CN115835664A - Thin film photovoltaic series module and preparation method thereof - Google Patents

Thin film photovoltaic series module and preparation method thereof Download PDF

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CN115835664A
CN115835664A CN202211622855.9A CN202211622855A CN115835664A CN 115835664 A CN115835664 A CN 115835664A CN 202211622855 A CN202211622855 A CN 202211622855A CN 115835664 A CN115835664 A CN 115835664A
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李美珍
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Abstract

The invention belongs to the technical field of semiconductors and discloses a thin film photovoltaic series module and a preparation method thereof. The thin film photovoltaic series module is composed of a plurality of sub-cells; the sub-battery sequentially comprises a substrate, an electrode A, an absorption layer and an electrode B from bottom to top, wherein two unconnected electrodes B correspond to the electrode A, and two unconnected electrodes A correspond to the electrode B. The thin film photovoltaic series module reduces the dead zone occupied power generation area to below 1%, correspondingly improves the geometric filling factor of the thin film photovoltaic series module to above 99%, and accordingly improves the efficiency of the thin film photovoltaic series module in equal proportion; the side wall of the battery material is prevented from being exposed, and the stability is improved; high series resistance loss of the side wall is eliminated, and efficiency is improved. The preparation method of the thin film photovoltaic series module reduces etching procedures and manufacturing cost.

