles of 20nm to 80nm is much smaller than the size of the textured surface. After the solvent of the suspension is volatilized, the nanoparticles with smaller particle sizes can be uniformly attached to the compact hole transport layer 108, so that the mesoporous inorganic hole transport layer 109 can be formed on the silicon heterojunction bottom cell in a shape-following manner, a perovskite top cell with a textured light trapping structure is formed, and the sunlight utilization rate is improved. Meanwhile, the nano particles are uniformly stacked to form a mesoporous inorganic hole transport layer 109 with uniform film density; a mesoporous structure with the aperture of 2nm to 50nm is formed among the accumulated nano particles, so that the surface area of the mesoporous inorganic hole transport layer 109 can be increased, the contact area between the mesoporous inorganic hole transport layer and a light absorption layer of a perovskite roof battery is increased, and the hole extraction efficiency is improved.
The solvent of the inorganic hole-transport nanoparticle suspension, as a transport carrier, needs to be volatilized in time after being sprayed on the compact hole-transport layer 108. In order to increase the volatilization rate of the solvent and further increase the manufacturing efficiency of the mesoporous inorganic hole transport layer 109, on one hand, the boiling point of the solvent for heating the inorganic hole transport nanoparticle suspension can be limited to be lower than 100 ℃, and on the other hand, the heating temperature for heating the silicon heterojunction bottom cell can be limited to be 100-180 ℃.
When the boiling point of the solvent of the inorganic hole transport nanoparticle suspension is lower than 100 ℃, the boiling point of the solvent is lower and is easy to volatilize, and the solvent can be volatilized as long as the heating temperature is ensured to be higher than 100 ℃.
In practical applications, the solvent of the inorganic hole transporting nanoparticle suspension may be water or alcohol, and is not limited thereto. When water and alcohol are used as solvents, the solvent is easy to volatilize, is nontoxic and pollution-free, and can ensure the safety of the laminated solar cell production process.
When the heating temperature for heating the silicon heterojunction bottom battery is 100-180 ℃, the volatilization of the solvent can be realized within the temperature range, the highest heating temperature is 180 ℃, and the highest heating temperature is still less than the tolerance temperature of the pn junction by 200 ℃, so that the damage of the pn junction in the process of heating the silicon heterojunction bottom battery can be avoided, and the performance of the silicon heterojunction bottom battery can be further ensured.
In order to further increase the volatilization rate of the solvent, the heating temperature of the silicon heterojunction bottom cell can be further limited to be in the range of 150-180 ℃. In this case, not only can damage to the pn junction caused by heating the silicon heterojunction bottom cell be avoided, but also volatilization of the solvent can be accelerated at a higher temperature, and the film formation rate of the mesoporous inorganic hole transport layer 109 can be increased. In addition, the solvent is volatilized quickly and efficiently, so that the water content of the inorganic hole transport nanoparticles left on the surface of the compact hole transport layer 108 is smaller, the quality of the formed mesoporous inorganic hole transport layer 109 is improved, and the hole transport performance is improved.
For example, the heating temperature of the silicon heterojunction bottom cell can be 100 ℃, 122 ℃, 130 ℃, 150 ℃, 166 ℃, 175 ℃ and 180 ℃.
In practical application, the silicon heterojunction bottom cell is heated, and the heating temperature can be realized by arranging a hot stage with a heating function, and placing the silicon heterojunction bottom cell on the hot stage, wherein the heating temperature of the silicon heterojunction bottom cell can be represented by using the temperature of the hot stage. The heating stage may be heated by an electric heating device, or may be heated by a resistance heating device, but is not limited thereto. Of course, other ways of heating the silicon heterojunction bottom cell can be adopted. For example, a silicon heterojunction bottom cell can be placed in a closed working chamber and the closed working chamber can be heated. For convenience of description, the thermal platform is used as a heat source for the silicon heterojunction bottom cell.
The thickness of the mesoporous inorganic hole transporting layer 109 may be 70nm to 150nm. For example, the mesoporous inorganic hole transporting layer 109 may have a thickness of 70nm, 85nm, 97nm, 100nm, 120nm, 130nm, or 150nm.
