阅读说明：本技术 一种钙钛矿与晶硅的三结叠层太阳能电池及其制备方法 (Perovskite and crystalline silicon triple-junction laminated solar cell and preparation method thereof ) 是由 不公告发明人 于 2020-05-14 设计创作，主要内容包括：本发明涉及一种钙钛矿与晶硅的三结叠层太阳能电池,包括背接触钙钛矿子电池、背接触式晶硅子电池以及位于中间的复合层,背接触钙钛矿子电池包括指叉式背接触钙钛矿太阳能电池或空间网状背接触太阳能电池,背接触式晶硅子电池包括指叉式背接触电池IBC、点接触式背接触电池PCC、背面指叉式单次沉积背接触电池RISE中的任意一种,背接触钙钛矿子电池的电极均埋在钙钛矿吸光材料之下,背接触式晶硅子电池是指其发射区电极和基区电极均位于电池背面的硅太阳能电池。本发明还公开该三结叠层太阳能电池的制备方法。本发明能更有效提取不同波长光的能量,结构紧凑简单,能有效减少寄生吸收,且不受电流匹配的限制,可以发挥两个子电池的最佳效果。(The invention relates to a perovskite and crystalline silicon triple-junction laminated solar cell, which comprises a back contact perovskite sub cell, a back contact crystalline silicon sub cell and a composite layer positioned in the middle, wherein the back contact perovskite sub cell comprises an interdigital back contact perovskite solar cell or a space net-shaped back contact solar cell, the back contact crystalline silicon sub cell comprises any one of an interdigital back contact cell IBC, a point contact type back contact cell PCC and a back interdigital single-deposition back contact cell RISE, electrodes of the back contact perovskite sub cell are all buried under a perovskite light absorption material, and the back contact crystalline silicon sub cell is a silicon solar cell of which an emitter region electrode and a base region electrode are both positioned on the back of the cell. The invention also discloses a preparation method of the three-junction laminated solar cell. The invention can more effectively extract the energy of light with different wavelengths, has compact and simple structure, can effectively reduce parasitic absorption, is not limited by current matching, and can exert the optimal effect of two sub-batteries.)

1. The three-junction laminated solar cell is characterized by comprising a back contact perovskite sub cell positioned on the upper part, a back contact crystalline silicon sub cell positioned on the lower part and a composite layer positioned in the middle, wherein the back contact perovskite sub cell comprises an interdigital back contact perovskite solar cell or a space net-shaped back contact solar cell, the back contact crystalline silicon sub cell comprises any one of an interdigital back contact cell, a point contact type back contact cell and a back interdigital single deposition back contact cell, electrodes of the back contact perovskite sub cell are all buried under a perovskite light absorption material, and the back contact crystalline silicon sub cell refers to a silicon solar cell of which an emitter region electrode and a base region electrode are both positioned on the back of the cell.

2. The perovskite and crystalline silicon triple-junction solar cell according to claim 1, wherein the internal structure of the back-contact crystalline silicon sub-cell comprises a silicon substrate, interdigitated first and second electrodes located at the bottom of the silicon substrate, and metal electrodes located at the bottom surfaces of the first and second electrodes, the composite layer being disposed on the top surface of the silicon substrate; the internal structure of back contact perovskite sub-battery is including setting up the first transmission layer at the composite bed top surface, setting up the first functional layer of interdigital formula or two-dimentional netted on first transmission layer top surface, the perovskite layer that covers first functional layer and set up the anti-reflection coating at perovskite layer top surface, and the internal structure of first functional layer is from up including insulating layer, third electrode and second transmission layer down in proper order, and first electrode, second electrode and third electrode are connected with outside wire respectively.

3. The perovskite and crystalline silicon triple-junction solar cell according to claim 2, wherein the metal electrode is made of any one metal or any one alloy of platinum, gold, silver, copper, aluminum, rhodium, indium, titanium, iron, nickel, tin and zinc, and has a thickness of 50nm to 500nm, or graphite and has a thickness of 500nm to 5 um.

4. The perovskite and crystalline silicon triple-junction solar cell according to claim 2, wherein the composite layer is made of any one of indium tin oxide, aluminum oxide doped zinc oxide, indium oxide doped zinc oxide, fluorine-doped tin oxide, zirconium-doped indium oxide and tungsten-doped indium oxide, and the thickness of the composite layer is 5nm to 80 nm.

