Perovskite crystalline silicon laminated solar cell based on graphical connection

Abstract

The utility model discloses a perovskite crystalline silicon laminated solar cell based on graphical connection, which comprises a hole transport layer and a graphical N-type substrate doping layer electrically connected with the hole transport layer, and a graphical unit is arranged on one end face, connected with the hole transport layer, of the graphical N-type substrate doping layer. The patterning unit is used for increasing the connection contact area and the connection stability of the hole transmission layer and the patterning N-type substrate doping layer, and through the arrangement, the patterning unit is arranged on the patterning N-type substrate doping layer, so that the hole transmission layer is in compact contact with the patterning unit of the N-type substrate doping layer, and the hole transmission layer and the patterning unit of the N-type substrate doping layer are in compact contact. Meanwhile, the interface contact area is increased, so that the top cell and the bottom cell in the lamination are efficiently connected, meanwhile, the graphical structure also increases the adhesive force between the film layers, and the stability of the lamination cell is improved.

Description

Technical Field

[0001] The utility model relates to the technical field of perovskite thin films and perovskite stacked solar cells, in particular to a perovskite crystalline silicon stacked solar cell based on graphic connection. Background Art

[0002] Solar energy is a highly anticipated clean energy source with the advantages of abundant resources and low cost. Currently, photovoltaic cells are one of the most effective ways to convert solar energy into electrical energy. Among them, solar cells such as monocrystalline silicon and polycrystalline silicon have relatively mature industrialization technologies.

[0003] In recent years, perovskite / crystalline silicon stacking technology has become a research hotspot in the field of photovoltaic technology and has attracted widespread attention. The development of this technology is of great significance for improving the photoelectric conversion efficiency of solar cells and reducing manufacturing costs, thereby promoting the further development and application of solar power generation technology. The theoretical effective photoelectric conversion efficiency of crystalline silicon / perovskite stacked solar cells is as high as 40%, far exceeding that of crystalline silicon solar cells. The basic principle of this technology is to stack perovskite materials and crystalline silicon materials together to form a heterojunction. The wide band gap, high absorption coefficient and high carrier mobility of perovskite materials and the stability and good electron transmission performance of crystalline silicon materials can improve the photoelectric conversion efficiency of solar cells. At present, the photoelectric conversion efficiency of crystalline silicon / perovskite stacked solar cells has reached more than 33%, but there is still a gap with the theoretical value, so there is still a lot of room for improvement. At present, it is generally believed in the industry that optimizing the device structure of the stack is the key direction to continue to improve the efficiency of stacked solar cells.

[0004] At present, crystalline silicon / perovskite tandem solar cells often use a fully covered transparent conductive oxide film as the middle tunneling layer. The thickness of this layer is usually around 10-100nm, and its light transmittance for 300-1200nm is usually below 90%, which causes the device to lose light absorption. On the other hand, efficient crystalline silicon / perovskite tandem solar cells require that the middle tunneling layer has good longitudinal conductivity rather than lateral conductivity. The fully covered middle tunneling layer can conduct electrons and holes laterally, and this characteristic will cause certain non-recombination losses, thereby reducing the efficiency of the device.

[0005] If the tunneling layer is eliminated and the hole transport layer of the top cell is directly in contact with the N-type doped layer in the crystalline silicon bottom cell, large recombination losses and contact resistance will be generated, thus affecting the device performance. This is because the perovskite hole transport layer widely used in the stack is generally a nickel oxide or organic small molecule film layer prepared by sputtering or spin coating. This film layer can make the perovskite top cell have efficient device performance, but it cannot form a good ohmic contact and dense interface with the N-type doped layer in the bottom cell, and cannot play the role of efficiently connecting the top cell and the bottom cell in the stack. At the same time, this structure also has the disadvantage of weak film adhesion, which makes the top and bottom cells of the stacked device easy to detach during long-term operation, and the stability is poor. Utility Model Content

[0006] The purpose of the utility model is to address the technical problems existing in the background technology and to propose a perovskite crystalline silicon stacked solar cell based on patterned connection, including a hole transport layer and a patterned N-type base doping layer electrically connected to the hole transport layer, wherein the patterned N-type base doping layer is provided with a patterned unit on one end face connected to the hole transport layer, and the patterned unit is used to increase the contact area between the hole transport layer and the patterned N-type base doping layer.

[0007] Furthermore, a plurality of grooves are formed on the patterned N-type base doping layer, and the patterned units are formed by the plurality of grooves.