Description

Thin film photovoltaic series module and preparation method thereof
Technical Field
The invention belongs to the technical field of semiconductors, and particularly relates to a thin film photovoltaic series module and a preparation method thereof.
Background
Nowadays, the photoelectric conversion efficiency and reliability of new generation thin film photovoltaic cells such as organic-inorganic hybrid perovskite cells (PSC), organic solar cells (OPV), polymer solar cells and the like are increasingly approaching to those of mainstream crystalline silicon solar cells, and the advantages of low cost, easy manufacture, low carbon emission in the production process, capability of being made into flexible devices and the like are incomparable with those of crystalline silicon cells. In particular, organic-inorganic hybrid perovskite cells are widely recognized as the next generation thin film photovoltaic cells most promising alternatives to crystalline silicon cells.
The structure of a new generation of organic-containing thin film photovoltaic cell device represented by a perovskite solar cell can be mainly divided into two types, namely a conventional structure (n-i-p) and an inverted structure (p-i-n). In both structures, the absorbing layer (i) is sandwiched by the charge transport layer to form a sandwich structure. n is an Electron Transport Layer (ETL) and p is a Hole Transport Layer (HTL). There are structures that omit the p or n layer, replace it with an electrode or dope the absorbing layer (i) p or n type.
Interconnecting individual thin-film photovoltaic cells into modules typically involves connecting each sub-cell in series by means of (laser) etching and electrodeposition, requiring at least 3 etching steps and 1 electrodeposition step for a total of 4 steps (see document: met al., “Laser patterning of CIGSe solar cells using nano- and picosecond pulses-possibilities and challenges,” 28th Eur. Photovolt. Sol. Energy Conf. Exhib.No. September, pp.2302-2306, 2013, doi: 10.4229/28th EUPVSEC 2013-3BV.5.39). For different cell materials, it is sometimes necessary to add 4 etching processes and 2 deposition processes for 6 processes in order to protect or insulate the cell sidewalls. The area influenced by etching is a dead zone and does not contribute to photovoltaic power generation. The electrode deposition processes are typically evaporation and magnetron sputtering, and are used to connect the back electrode of a sub-cell (which may be referred to as electrode B) and the top electrode of an adjacent sub-cell (which may be referred to as electrode a). This is a well established interconnect or tandem approach that is widely adopted. However, disadvantages of this interconnection or tandem approach include: 1) The dead space area typically accounts for around 5% or more of the total power generation area, and the Geometric Fill Factor (GFF) of the assembly does not exceed 95.5% (see literature: S.H. Reddy, F.Di Giacomo, and A.Di Carlo, "Low-Temperature-Processed Stable Perovskite Solar Cells and Modules A Comprehensive Review"Adv. Energy Mater.Vol.12, no. 13, pp.1-37, 2022, doi: 10.1002/aenm.202103534.); 2) Evaporation and magnetron sputtering are non-conformal deposition processes, so the (laser) scribed cell material sidewalls cannot be effectively covered by the electrode layer, resulting in large series resistance (reduced component fill factor/efficiency); and conformal deposition processes such asAtomic Layer Deposition (ALD) is too costly and can cause damage to device materials; 3) Too small of a region where the back electrode layer contacts the top electrode layer results in greater contact resistance (resulting in reduced component fill factor/efficiency), and too large increases dead space area; 4) The (laser) etched cell material sidewalls can have an impact on the device stability (see literature: E. biet al., “Efficient Perovskite Solar Cell Modules with High Stability Enabled by Iodide Diffusion Barriers,” JouleVol. 3, no. 11, pp. 2748-2760, 2019, doi 10.1016/j.joule.2019.07.030.). Therefore, there is much room for improvement in the interconnection or series connection of thin film batteries.
Taking perovskite cells as an example, the prior art is high in efficiency and small in area<1cm 2 ) The FF of the cell is 82-86%, and after the assembly is made by traditional interconnection methods, the FF is often only 70-80% (see literature: y, dinget al., “Single-crystalline TiO2 nanoparticles for stable and efficient perovskite modules,” Nat. Nanotechnol., vol. 17, no. 6, pp. 598–605, 2022, doi: 10.1038/s41565-022-01108-1. S.Chen, X. Xiao, H. Gu, and J. Huang, “Iodine reduction for reproducible and high-performance perovskite solar cells and modules,” Sci. Adv., vol. 7, no. 10, pp. 1–7, 2021, doi: 10.1126/sciadv.abe8130. Y.Gao et al., “Can Nanosecond Laser Achieve High-Performance Perovskite Solar Modules with Aperture Area Efficiency Over 21%,” Adv. Energy Mater.Vol.2202287, pp.1-8, 2022, doi: 10.1002/aenm.202202287.), and the GFF is up to 96% or less.
Therefore, it is desirable to provide a new interconnection or series method of thin film photovoltaic cells, which solves the above-mentioned disadvantages of the conventional interconnection or series method.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. The thin film photovoltaic series module reduces the dead zone occupied power generation area to below 1% through a new series method, correspondingly improves the GFF (geometric filling factor) of the thin film photovoltaic series module to above 99%, and accordingly improves the efficiency of the thin film photovoltaic series module in equal proportion; the side wall of the battery material is prevented from being exposed, and the stability is improved; high series resistance losses of the sidewalls, and contact resistance losses of the back electrode contacting the top electrode are eliminated, eliminating the resulting loss of Fill Factor (FF) and efficiency. The etching process is reduced, and the manufacturing cost is reduced.
The invention conception of the invention is as follows: the thin film photovoltaic series module comprises a plurality of sub-cells (the sub-cells sequentially comprise a substrate, an electrode A, an absorption layer and an electrode B from bottom to top, two unconnected electrodes B correspond to the electrode A, and two unconnected electrodes A correspond to the electrode B) which are connected in series through the electrode A and the electrode B in a staggered manner (because the sub-cells correspond to the electrode A, the two unconnected electrodes B and the electrode B, the electrode A and the electrode B form a staggered corresponding relationship). Further, an electron transport layer and a hole transport layer are arranged between the electrode A and the absorption layer, and a hole transport layer and an electron transport layer are arranged between the electrode B and the absorption layer. The thin film photovoltaic series module reduces the dead zone occupied power generation area to below 1%, correspondingly improves the GFF (geometric filling factor) of the thin film photovoltaic series module to above 99%, and accordingly improves the efficiency of the thin film photovoltaic series module in equal proportion; the side wall of the battery material is prevented from being exposed, and the stability is improved; high series resistance loss of the sidewalls and contact resistance loss of the back electrode (electrode B) contacting the top electrode (electrode a) are eliminated, resulting in a loss of Fill Factor (FF) and efficiency. The preparation method of the thin film photovoltaic series module reduces etching procedures and manufacturing cost.