In practical application, the spraying process for spraying the inorganic hole-transporting nanoparticle suspension can be an ultrasonic spraying process or a two-fluid spraying process.
When the spraying process is an ultrasonic spraying process, in the ultrasonic spraying process, the ultrasonic power is 0.5W-6W, the liquid inlet speed is 0.1 mL/s-0.4 mL/s, the pressure of a driving air source is 2 kPa-6 kPa, the distance from a nozzle to the compact cavity transmission layer 108 is 22 cm-28 cm, and the moving speed of the nozzle is 8 cm/s-13 cm/s. The ultrasonic spraying process utilizes ultrasonic oscillation to atomize the suspension, and the formed liquid particles are fine and uniform, so that the thickness of the film layer of the prepared mesoporous inorganic hole transport layer 109 is more uniform. In addition, extra atomization pressure is not needed in the suspension atomization process, so that the liquid particles can be prevented from rebounding and splashing, the material utilization rate can be improved, and the processing cost can be reduced.
In specific implementation, inorganic material nanoparticles with the particle size of 20-80 nm can be selected, 1-3 mg/ml of inorganic hole transport nanoparticle suspension is prepared by using purified water, and the suspension is stirred for 1-3 h by ultrasonic waves, so that the suspension is uniformly mixed. The fabricated silicon heterojunction bottom cell is placed on a hot stage with the compact hole transport layer 108 facing upward. And setting various working parameters of ultrasonic power, liquid inlet speed, driving air source pressure, distance between a nozzle and the compact hole transport layer 108, nozzle moving speed, moving path and the like of ultrasonic spraying equipment, controlling the ultrasonic spraying equipment according to the set working parameters to spray the inorganic hole transport nanoparticle suspension onto the surface of the compact hole transport layer 108, and forming the mesoporous inorganic hole transport layer 109 with the set thickness after multilayer spraying.
When the spraying process is a two-fluid spraying process, in the two-fluid spraying process, the air pressure of the nozzle is 1 bar-3 bar, the distance between the nozzle and the compact hole transport layer 108 is 22 cm-28 cm, and the moving speed of the nozzle is 8 cm/s-13 cm/s. The two-fluid spraying process is mature, the operation is convenient and fast, the equipment is cheap, and the manufacturing difficulty and the processing cost of the laminated solar cell can be reduced.
In specific implementation, inorganic material nanoparticles with the particle size of 20-80 nm can be selected, purified water is utilized to prepare 1-3 mg/ml inorganic hole transport nanoparticle suspension, and ultrasonic stirring is carried out for 1-3 h, so that the suspension is uniformly mixed. The fabricated silicon heterojunction bottom cell is placed on a hot stage with the compact hole transport layer 108 facing upward. And setting various working parameters of the two-fluid spraying equipment, such as nozzle air pressure, distance between the nozzle and the compact hole transport layer 108, nozzle moving speed, moving path and the like, controlling the two-fluid spraying equipment according to the set working parameters to spray the inorganic hole transport nanoparticle suspension on the surface of the compact hole transport layer 108, and forming the mesoporous inorganic hole transport layer 109 with the set thickness after multi-layer spraying.
As shown in fig. 9, a perovskite light absorbing layer 110 is formed on the mesoporous inorganic hole transporting layer 109. The perovskite light absorption layer 110 has a band gap of generally about 1.6eV and is composed of a combination of one or more perovskite-structured materials. The perovskite material may have the chemical formula ABX 3 Wherein A is CH 3 NH 3 Cation, C 4 H 9 NH 3 Cationic polymerSeed, NH 2 ＝CHNH 2 One or more of cations, cs cations; b is Pb 2+ 、Sn 2+ One or a combination of both; x is I - 、Cl - 、Br - One or more of (a).