[0008] Furthermore, the groove width is 0-50 um, the depth is 0-80 nm, the grooves are arranged in a grid shape on the patterned N-type base doping layer, and the grid side length is 0-100 mm.

[0009] Furthermore, a plurality of connection parts are provided on a protrusion of one end surface of the hole transport layer connected to the patterned N-type base doping layer, and the connection parts are electrically connected to the scribed grooves.

[0010] Furthermore, a substrate surface passivation layer, a silicon substrate, a substrate passivation layer, a P-type substrate doping layer, a first transparent electrode layer and a first metal electrode layer are sequentially arranged below the patterned N-type substrate doping layer, and a perovskite absorption layer, a passivation layer, an electron transport layer, a buffer layer, a second transparent electrode layer, a second metal electrode layer and an anti-reflection layer are sequentially arranged above the hole transport layer.

[0011] Furthermore, the chemical formula of the perovskite material of the perovskite absorber layer is ABX 3 , wherein A is a cation, including one of methylammonium, formamide, Cs, and Rb; B is a metal cation, including Pb; and X is a halide anion, including one of Br, Cl, and I.

[0012] Further, the passivation layer is one of propylenediamine iodide, propylenediamine bromide, butylammonium chloride, butylammonium bromide, butylammonium iodide, N,N-dimethyl-1,3-propylenediamine hydrochloride, dodecanediamine bromide, magnesium fluoride, lithium fluoride, and sodium fluoride;

[0013] The electron transport layer is one of zinc oxide, tin dioxide, titanium dioxide, [6,6]-phenyl C61 butyric acid methyl ester, carbon 60, and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline;

[0014] The buffer layer is one of zinc oxide, tin dioxide and titanium dioxide;

[0015] The first transparent electrode layer and the second transparent electrode layer are one of indium tin oxide, indium zinc oxide, and zinc aluminum oxide;

[0016] The second metal electrode layer is one of silver, gold, copper, aluminum, and carbon;

[0017] The anti-reflection layer is one of magnesium fluoride, lithium fluoride, sodium fluoride and silicon oxide;

[0018] The thickness of the hole transport layer, the perovskite absorption layer, the electron transport layer, the buffer layer, the second transparent electrode layer, the second metal electrode layer and the anti-reflection layer is 1-600nm.

[0019] Compared with the prior art, the utility model has the following beneficial technical effects: The utility model aims to provide a perovskite crystalline silicon stacked solar cell based on patterned connection, which is characterized in that by setting a patterned unit (patterned structure) on the patterned N-type base doping layer, the hole transport layer is in close contact with the patterned unit of the N-type base doping layer, and the interface contact area is increased, so that the top and bottom cells in the stack are efficiently connected. At the same time, the patterned structure also increases the adhesion between the film layers and improves the stability of the stacked cell. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 This is the battery structure diagram of test group 1;

[0021] Figure 2 This is the battery structure diagram of test group 2;

[0022] Figure 3 This is a structural diagram of the battery of the utility model (test group 3);

[0023] Figure 4 The top view and the side view of the patterned N-type base doping layer. DETAILED DESCRIPTION

[0024] It should be noted that, in the absence of conflict, the embodiments of the present invention and the features in the embodiments can be combined with each other.

[0025] In the description of the present utility model, it should be understood that the terms "center", "longitudinal", "lateral", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside" and the like indicate positions or positional relationships based on the positions or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present utility model and simplifying the description, rather than indicating or implying that the device or component referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation on the present utility model. In addition, the terms "first", "second", etc. are only used for descriptive purposes, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Therefore, features defined as "first", "second", etc. may explicitly or implicitly include one or more features. In the description of the present utility model, unless otherwise specified, "multiple" means two or more.

[0026] In the description of the present invention, it should be noted that, unless otherwise clearly specified and limited, the terms "installation", "connection" and "connection" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or a specific connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium, or it can be the internal communication of two components. For ordinary technicians in this field, the specific meanings of the above terms in the present invention can be understood by specific circumstances.

[0027] The specific embodiments of the present utility model are described in detail below with reference to the accompanying drawings.

[0028] like Figure 1-Figure 4 As shown, the utility model proposes a perovskite crystalline silicon stacked solar cell based on patterned connection, including a hole transport layer 210 and a patterned N-type base doping layer 116 electrically connected to the hole transport layer 210, and an end surface of the patterned N-type base doping layer 116 connected to the hole transport layer 210 is provided with a patterned unit 116a, and the patterned unit 116a is used to increase the connection contact area and connection stability between the hole transport layer 210 and the patterned N-type base doping layer 116.