5. The perovskite and crystalline silicon triple-junction tandem solar cell according to claim 2, wherein the first transport layer is an electron transport layer or a hole transport layer, respectively, and the second transport layer is a hole transport layer and an electron transport layer, respectively, wherein the electron transport layer is made of any one of n-type oxide or n-type organic material with a thickness of about 5nm to 80nm, the n-type oxide comprises any one of titanium dioxide, tin dioxide and zinc oxide, the n-type organic material comprises at least one of Di-PDI, ITCPTC-Th, carbon 60, carbon 70, alkyl fullerene phenyl-carbon 61-methyl butyrate, alkyl fullerene phenyl-carbon 72-methyl butyrate, PCBM and novel indene and C60 double adduct or a variant and dopant of the above fullerene organic material, and the hole transport layer is made of any one of p-type inorganic material or p-type organic material, the p-type inorganic substance comprises any one of nickel oxide, cobalt oxide, molybdenum oxide, tungsten oxide, vanadium oxide and cuprous thiocyanate, and the thickness of the p-type inorganic substance is 5-50 nm, or the p-type organic substance comprises at least one of poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid, poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ], 2',7,7' -tetra (N, N-p-methoxyanilino) -9,9' -spirobifluorene, 3, 4-ethylenedioxythiophene, poly (3-hexylthiophene-2, 5-diyl) and poly [ bis (4-phenyl) (4-butylphenyl) amine ], and the thickness of the p-type organic substance is 5-50 nm.

6. The perovskite and crystalline silicon triple-junction solar cell according to claim 2, wherein the insulating layer is made of alumina, silicon oxide or silicon nitride and has a thickness of 30nm to 200 nm; the third electrode is made of any one metal or any one alloy of platinum, gold, silver, copper, aluminum, rhodium, indium, titanium, iron, nickel, tin and zinc, and the thickness of the third electrode is 50 nm-100 nm.

7. The perovskite and crystalline silicon triple-junction tandem solar cell according to claim 2, wherein the perovskite layer has a band gap of not more than 3.0eV and has a compound structural formula of AMX₃Wherein A is a monovalent cation, A is an alkali metal cation or an organic cation, M is a divalent cation, M is any one of a transition metal and a divalent cation of a group 13 to 15 element, X is a monovalent anion, X is any one of a halogen anion and a thiocyanate ion, and the thickness of the perovskite layer is 300nm to 2 μ M.

8. The perovskite and crystalline silicon triple-junction solar cell according to claim 7, wherein the compound formula AMX in the perovskite layer₃Wherein A comprises any one of methylamine cation, formamidine cation, cesium cation and rubidium cation, and M comprises Pb²⁺、Ge²⁺、Sn²⁺、Cu²⁺、Bi²⁺Any one of them.

9. A method of manufacturing a triple-junction solar cell of perovskite and crystalline silicon according to any of claims 2 to 8, comprising the steps of:

step 1, preparing a composite layer on the upper surface of a back contact type crystalline silicon sub-battery with a first electrode, a second electrode and a metal electrode prepared at the bottom;

step 2, preparing a first transmission layer on the surface of the composite layer;

step 3, coating a thermoplastic polymer material layer for imprinting on the first transmission layer;

step 4, carrying out roller imprinting on the thermoplastic polymer material layer by using a roller with bulges in accordance with the design of the reticulate pattern of the two-dimensional reticular first functional layer, and obtaining a roller reticulate pattern on the surface of an imprinting material of the thermoplastic polymer material layer;

step 5, after the roller and the thermoplastic polymer material layer are separated and demoulded, removing the residual thermoplastic polymer material layer imprinting material thin layer between the bottom of the roller reticulate pattern and the first transmission layer by using directional etching to obtain reticulate pattern gullies capable of being filled into the first functional layer;

step 6, sequentially preparing an insulating layer, a second electrode layer and a second transmission layer on the surface of the thermoplastic polymer material layer and in the gullies of the reticulate pattern template layer by layer at the same time according to the sequence of the upper structure and the lower structure to obtain a first functional layer;

step 7, dissolving the thermoplastic polymer material layer imprinting material by using a solvent method, and simultaneously removing the first functional layer electrode material falling on the thermoplastic polymer material layer imprinting material;

and 8, sequentially preparing a perovskite layer and an antireflection layer on the first functional layer, wherein the perovskite layer fills the grid gaps of the first functional layer and covers the first functional layer until the manufacture of the perovskite and crystalline silicon triple-laminated solar cell is completed.