The fabrication of the perovskite light absorption layer 110 includes the following steps:
and preparing a perovskite precursor layer. Because the surface of the mesoporous inorganic hole transport layer 109 in contact with the perovskite precursor layer is of a mesoporous structure, under the capillary action of the mesoporous structure, the surface of the mesoporous inorganic hole transport layer 109 has a good adsorption effect on a solution, so that the perovskite precursor layer can be prepared by a solution method. Therefore, the perovskite precursor layer can be prepared by a solution method, and can also be prepared by a thermal evaporation method process with good shape following performance.
When the thermal evaporation process is adopted to prepare the perovskite precursor layer, the preparation process of the perovskite precursor layer comprises the following steps: lead iodide (PbI) with the thickness of 350nm to 450nm is evaporated on the mesoporous inorganic hole transport layer 109 by adopting a co-evaporation method 2 ) And cesium bromide (CsBr) at a rate of
Lead iodide (PbI) 2 ) At a rate of
Forming a perovskite precursor layer, which is also the main structure of the titanium ore absorption layer film.
When the perovskite precursor layer is prepared by a solution method, the preparation process of the perovskite precursor layer comprises the following steps: mixing lead iodide (PbI) 2 ) With cesium bromide (CsBr) at a molar ratio of 1: (0.1-0.2), and dissolving in a mixed solvent of N, N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) to prepare a precursor solution. The volume ratio of DMF to DMSO is (8-10): 1. Lead iodide (PbI) 2 ) The concentration of (2) is 1M/mL. The precursor solution is coated on the mesoporous inorganic hole transport layer 109 by methods such as spin coating, blade coating or slit coating, and then annealed for 20-50min at 60-90 ℃ after air knife treatment, so as to form the perovskite precursor layer.
And spin-coating 70-100 uL of mixed solution of formamidine hydroiodide (FAI) and formamidine hydrobromide (FABr) on the prepared perovskite precursor layer, so that the mixed solution of FAI and FABr reacts with lead iodide and cesium bromide to form a perovskite material film. The molar concentration (mol/ml) ratio of FAI to FABr may be (1.5. The solvent of the mixed solution of FAI and FABr may be ethanol or isopropanol.
The perovskite material thin film is annealed to form the perovskite light absorption layer 110. The annealing temperature can be 140-190 ℃, and the annealing time can be 20-50 min. The perovskite light absorption layer 110 is formed of a material composition of (Cs) 0.15 FA 0.85 )Pb(I 0.7 Br 0.3 ) 3 。
As shown in fig. 10, an electron transport layer 111 is formed on the perovskite light absorption layer 110 to achieve longitudinal transport of photogenerated carriers. The material of the electron transport layer 111 may be C60, [6,6 ] or]-phenyl-C61-butyric acid isopropyl ester (PCBM), snO 2 、TiO 2 And is not limited thereto.
In practical application, a C60 thin film layer or a PCBM thin film layer is prepared on the perovskite light absorption layer 110 as an electron transmission interface layer by adopting an evaporation process, and then the cycle is carried out for 130 to 190 times by utilizing an atomic layer deposition process (ALD) at the temperature of between 80 and 120 ℃, wherein the prepared material is SnO 2 Or TiO 2 The electron transport layer 111. The thickness of the electron transport layer 111 may be 10nm to 20nm. It will be appreciated that in practice, the electron-transporting interface layer may also be omitted.
As shown in fig. 11, a second transparent conductive layer 112 is formed on the electron transport layer 111 for the purpose of transporting electrons laterally to the electrodes and reducing optical reflection. The material, thickness and preparation method of the second transparent conductive layer 112 can refer to the first transparent conductive layer 106, and will not be described again.
It should be noted that a surface antireflection film layer may be added on the second transparent conductive layer 112, and an antireflection film (such as MgF) with a thickness of 70nm to 120nm is prepared by electron beam evaporation 2 And silicon nitride SiN x Etc.) toThe photoelectric conversion efficiency of the laminated solar cell is improved. The material of the antireflection film may be magnesium fluoride (MgF) 2 ) Or silicon nitride (SiN) x ) Etc., and are not limited thereto.
As shown in fig. 12, an electrode 113 is formed on the first transparent conductive layer 106 and the second transparent conductive layer 112 to collect current. In practical applications, the fine gate lines and the main gate lines of the electrode 113 may be manufactured by screen printing or mask evaporation. The electrode 113 may be made of a metal having a good conductivity, such as silver, copper, or aluminum.