[0029] It can be understood that the utility model provides a patterned unit on the patterned N-type base doping layer, so that the hole transport layer is in close contact with the patterned unit of the N-type base doping layer, and the interface contact area is increased, so that the top and bottom cells in the stack are efficiently connected. At the same time, the patterned structure also increases the adhesion between the film layers and improves the stability of the stacked battery.

[0030] Furthermore, in the present embodiment, a plurality of grooves 116b are provided on the patterned N-type base doping layer 116, and the plurality of grooves 116b are used to form a patterned unit 116a. Specifically, the groove 116b has a width of 0-50um and a depth of 0-80nm. The grooves 116b are arranged in a grid shape on the patterned N-type base doping layer 116, and the grid side length is 0-100mm. Furthermore, the hole transport layer 210 is provided with a plurality of connecting portions 210a on one end surface protrusion connected to the patterned N-type base doping layer 116, and the connecting portion 210a is electrically connected to the groove 116b.

[0031] It can be understood that the utility model provides a plurality of grooves 116b and a plurality of connecting portions 210a matching the grooves 116b. When the hole transport layer 210 is electrically connected to the patterned N-type base doping layer 116, the dense connection between the connecting portions 210a and the grooves 116b increases the contact area between the hole transport layer 210 and the patterned N-type base doping layer 116, thereby increasing the adhesion between the film layers.

[0032] Furthermore, in the present embodiment, a substrate surface passivation layer 115, a silicon substrate 114, a substrate passivation layer 113, a P-type substrate doping layer 112, a first transparent electrode layer 111 and a first metal electrode layer 110 are sequentially arranged below the patterned N-type substrate doping layer 116, and a perovskite absorption layer 211, a passivation layer 212, an electron transport layer 213, a buffer layer 214, a second transparent electrode layer 215, a second metal electrode layer 216 and an anti-reflection layer 217 are sequentially arranged above the hole transport layer 210.

[0033] Furthermore, this embodiment also provides a method for preparing a perovskite crystalline silicon tandem solar cell based on patterned connection, comprising the following steps:

[0034] Prepare a base passivation layer 113 on the back side of the silicon substrate 114;

[0035] Prepare a P-type base doping layer 112 on the surface of the base passivation layer 113;

[0036] Prepare a first transparent electrode layer 111 on the surface of the P-type base doping layer 112;

[0037] Prepare a first metal electrode layer 110 on the surface of the first transparent electrode layer 111;

[0038] Prepare a substrate surface passivation layer 115 on the surface of the silicon substrate 114;

[0039] A patterned N-type substrate doping layer 116 is prepared on the surface of the substrate surface passivation layer 115;

[0040] Performing patterned etching on the patterned N-type base doping layer 116 to form a patterned unit 116a;

[0041] Prepare a hole transport layer 210 on the surface of the patterned N-type base doping layer 116;

[0042] A perovskite absorption layer 211 is formed on the surface of the hole transport layer 210;

[0043] A passivation layer 212 is prepared on the perovskite absorption layer 211;

[0044] Prepare an electron transport layer 213 on the surface of the passivation layer 212;

[0045] Prepare a buffer layer 214 on the surface of the electron transport layer 213;

[0046] Forming a second transparent electrode layer 215 on the buffer layer 214;

[0047] Prepare a second metal electrode layer 216 on the surface of the second transparent electrode layer 215;

[0048] An anti-reflection layer 217 is formed on the surface of the second metal electrode layer 216;

[0049] In this embodiment, the first transparent electrode layer 111 is prepared by magnetron sputtering; the first metal electrode layer 110 is prepared by evaporation; the patterned N-type base doping layer 116 is prepared by etching using a laser process; the hole transport layer 210 is prepared by atomic layer deposition; the perovskite absorption layer 211 is prepared by spin coating, flash evaporation or evaporation; the passivation layer 212 is prepared by evaporation, spin coating, spraying; the electron transport layer 213 is prepared by spin coating, inkjet or evaporation; the buffer layer 214 is prepared by spin coating, atomic layer deposition or evaporation; the second transparent electrode layer 215 is prepared by magnetron sputtering or evaporation; the second metal electrode layer 216 is prepared by evaporation; the anti-reflection layer 217 is prepared by magnetron sputtering or evaporation.