Technical Field

The invention belongs to the technical field of structural design and production preparation of perovskite solar cells, and particularly relates to a novel perovskite and crystalline silicon triple-junction laminated solar cell and a preparation method thereof.

Background

Theoretically, any semiconductor material can only absorb photons with energy value larger than the forbidden band width, and because the energy distribution of the solar spectrum is wide, a solar cell made of a single light-absorbing semiconductor material cannot effectively absorb all photons, so that the light energy conversion is realized to the maximum extent. The common solution is to use light absorbing materials with different band gap widths to prepare a tandem solar cell, so that the light absorbing material with a wider band gap absorbs short wavelength light with larger energy, and the long wavelength light passes through a wide band gap light absorbing layer to be absorbed by a rear narrow band gap light absorbing material, thereby extracting the energy contained in the light quantum to a greater extent. Currently, the efficiency of silicon-based solar cells has reached 25.6%, approaching the Shockley-queeiser limit efficiency (29.4%). Perovskite solar cells undergo rapid development, and the photoelectric conversion efficiency thereof is now close to that of single crystalline silicon solar cells. The perovskite and the silicon have different band gap widths, the perovskite solar cell is used as a laminated solar cell formed by the top cell and the silicon cell, the spectral response range of the cell can be widened, the efficiency of the solar cell is improved, and meanwhile, the perovskite solar cell has the characteristics of low cost and easiness in preparation, and the cost cannot be greatly increased when the laminated cell is manufactured. Therefore, the perovskite and silicon laminated solar cell has considerable application prospect.

Conventional perovskite tandem cell devices generally employ a four-junction (also known as four-terminal, 4T) or two-junction (also known as two-terminal, 2T) structure. As shown in FIG. 1a, the internal structure and current flow of the four-junction stacked battery are schematically shown. The 4T structure has two independent subcells, the lower subcell is provided with substrate a, electrode B, narrow bandwidth light absorbing material C and electrode D, and the upper subcell is provided with substrate E, electrode F, wide bandwidth light absorbing material G and electrode H. The two sub-batteries with the 4T structure are independent batteries and are respectively connected with a load in the circuit. The current I1 and the current I2 are not directly related and do not influence each other in the manufacturing process or the working condition, so that the processing and preparation complexity of the battery does not need to be improved on the basis of preparing a single sub-battery. However, the subcell located at the lower part for absorbing long-wavelength light has a disadvantage in that the absorption of light by the upper subcell and its own upper electrode is greatly affected, and there is a higher long-wavelength transmittance requirement for the upper subcell and its own upper electrode. In addition, the four-junction stack consumes substantially twice as much substrate and manufacturing raw materials as a single sub-cell from a mass-production-scale point of view, which is too high for cost control.

As shown in fig. 1b, the internal structure and current flow of the two-junction stacked cell are schematically shown, and two sub-cells in the 2T structure are connected in series by a composite layer. The light-absorbing material comprises a substrate A, an electrode B, a narrow-bandwidth light-absorbing material C, a composite layer K, a wide-bandwidth light-absorbing material G, an electrode D and an antireflection/packaging layer J. Two sub-batteries in the 2T structure are connected in series in the battery, the current I1 is equal to the current I2, and a composite layer is equivalent to replace two groups of electrodes in the 4T structure and the substrate of the upper sub-battery, so that parasitic absorption generated by the electrodes is greatly reduced, and the relatively simple and compact structure is favorable for reducing the manufacturing cost. However, due to the series connection of the sub-cells, the maximum power output of the two-junction tandem cell requires that the currents generated by the sub-cells match (i.e., the two sub-cells limit the current to each other, and the final output current is based on the sub-cell generating the smaller current). The requirements on the band gap width and the thickness of the perovskite thin film of the perovskite material selected by the sub-battery are strict, the selection of the light absorbing material used by the sub-battery is greatly limited, and the advantages of the perovskite laminated battery cannot be exerted to the maximum extent.