As shown in fig. 13, embodiments of the present invention also provide a perovskite-silicon heterojunction tandem solar cell. The perovskite-silicon heterojunction tandem solar cell is obtained by adopting the manufacturing method of the perovskite-silicon heterojunction tandem solar cell.
The perovskite-silicon heterojunction laminated solar cell provided by the embodiment of the invention has the same beneficial effect as that of the manufacturing method of the perovskite-silicon heterojunction laminated solar cell.
In order to verify the performance of the perovskite-silicon heterojunction tandem solar cell manufactured by the method for manufacturing a perovskite-silicon heterojunction tandem solar cell provided by the embodiment of the invention, the following description will be made in a manner of comparing the embodiment with a comparative example.
Example one
The embodiment of the invention provides a manufacturing method of a perovskite-n type silicon heterojunction tandem solar cell, which comprises the following specific steps:
firstly, providing an n-type M6 silicon wafer with the resistivity of 5 omega-cm and the thickness of 180 mu M. And carrying out polishing, texturing and cleaning treatment on the silicon wafer to form an n-type monocrystalline silicon substrate with a textured surface.
And secondly, depositing intrinsic amorphous silicon passivation layers (with the thickness of 8 nm) on two sides of the n-type monocrystalline silicon substrate by using PECVD equipment to form a first passivation layer positioned on the front side of the n-type monocrystalline silicon substrate and a second passivation layer positioned on the back side of the n-type monocrystalline silicon substrate.
Thirdly, depositing phosphorus doping (doping concentration 10) on the first passivation layer by using PECVD equipment 19 cm -3 ) N-type amorphous silicon layer (thick)Degree 10 nm) to form a top field structure.
Fourthly, depositing boron doping (with the doping concentration of 10) on the second passivation layer by utilizing PECVD equipment 19 cm -3 ) A p-type amorphous silicon layer (thickness 10 nm) forming a back emitter.
And fifthly, preparing a first transparent conducting layer (with the thickness of 110 nm) made of an ITO material on the p-type amorphous silicon layer by adopting a magnetron sputtering process.
And sixthly, forming a tunneling composite layer (with the thickness of 50 nm) made of an ITO material on the n-type amorphous silicon layer by adopting a magnetron sputtering process.
Seventhly, forming NiO on the tunneling composite layer by adopting a magnetron sputtering process y A dense hole transport layer (thickness 30 nm) of material.
Eighth step, niO with particle size of 50nm is selected y And (3) preparing 2mg/ml of inorganic hole-transporting nanoparticle suspension by using purified water, and stirring for 2 hours by using ultrasonic waves to uniformly mix the suspension. And (3) placing the manufactured silicon heterojunction bottom battery on a hot table at 150 ℃, and enabling the compact hole transport layer to face upwards. The ultrasonic power of ultrasonic spraying equipment is set to be 4W, the liquid inlet speed is set to be 0.2mL/s, the pressure of a driving gas source is set to be 4KPa, the distance between a nozzle and a compact hole transport layer is set to be 25cm, and the moving speed of the nozzle is set to be 10cm/s.
And controlling ultrasonic spraying equipment according to set working parameters to spray the inorganic hole-transport nanoparticle suspension on the surface of the compact hole-transport layer to form a mesoporous inorganic hole-transport layer with the thickness of 100nm.
Ninthly, adopting a co-evaporation method to form lead iodide and cesium bromide on the mesoporous inorganic hole transport layer, wherein the rate of the cesium bromide (CsBr) is
Lead iodide (PbI) 2 ) At a rate of
The total thickness is 400nm.
Preparing a mixed solution of FAI and FABr, wherein the molar concentration ratio of FAI to FABr is 1. And (3) coating 80 mu L of mixed solution of FAI and FABr on the lead iodide and cesium bromide layers in a spinning mode, and reacting to form the perovskite material film.
Annealing the perovskite material film for 30min at the temperature of 150 ℃ to form a compact and uniform perovskite light absorption layer.