[0050] Furthermore, the first transparent electrode layer 111 is prepared by magnetron sputtering. Specifically, the silicon substrate 114 on which the P-type base doping layer 112, base passivation layer 113, base surface passivation layer 115 and N-type base doping layer 116 are prepared can be placed in a magnetron sputtering device, and the power can be controlled between 50-200W.

[0051] Furthermore, the first metal electrode layer 110 can be prepared by evaporation. Specifically, the prepared substrate sample can be placed on a mask plate for evaporation. The evaporation vacuum is 5×10 -5 -2×10 -4 Pa, the evaporation temperature is 500-2000℃, and the evaporation rate is

[0052] Further, the patterned N-type base doping layer 116 is prepared by a laser process. Specifically, the silicon substrate 114 having the N-type base doping layer can be placed in a laser device, and a patterned groove is prepared by scribing the N-type doping layer using a laser scribing process. The laser power is between 0-90W, the scribing width is controlled between 0-50um, and the scribing depth is controlled between 0-80nm. The scribing pattern is a square grid, and the grid side length is controlled between 0-100mm.

[0053] Further, the hole transport layer 210 is prepared by atomic layer deposition. Specifically, the hole transport layer 210 material can be deposited onto the surface of the patterned N-type doped layer using an atomic layer deposition device, the deposition vacuum is 0-1×104Pa, the deposition pipeline temperature is between 50-150°C, and the deposition chamber temperature is 40-150°C. The thickness is controlled between 0-200nm. At this point, the patterned interface contact between the N-type doped layer and the hole transport layer 210 is formed.

[0054] Furthermore, the perovskite absorption layer 211 is prepared by spin coating. Specifically, the prepared perovskite precursor solution can be evenly coated on the surface of the hole transport layer 210, and then the anti-solvent is used for dynamic spin coating. The spin coating speed is 1200-6000rpm, the spin coating time is 20-120s, and the anti-solvent titration time is 10-50s after the start of the spin coating. After the spin coating is completed, an annealing operation is performed, the annealing temperature is 50-150°C, and the annealing time is 5-40min;

[0055] In some embodiments, the perovskite absorption layer 211 can also be prepared by flash evaporation. Specifically, the perovskite precursor liquid can be evenly coated on the surface of the hole transport layer 210, the spin coating speed is 1000-6000rpm, and the spin coating time is 20-120s. After the spin coating is completed, a flash evaporation operation is performed, the flash evaporation time is 10-60s, the flash evaporation temperature is 0-100°C, and after the flash evaporation is completed, an annealing treatment is performed, the annealing temperature is 50-150°C, and the annealing time is 5-40min;

[0056] In some embodiments, the perovskite absorption layer 211 can also be prepared by evaporation. Specifically, the prepared perovskite precursor powder can be evaporated onto the surface of the hole transport layer 210. The evaporation vacuum degree is 1-3×10 -4 Pa, and the evaporation temperature is 200-700℃.

[0057] In this embodiment, the perovskite precursor solution or perovskite precursor powder has a chemical formula of ABX 3 The structured perovskite is adjusted using a stoichiometric ratio and dissolved in an organic solvent with a concentration between 1.5-2M.

[0058] Furthermore, the passivation layer 212 is prepared by evaporation. Specifically, propylene diamine iodide can be evaporated onto the surface of the perovskite absorption layer 211. The evaporation vacuum degree is 1-5×10 -4 Pa, the evaporation temperature is 50-400℃, and the evaporation rate is After evaporation, annealing is performed, the annealing temperature is 0-150°C, and the annealing time is 0-30min;

[0059] In some embodiments, the passivation layer 212 can also be spin-coated. Specifically, the first passivation layer 212 can be dispersed and evenly coated on the surface of the perovskite absorption layer 211. The propylene diamine iodine is dissolved in an organic solvent including but not limited to methanol, ethanol or isopropanol, ultrasonically dissolved and spin-coated. The concentration of propylene diamine iodine is 0.1-6 mg / ml, the ultrasonic time is 0-30 min, the spin coating speed is 1000-7000 rpm, and the spin coating time is 20-120 s. After the spin coating is completed, an annealing operation is performed, the annealing temperature is 40-160 ° C, and the annealing time is 5-40 min;

[0060] In some embodiments, the passivation layer 212 can also be sprayed. Specifically, the first passivation layer 212 dispersion can be sprayed on the perovskite absorption layer 211 at a spraying rate of 0-100 cm / s. After spraying, annealing is performed at a temperature of 20-170° C. and a time of 0-30 min.