Although the current matching problem due to the series connection of the upper and lower sub-cells can be solved by using a triple-junction stack scheme, the 3T cell structure is shown in fig. 1C, which is provided with a substrate a, an electrode B, an electrode D, a narrow-bandwidth light-absorbing material C, a composite layer K, a wide-bandwidth light-absorbing material G, an electrode H, and an anti-reflection/encapsulation layer J. The top electrode (electrode H in the figure) of the upper subcell inevitably generates parasitic absorption, thereby affecting the light absorption utilization of the upper and lower subcells. In order to further improve the light utilization rate of the tandem cell and the efficiency of the perovskite tandem cell, it is necessary to minimize the parasitic absorption of the upper sub-cell and the electrode to the incident light.

Disclosure of Invention

The invention provides a perovskite and crystalline silicon triple-junction laminated solar cell and a preparation method thereof, a sub-cell design of a back contact type perovskite cell is used, and a novel perovskite laminated cell structure is provided from a triple-junction laminated cell structure design.

The invention is realized in such a way, and provides a perovskite and crystalline silicon triple-junction tandem solar cell, which comprises a Back Contact perovskite sub cell positioned on the upper part, a Back Contact crystalline silicon sub cell positioned on the lower part and a composite layer positioned in the middle, wherein the Back Contact perovskite sub cell comprises an interdigital Back Contact perovskite solar cell or a space net-shaped Back Contact solar cell, the Back Contact crystalline silicon sub cell comprises any one of an interdigital Back Contact cell IBC (Interdigitated Back Contact), a point Contact type Back Contact cell PCC (Point Contact cell) and a Back interdigital Single deposition Back Contact cell RISE (real Interdigitated Single deposition), the electrodes of the Back Contact perovskite sub cells are all buried under a light absorption perovskite material, and the Back Contact crystalline silicon sub cell is a silicon solar cell of which the emitting region electrode and the base region electrode are both positioned on the Back of the cell.

Furthermore, the internal structure of the back contact type crystalline silicon sub-cell comprises a silicon substrate, a first electrode and a second electrode which are in a finger fork shape and are positioned at the bottom of the silicon substrate, and metal electrodes positioned at the bottom surfaces of the first electrode and the second electrode, wherein a composite layer is arranged on the top surface of the silicon substrate; the internal structure of back contact perovskite sub-battery is including setting up the first transmission layer at the composite bed top surface, setting up the first functional layer of interdigital formula or two-dimentional netted on first transmission layer top surface, the perovskite layer that covers first functional layer and set up the anti-reflection coating at perovskite layer top surface, and the internal structure of first functional layer is from up including insulating layer, third electrode and second transmission layer down in proper order, and first electrode, second electrode and third electrode are connected with outside wire respectively.

The invention is realized in such a way that the preparation method of the perovskite and crystalline silicon triple-junction solar cell comprises the following steps:

step 1, preparing a composite layer on the upper surface of a back contact type crystalline silicon sub-battery with a first electrode, a second electrode and a metal electrode prepared at the bottom;

step 2, preparing a first transmission layer on the surface of the composite layer;

step 3, coating a thermoplastic polymer material layer for imprinting on the first transmission layer;

step 4, carrying out roller imprinting on the thermoplastic polymer material layer by using a roller with bulges in accordance with the design of the reticulate pattern of the two-dimensional reticular first functional layer, and obtaining a roller reticulate pattern on the surface of an imprinting material of the thermoplastic polymer material layer;

step 5, after the roller and the thermoplastic polymer material layer are separated and demoulded, removing the residual thermoplastic polymer material layer imprinting material thin layer between the bottom of the roller reticulate pattern and the first transmission layer by using directional etching to obtain reticulate pattern gullies capable of being filled into the first functional layer;

step 6, sequentially preparing an insulating layer, a second electrode layer and a second transmission layer on the surface of the thermoplastic polymer material layer and in the gullies of the reticulate pattern template layer by layer at the same time according to the sequence of the upper structure and the lower structure to obtain a first functional layer;

step 7, dissolving the thermoplastic polymer material layer imprinting material by using a solvent method, and simultaneously removing the first functional layer electrode material falling on the thermoplastic polymer material layer imprinting material;

and 8, sequentially preparing a perovskite layer and an antireflection layer on the first functional layer, wherein the perovskite layer fills the grid gaps of the first functional layer and covers the first functional layer until the manufacture of the perovskite and crystalline silicon triple-laminated solar cell is completed.