Tenth, preparing a C60 thin film layer on the perovskite light absorption layer by adopting an evaporation process, and then performing 160 cycles by utilizing an Atomic Layer Deposition (ALD) process at the temperature of 100 ℃, wherein the preparation material is SnO 2 The electron transport layer of (1). The thickness of the electron transport layer may be 15nm.
And eleventh, forming a second transparent conductive layer (with the thickness of 110 nm) made of an ITO material on the electron transmission layer by adopting a magnetron sputtering process.
And a twelfth step of forming silver electrodes on the first transparent conductive layer and the second transparent conductive layer by using a screen printing process.
Example two
The embodiment of the invention provides a manufacturing method of a perovskite-n type silicon heterojunction laminated solar cell, which comprises the following steps:
firstly, providing an n-type M6 silicon wafer with the resistivity of 8 omega cm and the thickness of 100 mu M. And carrying out polishing, texturing and cleaning treatment on the silicon wafer to form an n-type monocrystalline silicon substrate with a textured surface.
And secondly, depositing intrinsic amorphous silicon passivation layers (with the thickness of 6 nm) on the two sides of the n-type monocrystalline silicon substrate by using PECVD equipment to form a first passivation layer positioned on the front side of the n-type monocrystalline silicon substrate and a second passivation layer positioned on the back side of the n-type monocrystalline silicon substrate.
Thirdly, depositing phosphorus doping (doping concentration 10) on the first passivation layer by utilizing PECVD equipment 20 cm -3 ) The n-type microcrystalline silicon layer (thickness 8 nm) formed a front field structure.
Fourthly, depositing boron doping (with the doping concentration of 10) on the second passivation layer by utilizing PECVD equipment 20 cm -3 ) A p-type microcrystalline silicon layer (thickness 8 nm) to form a back emission stage.
And fifthly, preparing a first transparent conducting layer (with the thickness of 110 nm) made of IWO material on the p-type amorphous silicon layer by adopting a magnetron sputtering process.
And sixthly, forming a tunneling composite layer (with the thickness of 60 nm) made of an ITO material on the n-type amorphous silicon layer by adopting a magnetron sputtering process.
Seventhly, forming MoO on the tunneling composite layer by adopting an electron beam evaporation process x A dense hole transport layer (thickness 20 nm) of the material.
Eighthly, selecting MoO with the particle size of 80nm x And (3) preparing an inorganic hole-transporting nanoparticle suspension of 3mg/ml by using ethanol, and stirring for 1.5 hours by using ultrasonic waves to uniformly mix the suspension. The prepared silicon heterojunction bottom cell is placed on a hot bench at 175 ℃, and the compact hole transport layer faces upwards. The air pressure of the two-fluid spraying equipment is set to be 2bar, the distance between the nozzle and the compact hole transport layer is 26cm, and the moving speed of the nozzle is 11cm/s.
And controlling two-fluid spraying equipment according to the set working parameters to spray the inorganic hole-transporting nanoparticle suspension on the surface of the compact hole-transporting layer to form a mesoporous inorganic hole-transporting layer with the thickness of 120nm.
Ninth, lead iodide (PbI) 2 ) With cesium bromide (CsBr) at a molar ratio of 1:0.5, and dissolving the mixture in a mixed solvent of DMF and DMSO with a volume ratio of 9. The precursor solution is coated on the mesoporous inorganic hole transport layer by a spin coating method, and is annealed for 30min at the temperature of 80 ℃ after being treated by an air knife to form a perovskite precursor layer.
Preparing a mixed solution of FAI and FABr, wherein the molar concentration ratio of FAI to FABr is 2.5. And (3) taking 90 mu L of mixed solution of FAI and FABr to be coated on the lead iodide and cesium bromide layers in a spinning mode and react to form the perovskite material film.
Annealing the perovskite material film for 40min at the temperature of 160 ℃ to form a compact and uniform perovskite light absorption layer.