[0061] Furthermore, the electron transport layer 213 is prepared by spin coating. Specifically, the electron transport layer 213 dispersion can be evenly coated on the surface of the second passivation layer 212 at a spin coating speed of 500-4000 rpm and a spin coating time of 10-80 s.

[0062] In some embodiments, the electron transport layer 213 may also be formed by evaporation. Specifically, the electron transport layer 213 material may be evaporated onto the surface of the second passivation layer 212. The evaporation vacuum degree is 5×10 -5 -5×10 -4 Pa, the evaporation temperature is 100-400℃, and the evaporation rate is

[0063] Furthermore, the buffer layer 214 is prepared by atomic layer deposition. Specifically, the material of the electron transport layer 213 can be deposited on the surface of the electron transport layer 213 by atomic layer deposition equipment. The deposition vacuum is 0-1×10 4 Pa, the deposition pipeline temperature is between 50-150°C, and the deposition chamber temperature is 40-150°C;

[0064] In some embodiments, the first buffer layer 214 can also be formed by evaporation. Specifically, the modification layer material of the electron transport layer 213 is evaporated onto the surface of the electron transport layer 213. The evaporation vacuum is 6×10 -5- 4×10 -4 Pa, the evaporation temperature is 100-500℃, and the evaporation rate is

[0065] Furthermore, the second transparent electrode layer 215 is prepared by magnetron sputtering. Specifically, the transparent electrode material can be sputtered onto the surface of the modified layer of the electron transport layer 213, and the control power is 30-200W;

[0066] In some embodiments, the second transparent electrode layer 215 can also be formed by evaporation. Specifically, the transparent electrode material can be evaporated onto the surface of the modified layer of the electron transport layer 213. The evaporation vacuum is 1×10 -5 -5×10 -4 Pa, the evaporation temperature is 1000-2000℃, and the evaporation rate is

[0067] Furthermore, the second metal electrode layer 216 is deposited by evaporation, which is similar to the first metal electrode layer 110 except that the mask is different; the anti-reflection layer 217 is deposited by magnetron sputtering, which is similar to the second transparent electrode layer 215; the anti-reflection layer 217 is deposited by evaporation, which is similar to the second passivation layer 212, and the evaporation rate is

[0068] Furthermore, in this embodiment, the hole transport layer 210 is vanadium oxide VOx;

[0069] Perovskite materials can be expressed by the following chemical formula: ABX 3 (I). Wherein: A is a cation selected from the group consisting of methylammonium MA, formamide FA, Cs, or Rb or any combination thereof, B is a metal cation, Pb; and X is a halide anion selected from the group consisting of Br, Cl and I, so that the ratio of Br, Cl and I is between 0:1. The ratio of I is in the range of 0:1 to 1:0.

[0070] Further, in this embodiment, A includes one or more cations, and the selection method is that the molar percentage of A is: formamidine from 0% to 100%; methylammonium from 0% to 100%; Cs from 0% to 30%; Rb from 0% to 30%.

[0071] Furthermore, in the present embodiment, the perovskite material of the perovskite absorption layer 211 is Cs0.05Rb0.05FA0.765MA0.135PbI2.55Br0.45, Cs0.1FA0.765MA0.135PbI2.4Br0.6, Cs0.1FA0.765MA0.135PbI2.22Br0.78 or Cs0.1FA0.765MA0.135PbIBr, etc.

[0072] Furthermore, the passivation layer 212 is propylenediamine iodide, including but not limited to at least one of propylenediamine bromide (PDADBr), butylammonium chloride (BACl), butylammonium bromide (BABr), butylammonium iodide (BAI), N,N-dimethyl-1,3-propylenediamine hydrochloride (DMePDADCl), and dodecanediamine bromide (DDDADBr); it can also be magnesium fluoride; including but not limited to at least one of lithium fluoride (LiF) and sodium fluoride (NaF).