Compared with the prior art, the perovskite and crystalline silicon triple-junction laminated solar cell and the preparation method thereof have the following characteristics:

1) the energy of light with different wavelengths can be more effectively extracted;

2) the top electrode of the upper sub-cell is not arranged, so that the parasitic absorption of incident light is greatly reduced;

3) the structure is compact and simple, and the parasitic absorption is less than that of a four-junction laminated layer;

4) the current matching is not limited, and the best effect of the two sub-batteries can be exerted;

5) the preparation method can be used for preparing a large-area laminated battery and is easy to produce in mass production.

Drawings

FIG. 1a is a schematic diagram of the internal structure of a conventional four-junction tandem solar cell;

FIG. 1b is a schematic diagram of the internal structure of a conventional two-junction tandem solar cell;

FIG. 1c is a schematic diagram of the internal structure of a conventional triple-junction tandem solar cell;

FIG. 2 is a schematic diagram of the internal structure of a triple-junction solar cell of perovskite and crystalline silicon according to the present invention;

FIG. 3 is a schematic diagram showing details of the internal structure of a triple-junction solar cell of perovskite and crystalline silicon according to the present invention;

fig. 4 is a schematic diagram of the preparation steps for preparing the two-dimensional reticulated back-contact perovskite solar subcell of example 1;

fig. 5 is a schematic diagram of the operating principle of the roller impression in embodiment 1 at part (a) and an enlarged schematic diagram of part P in part (b).

Detailed Description

In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, 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.

Referring to fig. 2, the preferred embodiment of the perovskite and crystalline silicon triple-junction tandem solar cell of the present invention includes a back-contact perovskite sub-cell 1 at the upper portion, a back-contact crystalline silicon sub-cell 2 at the lower portion, and a composite layer 3 in the middle.

The back contact perovskite sub-cell 1 comprises an interdigitated back contact perovskite solar cell or a spatially meshed back contact solar cell. The Back Contact type crystal silicon sub-battery 2 comprises any one of an interdigital Back Contact battery IBC (Interdigitated Back Contact), a point Contact type Back Contact battery PCC (point Contact cell), and a Back interdigital Single deposition Back Contact battery RISE (r interdigital Single evolution). The electrodes of the back contact perovskite sub-cell 1 are all buried under perovskite light absorption materials, and the back contact crystalline silicon sub-cell 2 refers to a silicon solar cell of which the emitter region electrode and the base region electrode are both positioned on the back of the cell.

Referring to fig. 3, the internal structure of the back-contact type crystalline silicon sub-cell 2 includes a silicon substrate 7, a first electrode 5 and a second electrode 6 in a finger-shaped shape at the bottom of the silicon substrate, and a metal electrode 4 at the bottom of the first electrode and the second electrode, wherein a composite layer 3 is disposed on the top surface of the silicon substrate 7. The first electrode 5 and the second electrode 6 are isolated by the silicon substrate 7.

The internal structure of the back contact perovskite sub-battery 1 comprises a first transmission layer 8 arranged on the top surface of the composite layer 3, a first functional layer 9 in an interdigital or two-dimensional net shape arranged on the top surface of the first transmission layer 8, a perovskite layer 10 covering the first functional layer, and an anti-reflection layer 11 arranged on the top surface of the perovskite layer 10. The internal structure of the first functional layer 9 comprises an insulating layer 12, a third electrode 13 and a second transmission layer 14 in sequence from bottom to top.

The first electrode 5, the second electrode 6, and the third electrode 13 are connected to external leads, respectively. The connection mode is that the first electrode 5 and the third electrode 13 are connected with a negative electrode, the second electrode 6 is connected with a positive electrode, at this time, the first transmission layer 8 is a hole transmission layer, and the second transmission layer 14 is an electron transmission layer, or the first electrode 5 and the third electrode 13 are connected with a positive electrode, the second electrode 6 is connected with a negative electrode, at this time, the first transmission layer 8 is an electron transmission layer, and the second transmission layer 14 is a hole transmission layer.

The metal electrode 4 is made of any one metal or any one alloy of platinum, gold, silver, copper, aluminum, rhodium, indium, titanium, iron, nickel, tin and zinc, and has a thickness of 50 nm-500 nm, or graphite and has a thickness of 500 nm-5 um. The preparation method comprises any one of the processing modes of thermal evaporation, electron beam evaporation and magnetron sputtering, and the specific position is coated by combining a mask or a photoetching technology.