Tenth, preparing a PCBM thin film layer on the perovskite light absorption layer by adopting an evaporation process, and then performing 150 cycles by utilizing an Atomic Layer Deposition (ALD) process at 90 ℃ to prepare the TiO material 2 The electron transport layer of (1). The thickness of the electron transport layer may be 18nm.
And eleventh, forming a second transparent conductive layer (with the thickness of 110 nm) made of an ITO material on the electron transmission layer by adopting a magnetron sputtering process.
And a twelfth step of forming silver electrodes on the first transparent conductive layer and the second transparent conductive layer by a screen printing process.
EXAMPLE III
The embodiment of the invention provides a manufacturing method of a perovskite-n type silicon heterojunction laminated solar cell, which comprises the following steps:
in the first step, an n-type M6 silicon wafer with the resistivity of 4 omega cm and the thickness of 50 mu M is provided. And polishing, texturing and cleaning the silicon wafer to form the n-type monocrystalline silicon substrate with the textured surface.
And secondly, depositing intrinsic amorphous silicon passivation layers (with the thickness of 5 nm) on two sides of the n-type monocrystalline silicon substrate by using PECVD equipment to form a first passivation layer positioned on the front side of the n-type monocrystalline silicon substrate and a second passivation layer positioned on the back side of the n-type monocrystalline silicon substrate.
Thirdly, depositing phosphorus doping (doping concentration 10) on the first passivation layer by using PECVD equipment 20 cm -3 ) The n-type microcrystalline silicon layer (thickness 5 nm) formed a front field structure.
Fourthly, depositing boron doping (with the doping concentration of 10) on the second passivation layer by utilizing PECVD equipment 20 cm -3 ) A p-type microcrystalline silicon layer (thickness 5 nm) to form a back emission stage.
And fifthly, preparing a first transparent conducting layer (with the thickness of 110 nm) made of an ITiO material on the p-type amorphous silicon layer by adopting a magnetron sputtering process.
And sixthly, forming a tunneling composite layer (with the thickness of 50 nm) made of heavily doped silicon opposite to the pn junction of the bottom cell on the n-type amorphous silicon layer by adopting a magnetron sputtering process.
Seventhly, forming NiO on the tunneling composite layer by adopting a magnetron sputtering process y A dense hole transport layer (thickness 30 nm) of the material.
Eighthly, selecting CuGaO with the grain diameter of 70nm 2 And (3) preparing an inorganic hole transport nanoparticle suspension of 3mg/ml by using purified water, and stirring for 1 hour by using ultrasonic waves to uniformly mix the suspension. Silicon heterojunction bottom to be fabricatedThe cell was placed on a 100 ℃ hot plate with the dense hole transport layer facing up. Setting the air pressure of the two-fluid spraying equipment to be 1bar, the distance between the nozzle and the compact hole transport layer to be 22cm, and the moving speed of the nozzle to be 8cm/s.
And controlling two-fluid spraying equipment according to the set working parameters to spray the inorganic hole-transporting nanoparticle suspension on the surface of the compact hole-transporting layer to form a mesoporous inorganic hole-transporting layer with the thickness of 70 nm.
Ninth, lead iodide and cesium bromide are formed on the mesoporous inorganic hole transport layer by a co-evaporation method, wherein the rate of the cesium bromide (CsBr) is
Lead iodide (PbI) 2 ) At a rate of
The total thickness is 350nm.
Preparing a mixed solution of FAI and FABr, wherein the molar concentration ratio of FAI to FABr is 1.5. 70 mu L of mixed solution of FAI and FABr is taken to be coated on the lead iodide and cesium bromide layer in a spinning way and reacts to form the perovskite material film.
And annealing the perovskite material film for 20min at the temperature of 140 ℃ to form a compact and uniform perovskite light absorption layer.
Tenth, preparing a PCBM thin film layer on the perovskite light absorption layer by adopting an evaporation process, and then performing 130 cycles by utilizing an Atomic Layer Deposition (ALD) process at the temperature of 80 ℃ to prepare the TiO material 2 The electron transport layer of (3). The thickness of the electron transport layer may be 10nm.
And eleventh, forming a second transparent conductive layer (with the thickness of 110 nm) made of an ITO material on the electron transmission layer by adopting a magnetron sputtering process.