[0073] Further, the dissolving solvent of the perovskite precursor solution includes at least one of dimethylformamide (DMF), G-butyrolactone (GBL), dimethyl sulfoxide (DMSO) and N, N-dimethylacetamide (DMA), and the solvent ratio is between 0-3:10-7. The anti-solvent includes at least one of toluene (Tol), chlorobenzene (CB), and ethyl acetate (EA). The electron transport layer 213 is at least one of zinc oxide (ZnO), tin dioxide (SnO2), titanium dioxide (TiO2), [6,6]-phenyl C61 butyric acid methyl ester (PC61BM), carbon 60 (C60), and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP). The buffer layer 214 is at least one of zinc oxide (ZnO), tin dioxide (SnO2), and titanium dioxide (TiO2). The first transparent electrode layer 111 and the second transparent electrode layer 215 are at least one of indium tin oxide (ITO), indium zinc oxide (IZO), and aluminum zinc oxide (AZO). The second metal electrode layer 216 is at least one of silver (Ag), gold (Au), copper (Cu), aluminum (Al), and carbon (C). The anti-reflection layer 217 is at least one of magnesium fluoride, lithium fluoride (LiF), sodium fluoride (NaF), and silicon oxide (SiO2). The thickness of the hole transport layer 210, the perovskite absorption layer 211, the electron transport layer 213, the buffer layer 214, the second transparent electrode layer 215, the second metal electrode layer 216, and the anti-reflection layer 217 is 1-600nm.

[0074] Furthermore, this embodiment also provides three groups of specific implementation methods for preparing "perovskite / crystalline silicon tandem solar cell devices" for comparative analysis, as follows:

[0075] Test Group 1: Preparation of perovskite / crystalline silicon tandem solar cell devices without tunneling layer

[0076] The device structure from bottom to top is a first metal electrode layer 110, a first transparent electrode layer 111, a P-type base doping layer 112, a base passivation layer 113, a silicon substrate 114, a base surface passivation layer 115, an N-type base doping layer 116, a porous tunneling layer, a hole transport layer 210, a perovskite absorption layer 211, a passivation layer 212, an electron transport layer 213, a buffer layer 214, a second transparent electrode layer 215, a second metal electrode layer 216, and an anti-reflection layer 217.

[0077] Step 1: a substrate passivation layer 113 and a P-type substrate doping layer 112 are sequentially prepared on the back side of the silicon substrate 114, and a substrate surface passivation layer 115 and an N-type substrate doping layer 116 are sequentially prepared on the surface;

[0078] Step 2: Prepare the first transparent electrode layer 111; use the magnetron sputtering method to place the above sample in a magnetron sputtering device, set an ITO target, control the power to 60W, run time to 1.5h, and the film thickness to 100nm;

[0079] Step 3: Prepare the first metal electrode layer 110; using the evaporation method, place the substrate sample on the mask, put it into the evaporation chamber, and perform evaporation when the evaporation vacuum is 2×10 -4Pa, adjust the evaporation voltage to the evaporation temperature, and control the evaporation rate to Silver was evaporated onto the layer film with a thickness of 200 nm;

[0080] Step 4: Prepare a hole transport layer 210 on the surface of the N-type base doping layer 116; treat the sample with UV-Ozone for 15 minutes, use the spin coating method, prepare the hole transport layer 210 dispersion, weigh 0.05 mol NiOx powder and dissolve it in 1 ml ultrapure water, and ultrasonically vibrate for 20 minutes. Evenly coat the surface of the sample with the hole transport layer 210 dispersion, set the spin coating speed to 2000 rpm, the spin coating time to 40 seconds, and the solution volume to 100 ul. After the spin coating is completed, perform annealing operation, the annealing temperature is 450°C, the annealing time is 30 minutes, and the thickness is about 20 nm;

[0081] Step 5: Prepare the perovskite absorption layer 211; use the flash evaporation method, prepare the perovskite precursor solution, weigh the perovskite raw material powder of equal ratio and dissolve it in 1ml DMF and DMSO solvent, the solvent ratio is 8:2, magnetic stirring is carried out for 30min, then the sample is placed on the base of the spin coater, the spin coating speed is set to 3500rpm, the spin coating time is 30s, the perovskite precursor solution volume is 120ul to coat the surface of the sample, after the spin coating is completed, the sample is placed on the flash evaporation table, the flash evaporation time is set to 30s, the flash evaporation temperature is set to 30°C, and annealing is performed after the flash evaporation, the annealing temperature is set to 100°C, the annealing time is 15min, and the thickness is about 500nm;

[0082] Step 6: Prepare the passivation layer 212; using the evaporation method, weigh 3 mg of propylene diamine iodine and place it in a crucible, place the substrate sample on the mask, put it into the evaporation chamber, and perform evaporation when the evaporation vacuum is 2×10 -4Pa, adjust the evaporation voltage to the evaporation temperature, and control the evaporation rate at Propylene diamine iodide was evaporated onto the film with a thickness of 4 nm. After the annealing table temperature was set to 100°C, and the annealing operation was performed for 8 minutes.