The composite layer 3 is made of any one of Indium Tin Oxide (ITO), aluminum oxide doped zinc oxide (AZO), indium oxide doped zinc oxide (IZO), fluorine-doped tin oxide (FTO), zirconium-doped indium oxide (IZOZ) and tungsten-doped indium oxide (IWO), and the thickness of the composite layer is 5 nm-80 nm. The preparation method comprises any one of processing modes of magnetron sputtering, plasma enhanced chemical vapor deposition and monoatomic layer deposition.

The first transport layer 8 is an electron transport layer or a hole transport layer, and correspondingly, the second transport layer 14 is a hole transport layer and an electron transport layer. Wherein the electron transport layer is made of n-type oxide or n-type organic matter with a thickness of 5-80 nm, and the n-type oxide comprises titanium dioxide (TiO)₂) Tin dioxide (SnO)₂) And zinc oxide (ZnO), wherein the n-type organic substance comprises Di-PDI, ITCPTC-Th, carbon 60 (C60), carbon 70 (C70), and alkyl fullerene phenyl-carbon 61-methyl butyrate (PC)₆₁BM), alkyl fullerene phenyl-C72-butyric acid-methyl ester (PC)₇₂BM), PCBM and novel indene and C60 bis-adducts or variants and dopants of the above fullerene-based organic compounds. The preparation material of the hole transport layer is any one of a p-type inorganic substance or a p-type organic substance, the p-type inorganic substance comprises any one of nickel oxide, cobalt oxide, molybdenum oxide, tungsten oxide, vanadium oxide and cuprous thiocyanate, the thickness of the p-type inorganic substance is 5 nm-50 nm, or the p-type organic substance comprises poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid and poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine]2,2',7,7' -tetrakis (N, N-p-methoxyanilino) -9,9' -spirobifluorene, 3, 4-ethylenedioxythiophene, poly (3-hexylthiophene-2, 5-diyl), poly [ bis (4-phenyl) (4-butylphenyl) amine]At least one of them, the thickness of which is 5nm to 50 nm. The preparation method of the first transmission layer and the second transmission layer comprises any one of spraying, coating, electrochemical deposition, thermal evaporation, electron beam evaporation and sputtering processing modes.

The insulating layer 12 is made of alumina (Al)₂O₃) Silicon oxide (SiO)₂) Or silicon nitride (Si)₃N₄) The thickness of the film is 30nm to 200 nm. The preparation method comprises any one of electrochemical deposition, electron beam evaporation, vapor deposition and sputtering processing modes.

The third electrode 13 is made of any one metal or any one alloy of platinum, gold, silver, copper, aluminum, rhodium, indium, titanium, iron, nickel, tin and zinc, and has a thickness of 50nm to 100 nm. The preparation method comprises any one of the processing modes of thermal evaporation, electron beam evaporation and magnetron sputtering.

The band gap of the perovskite layer 10 is not more than 3.0eV, and the structural formula of the compound is AMX₃Wherein A is a monovalent cation, A is an alkali metal cation or an organic cation, M is a divalent cation, M is any one of a transition metal and a divalent cation of a group 13 to 15 element, X is a monovalent anion, and X is a halogen anion and a thiocyanato ion (SCN)^-) The A, M and X positions are occupied by various ions, the thickness of the perovskite layer is 300 nm-2 mu m, and the preparation method comprises any one of coating, spraying and thermal evaporation processing modes.

Wherein A comprises a methylamine Cation (CH)₃NH³⁺) Formamidine cation (NH)₂CHNH²⁺) Cesium cation (Cs)⁺) And rubidium cation (Rb)⁺) Any one of, M includes Pb²⁺、Ge²⁺、Sn²⁺、Cu²⁺、Bi²⁺Any one of them. Perovskite Compounds AMX in general₃Is MAPbI₃、MAPbBr₃、MAPbI_xBr_3-x、MAPbI_xCl_3-x、FAPbI₃、FAPbBr₃、FAPbI_xBr_3-x、FAPbI_xCl_3-x、BAPbI₃、BAPbBr₃、BAPbI_xBr_3-x、BAPbI_xCl_3-x、MASnI₃、MASnBr₃、MASnI_xBR_3-x、FASnI₃、FASnBr₃、FASnI_xBr_3-x、FASnI_xCl_3-x、BASnI₃、BASnBr₃、BASnI_xBr_3-x、BASnI_xCl_3-xAt least one of them, wherein 0<x<3。

The following will further illustrate the preparation method of the triple-junction solar cell of perovskite and crystalline silicon according to the present invention with reference to specific examples.