And a twelfth step of forming silver electrodes on the first transparent conductive layer and the second transparent conductive layer by a screen printing process.
Example four
The embodiment of the invention provides a manufacturing method of a perovskite-n type silicon heterojunction tandem solar cell, which comprises the following specific steps:
in the first step, an n-type M6 silicon wafer with the resistivity of 10 omega cm and the thickness of 200 mu M is provided. And carrying out polishing, texturing and cleaning treatment on the silicon wafer to form an n-type monocrystalline silicon substrate with a textured surface.
And secondly, depositing intrinsic amorphous silicon passivation layers (with the thickness of 10 nm) on the two sides of the n-type monocrystalline silicon substrate by using PECVD equipment to form a first passivation layer positioned on the front side of the n-type monocrystalline silicon substrate and a second passivation layer positioned on the back side of the n-type monocrystalline silicon substrate.
Thirdly, depositing phosphorus doping (doping concentration 10) on the first passivation layer by using PECVD equipment 19 cm -3 ) Forming a front field structure on the n-type amorphous silicon layer (thickness 15 nm).
Fourthly, using PECVD equipment to deposit boron doping (with the doping concentration of 10) on the second passivation layer 19 cm -3 ) A p-type amorphous silicon layer (thickness 15 nm) forming a back emitter.
And fifthly, preparing a first transparent conducting layer (with the thickness of 110 nm) made of an ITO material on the p-type amorphous silicon layer by adopting a magnetron sputtering process.
And sixthly, forming a tunneling composite layer (with the thickness of 10 nm) made of an ITO material on the n-type amorphous silicon layer by adopting a magnetron sputtering process.
Seventhly, forming Cu on the tunneling composite layer by adopting a magnetron sputtering process 2 A dense hole transport layer (50 nm thick) of O material.
And eighthly, selecting NiOy nanoparticles with the particle size of 60nm, preparing 3mg/ml inorganic hole transport nanoparticle suspension by using purified water, and stirring for 3 hours by using ultrasonic waves to uniformly mix the suspension. And placing the prepared silicon heterojunction bottom cell on a hot bench at 180 ℃ and enabling the compact hole transport layer to face upwards. The ultrasonic power of ultrasonic spraying equipment is set to be 6W, the liquid inlet speed is set to be 0.4mL/s, the pressure of a driving gas source is set to be 6KPa, the distance between a nozzle and a compact hole transport layer is set to be 28cm, and the moving speed of the nozzle is set to be 13cm/s.
And controlling ultrasonic spraying equipment according to set working parameters to spray the inorganic hole-transport nanoparticle suspension on the surface of the compact hole-transport layer to form a 150 nm-thick mesoporous inorganic hole-transport layer.
Ninth, lead iodide and cesium bromide are formed on the mesoporous inorganic hole transport layer by a co-evaporation method, wherein the rate of the cesium bromide (CsBr) is
Lead iodide (PbI) 2 ) At a rate of
The total thickness is 450nm.
Preparing a mixed solution of FAI and FABr, wherein the molar concentration ratio of FAI to FABr is 3.5. And (3) coating 100 mu L of mixed solution of FAI and FABr on the lead iodide and cesium bromide layers in a spinning mode, and reacting to form the perovskite material film.
Annealing the perovskite material film for 50min at the temperature of 190 ℃ to form a compact and uniform perovskite light absorption layer.
Tenth, preparing a C60 thin film layer on the perovskite light absorption layer by adopting an evaporation process, and then performing 190 cycles by utilizing an Atomic Layer Deposition (ALD) process at 120 ℃, wherein the preparation material is SnO 2 The electron transport layer of (3). The thickness of the electron transport layer may be 20nm.
And eleventh, forming a second transparent conductive layer (with the thickness of 119 nm) made of an ITO material on the electron transmission layer by adopting a magnetron sputtering process.
And a twelfth step of forming silver electrodes on the first transparent conductive layer and the second transparent conductive layer by using a screen printing process.