[0083] Step 7: Prepare the electron transport layer 213; Use the evaporation method to place the substrate sample on the mask and put it into the evaporation chamber. When the evaporation vacuum is 1×10 -4Pa, perform evaporation. Adjust the evaporation voltage to the evaporation temperature and control the evaporation rate to C60 was evaporated onto the film with a thickness of 20 nm;

[0084] Step 8: Prepare the buffer layer 214; use the atomic layer deposition method, set the vacuum degree of the atomic layer deposition equipment to 0.5×104Pa, the deposition pipeline temperature to 60°C, the deposition chamber temperature to 70°C, and evaporate SnO2 onto the layer film with a thickness of 15nm;

[0085] Step nine: preparing the second transparent electrode layer 215; similar to preparing the first transparent electrode layer 111, setting an IZO target, controlling the power to 50W, the operating time to 1h, and the film thickness to 100nm;

[0086] Step 10: Prepare the second metal electrode layer 216; similar to the preparation of the first metal electrode layer 110, the mask is different and the thickness is 100 nm;

[0087] Step 11: Prepare the anti-reflection layer 217; similar to the preparation of the second passivation layer 212, control the evaporation rate to Magnesium fluoride was evaporated onto the film to a thickness of 100 nm.

[0088] Test Group 2: Preparation of traditional perovskite / crystalline silicon tandem solar cell devices with tunneling layer:

[0089] The preparation method of this group is basically the same as that of the test group 1, except that the step of preparing the tunneling layer 117 is added before step 4 as follows:

[0090] A tunneling layer 117 is prepared on the surface of the N-type base doping layer 116. The sample is placed on a mask and then placed in a magnetron sputtering device using a magnetron sputtering method. The control power is 60W, the operation time is 1h, and the film thickness is 40nm.

[0091] Test Group 3: Preparation of perovskite / crystalline silicon tandem solar cell device based on the graphical tunneling layer-free structure of the utility model:

[0092] The device structure from bottom to top is a first metal electrode layer 110, a first transparent electrode layer 111, a P-type substrate doping layer 112, a substrate passivation layer 113, a silicon substrate 114, a substrate surface passivation layer 115, a patterned N-type substrate doping layer 116, a hole transport layer 210, a first perovskite absorption layer 211, a second perovskite absorption layer 211, a passivation layer 212, an electron transport layer 213, a buffer layer 214, a second transparent electrode layer 215, a second metal electrode layer 216, and an anti-reflection layer 217.

[0093] The preparation method of this group is basically the same as that of test group 1, except that a laser patterning etching step is added before step 4 as follows:

[0094] The N-type doped layer patterning method is to place the silicon substrate 114 having the N-type base doped layer 116 in a laser device by using a laser process, and to scribe the N-type doped layer to prepare a patterned groove by using a laser scribing process. The laser power is between 60W, the scribing width is controlled at 50um, and the scribing depth is controlled at 40nm. The scribing pattern is a square grid, and the grid side length is controlled at 50mm.

[0095] A hole transport layer 210 is prepared on the N-type base doping layer 116. The hole transport layer 210 is formed by atomic layer deposition, where vanadium oxide, the material of the hole transport layer 210, is deposited onto the surface of the patterned N-type doping layer using an atomic layer deposition device, the deposition vacuum is 1×10-4Pa, the deposition pipeline temperature is between 100°C, and the deposition chamber temperature is 100°C. The thickness is controlled at 80nm.

[0096] It can be understood that this group has no tunneling layer, and the patterned contact between the N-type doped layer and the hole transport layer 210 is achieved by setting a patterned structure.

[0097] The following is a comparative analysis of the three test groups:

[0098] The three test groups were calibrated with standard sunlight intensity using a solar simulator, and each solar cell device with an area of ​​1.0 cm2 was subjected to a long-term IV test. The starting voltage was set to 2.1 V, the cutoff voltage was set to 0 V, the range was set to 100 mA, and the results were rounded to two decimal places. The test results are shown in the table below.