Example 1

Referring to fig. 3 and 4, a first method for manufacturing a triple-junction solar cell of perovskite and crystalline silicon according to the present invention includes the following steps:

step 1, cleaning a silicon substrate 7, removing a surface oxidation layer, texturing the lower surface of the silicon substrate 7 to form a interdigital subarea, doping the interdigital subarea to obtain a first electrode 5 and a second electrode 6 respectively, and preparing metal electrodes 4 on the lower surfaces of the first electrode 5 and the second electrode 6 respectively.

And 2, sequentially preparing a composite layer 3 and a first transmission layer 8 on the upper surface of the silicon substrate 7 respectively.

Step 3, a layer 15 of thermoplastic polymer material for imprinting, such as Polymethylmethacrylate (PMMA), is coated on the first transfer layer 8.

And 4, carrying out roller imprinting on the thermoplastic polymer material layer 15 by using a roller 16 with protrusions matched with the design of the reticulate pattern of the two-dimensional reticular first functional layer 9, and obtaining a roller reticulate pattern 17 on the surface of an imprinting material of the thermoplastic polymer material layer 15.

The operation principle of the roller embossing is shown in fig. 5a and 5b, and the roller 16 is pressed on the surface of the thermoplastic polymer material layer 15 through the embossing reticulate patterns arranged on the surface of the thermoplastic polymer material layer 15 in the rolling process of the surface of the thermoplastic polymer material layer 15 to obtain the roller reticulate pattern 17.

Step 5, after the roller 16 and the thermoplastic polymer material layer 15 are separated and demolded, a residual thin layer of the thermoplastic polymer material layer imprinting material between the bottom of the roller screen pattern 17 and the first transmission layer 8 is removed by directional etching (e.g., Reactive Ion Etching (RIE)), so as to obtain screen template gullies 18 for filling the first functional layer.

And 6, sequentially preparing an insulating layer 12, a second electrode layer 13 and a second transmission layer 14 on the surface of the thermoplastic polymer material layer 15 and in the grooves 18 of the reticulate pattern template layer by layer according to the sequence of the upper structure and the lower structure to obtain the first functional layer 9.

And 7, dissolving the thermoplastic polymer material layer imprinting material by using a solvent method, removing the electrode material of the first functional layer 9 falling on the thermoplastic polymer material layer imprinting material simultaneously, and finally leaving the network-shaped first functional layer 9 on the first transmission layer 8.

And 8, sequentially preparing a perovskite layer 10 and an antireflection layer 11 on the first functional layer 9, wherein the perovskite layer 10 fills the grid gaps of the first functional layer 9 and covers the first functional layer 9 until the manufacture of the perovskite and crystalline silicon triple-junction laminated solar cell is completed.

In order to facilitate the dissolving of the excess imprint material of the thermoplastic polymer material layer in step 7, so that the electrode material of the first functional layer 9 that falls on the imprint material of the thermoplastic polymer material layer is removed at the same time, the thickness of the thermoplastic polymer material layer 15 is greater than the total thickness of the first functional layer 9, i.e. greater than the sum of the thicknesses of the insulating layer 12, the third electrode 13 and the second transfer layer 14.

In this embodiment, the surface of the roller for imprinting is provided with a machined minute precision structure, the shape of which corresponds to the design of the cross-hatch pattern of the first functional layer. The pressure of the roller and the temperature of the roller/substrate are controlled, so that the roller rolls on the thermoplastic polymer material layer imprinting material continuously, and continuous reticulate patterns can be generated. The reticulate pattern comprises a square grid pattern, a circular square continuous pattern, a hexagonal square continuous pattern and the like. The roller type embossing method of the two-dimensional mesh electrode has the characteristics of continuously producing large-area precise two-dimensional mesh electrodes, is high in yield and processing precision, and provides powerful support for producing large-area two-dimensional mesh perovskite photovoltaic modules.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.