In order to verify the performance of the tandem solar cell, the photoelectric conversion efficiency, the fill factor, the open-circuit voltage, the short-circuit current, and other performance parameters of the devices prepared in example one, example two, example three, and example four were tested, and the performance parameters are compared in table 1.
Table 1 tabulated performance of perovskite-silicon heterojunction tandem solar cells provided by embodiments of the present invention
As can be seen from table 1, the perovskite-silicon heterojunction tandem solar cell provided by the embodiment of the invention has higher conversion efficiency compared with the conventional 23% conversion efficiency. Therefore, the perovskite-silicon heterojunction tandem solar cell manufactured by the manufacturing method provided by the embodiment of the invention can obviously improve the filling factor and the conversion efficiency.
In the foregoing description of embodiments, the particular features, structures, materials, or characteristics may be combined in any suitable manner in any one or more embodiments or examples.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (9)
1. A manufacturing method of a perovskite-silicon heterojunction tandem solar cell is characterized by comprising the following steps:
providing a silicon heterojunction bottom cell;
forming a tunneling composite layer on the silicon heterojunction bottom cell;
forming a perovskite top battery on the tunneling composite layer;
the method of forming a perovskite roof battery includes the steps of:
forming a compact hole transport layer on the tunneling composite layer;
heating the silicon heterojunction bottom battery at a temperature lower than the tolerance temperature of a pn junction of the silicon heterojunction bottom battery, simultaneously spraying an inorganic hole-transport nanoparticle suspension on the compact hole-transport layer by using a spraying process, spraying the next layer of inorganic hole-transport nanoparticle suspension after the solvent of one layer of inorganic hole-transport nanoparticle suspension sprayed on the compact hole-transport layer is volatilized, and volatilizing the solvent to form a mesoporous inorganic hole-transport layer; and forming a perovskite light absorption layer, an electron transport layer and a transparent conducting layer on the mesoporous inorganic hole transport layer.
2. The method for fabricating a perovskite-silicon heterojunction stack solar cell according to claim 1, wherein the boiling point of the solvent of the inorganic hole transporting nanoparticle suspension is lower than 100 ℃ and the heating temperature is 100 ℃ to 180 ℃.
3. The method of fabricating a perovskite-silicon heterojunction tandem solar cell as claimed in claim 2, wherein the heating temperature is 150 ℃ to 180 ℃.
4. The method according to claim 2, wherein the solvent is water or alcohol.
5. The method for fabricating the perovskite-silicon heterojunction tandem solar cell as claimed in any one of claims 1 to 4, wherein the inorganic hole transporting nanoparticle suspension contains nanoparticles with a particle size of 20nm to 80nm.
6. The method for manufacturing a perovskite-silicon heterojunction tandem solar cell according to any one of claims 1 to 4, wherein the material of the nanoparticles contained in the inorganic hole-transporting nanoparticle suspension is MoO x 、NiO y 、Cu 2 O、CuGaO 2 Wherein x =1 to 3, y =1 to 1.5.
7. The method for fabricating a perovskite-silicon heterojunction tandem solar cell according to any one of claims 1 to 4, wherein the spray coating process is an ultrasonic spray coating process or a two-fluid spray coating process.
8. The method for manufacturing the perovskite-silicon heterojunction tandem solar cell according to claim 7, wherein when the spraying process is an ultrasonic spraying process, the ultrasonic power is 0.5W to 6W, the liquid inlet speed is 0.1mL/s to 0.4mL/s, the driving gas source pressure is 2kPa to 6kPa, the distance between the nozzle and the compact hole transport layer is 22cm to 28cm, the nozzle moving speed is 8cm/s to 13cm/s, and/or,
when the spraying process is a two-fluid spraying process, in the two-fluid spraying process, the air pressure of a nozzle is 1 bar-3 bar, the distance between the nozzle and the compact hole transport layer is 22 cm-28 cm, and the moving speed of the nozzle is 8 cm/s-13 cm/s.
9. A perovskite-silicon heterojunction tandem solar cell manufactured by the method for manufacturing a perovskite-silicon heterojunction tandem solar cell according to any one of claims 1 to 8.
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