[0099]

[0100]

[0101] It can be concluded from the above table that for test group 1 and test group 3, in the structure without a tunneling layer, test group 3 with a graphical connection has a significantly reduced interface contact resistance and lower interface non-composite loss. This results in the devices in test group 3 having a much higher photoelectric conversion efficiency than test group 1. At the same time, because of the absorption loss caused by the absence of a tunneling layer, test group 3 has a higher short-circuit current density and photoelectric conversion efficiency than test group 2. Considering the convenience of stability, this graphical contact of test group 3 greatly improves the adhesion of the contact film layer between the top and bottom cells. Therefore, test group 3 has a much higher stability than test groups 1 and 2, which is reflected in the fact that the devices in test group 3 have a smaller attenuation rate than those in test groups 1 and 2.

[0102] The above are one or more implementation methods provided in combination with specific content, and it is not intended that the specific implementation of the utility model is limited to these descriptions. Any method, structure, etc. similar to or identical to the method, structure, etc. of the utility model, or any technical deduction or replacement based on the concept of the utility model, shall be deemed to be within the protection scope of the utility model.

Claims

1. A perovskite crystalline silicon tandem solar cell based on patterned connection, characterized in that: It comprises a hole transport layer (210) and a patterned N-type base doping layer (116) electrically connected to the hole transport layer (210), wherein an end surface of the patterned N-type base doping layer (116) connected to the hole transport layer (210) is provided with a patterned unit (116a), and the patterned unit (116a) is used to increase the contact area between the hole transport layer (210) and the patterned N-type base doping layer (116); The patterned N-type base doping layer (116) is provided with a plurality of grooves (116b), and the plurality of grooves (116b) form the patterned unit (116a). The hole transport layer (210) is provided with a plurality of connecting portions (210a) on an end surface protruding from the end surface connected to the patterned N-type base doping layer (116), and the connecting portions (210a) are electrically connected to the grooves (116b).

2. A perovskite crystalline silicon tandem solar cell based on patterned connection according to claim 1, characterized in that: The grooves (116b) have a width of 0-50um and a depth of 0-80nm. The grooves (116b) are arranged in a grid shape on the patterned N-type base doping layer (116). The side length of the grid is 0-100mm.

3. A perovskite crystalline silicon tandem solar cell based on patterned connection according to claim 2, characterized in that: A substrate surface passivation layer (115), a silicon substrate (114), a substrate passivation layer (113), a P-type substrate doping layer (112), a first transparent electrode layer (111) and a first metal electrode layer (110) are sequentially arranged below the patterned N-type substrate doping layer (116), and a perovskite absorption layer (211), a passivation layer (212), an electron transport layer (213), a buffer layer (214), a second transparent electrode layer (215), a second metal electrode layer (216) and an anti-reflection layer (217) are sequentially arranged above the hole transport layer (210).

4. A perovskite crystalline silicon tandem solar cell based on patterned connection according to claim 3, characterized in that: The perovskite material of the perovskite absorption layer (211) has a chemical formula of ABX3, wherein A is a cation, including one of methylammonium, formamide, Cs, and Rb; B is a metal cation, including Pb; and X is a halide anion, including one of Br, Cl, and I.

5. The perovskite crystalline silicon tandem solar cell based on patterned connection according to claim 3, characterized in that: The passivation layer (212) comprises one of propylenediamine iodide, propylenediamine bromide, butylammonium chloride, butylammonium bromide, butylammonium iodide, N,N-dimethyl-1,3-propylenediamine hydrochloride, dodecanediamine bromide, magnesium fluoride, lithium fluoride, and sodium fluoride.

6. The perovskite crystalline silicon tandem solar cell based on patterned connection according to claim 3, characterized in that: The electron transport layer (213) includes one of zinc oxide, tin dioxide, titanium dioxide, [6,6]-phenyl C61 butyric acid methyl ester, carbon 60, and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline.

7. The perovskite crystalline silicon tandem solar cell based on patterned connection according to claim 3, characterized in that: The buffer layer (214) comprises one of zinc oxide, tin dioxide and titanium dioxide; The first transparent electrode layer (111) and the second transparent electrode layer (215) include one of indium tin oxide, indium zinc oxide, and zinc aluminum oxide; The second metal electrode layer (216) includes one of silver, gold, copper, aluminum and carbon; The anti-reflection layer (217) includes one of magnesium fluoride, lithium fluoride, sodium fluoride, and silicon oxide.

8. The perovskite crystalline silicon tandem solar cell based on patterned connection according to claim 3, characterized in that: The hole transport layer (210), the perovskite absorption layer (211), the electron transport layer (213), the buffer layer (214), the second transparent electrode layer (215), the second metal electrode layer (216) and the anti-reflection layer (217) have a thickness of 1-600 nm.

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