A first aspect of the invention provides a thin film photovoltaic tandem module.
Specifically, the thin film photovoltaic series module is composed of a plurality of sub-cells;
the sub-battery sequentially comprises a substrate, an electrode A, an absorption layer and an electrode B from bottom to top, wherein the electrode A corresponds to the two unconnected electrodes B, and the electrode B corresponds to the two unconnected electrodes A.
Preferably, an electron transport layer and a hole transport layer are further disposed between the electrode a and the absorption layer. The electron transport layer and the hole transport layer between the electrode a and the absorption layer may be selectively provided as needed.
Preferably, a hole transport layer and an electron transport layer are further disposed between the electrode B and the absorption layer. The hole transport layer and the electron transport layer between the electrode B and the absorption layer may be selectively provided as needed.
Preferably, an electron transport layer and a hole transport layer are further disposed between the electrode a and the absorption layer, and a hole transport layer and an electron transport layer are further disposed between the electrode B and the absorption layer. The corresponding positions of the upper side and the lower side of the absorption layer are an electron transport layer and a hole transport layer (namely, the hole transport layer between the electrode B and the absorption layer corresponds to the position of the electron transport layer between the electrode A and the absorption layer, and the electron transport layer between the electrode B and the absorption layer corresponds to the position of the hole transport layer between the electrode A and the absorption layer). The current can flow from the electrode B of one sub-cell, sequentially pass through the electron transport layer, the absorption layer, the hole transport layer and the electrode a below the electrode B, then flow from the electrode a into the adjacent sub-cell of the common electrode a, and the current continues to flow from the electrode a of the adjacent sub-cell of the common electrode a sequentially into the electron transport layer, the absorption layer, the hole transport layer and the electrode B. Current then flows from electrode B into the adjacent subcells of common electrode B, in such a way that the subcells are connected in series.
Preferably, the thin film photovoltaic tandem module is a solar cell module.
Further preferably, the solar cell module comprises at least one of a perovskite solar cell module, an organic solar cell module, a polymer solar cell module, and a cadmium telluride solar cell module.
Preferably, in the thin film photovoltaic tandem module, the number of the sub-cells is n, and n is a positive integer (e.g., an even number), for example, n is 2 to 10.
Preferably, the substrate comprises glass, metal or organic.
Preferably, the substrate is replaced with a superstrate.
Preferably, the electrode a is a conductive oxide or a conductive organic, such as indium-doped tin oxide (ITO).
Preferably, the thickness of the electrode A is 10nm-1 μm; further preferably, the thickness of the electrode A is 200-600nm.
Preferably, the electron transport layer comprises tin oxide and C 60 And 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthroline (CAS number: 4733-39-5). The composition of the electron transport layer between the electrode a and the absorbing layer and the composition of the electron transport layer between the electrode B and the absorbing layer may be the same or different.
Preferably, the hole transport layer includes at least one of poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] (CAS number 1333317-99-9), poly (3-hexylthiophene-2, 5-diyl) (CAS number 156074-98-5, 104934-50-1), and nickel oxide.
Preferably, the thickness of the electron transport layer is 1 to 200nm, preferably 10 to 100nm.
Preferably, the thickness of the hole transport layer is 1 to 200nm, preferably 10 to 100nm.
Preferably, the absorption layer is at least one of a perovskite absorption layer, an organic absorption layer, a polymer absorption layer and a cadmium telluride absorption layer. Such as Cs 0.17 FA 0.83 PbI 3 An absorption layer.
Preferably, the thickness of the absorption layer is 100 to 2000nm, preferably 300 to 700nm.
Preferably, the electrode B is a conductive oxide or metal, such as Indium Tin Oxide (ITO), gold, silver, or copper. Preferably, the thickness of the electrode B is 10nm to 1 μm, preferably 50 to 200nm.
Preferably, the dead zone occupation area of the thin film photovoltaic series module is reduced to below 1%.
Preferably, the GFF (geometric fill factor) of the thin film photovoltaic tandem module is increased to more than 99%.
The invention provides a preparation method of a thin film photovoltaic tandem module.
Specifically, the preparation method of the thin film photovoltaic series module comprises the following steps:
depositing an electrode A on a substrate;
blocking the electrode A;
preparing an absorption layer;
depositing an electrode B;
and blocking the electrode B to obtain the thin film photovoltaic series module.
Preferably, the deposition method includes at least one of evaporation, sputtering, atomic Layer Deposition (ALD), vapor deposition (CVD), remote plasma deposition (remote plasma deposition), printing, and spraying.
Preferably, the electrode may be a transparent or opaque electrode, such as indium-doped tin oxide (ITO).
Preferably, the method for blocking the electrode a includes at least one of laser ablation, probe scribing and photolithography.
Preferably, when the electrode a is deposited, a mask is used for shielding, so that a blocked electrode a can be formed, and the electrode a does not need to be blocked independently.
Preferably, the method for preparing the absorption layer includes at least one of evaporation, sputtering, atomic Layer Deposition (ALD), vapor deposition (CVD), remote plasma deposition (remote plasma deposition), printing, and spraying. Different absorbing layers can be deposited on the electron and hole transport layers on the electrode a, and the same absorbing layer can also be deposited.
Preferably, the method for depositing the electrode B includes at least one of evaporation, sputtering, atomic Layer Deposition (ALD), vapor deposition (CVD), remote plasma deposition (remote plasma deposition), printing, and spraying.
Preferably, the method for blocking the electrode B includes at least one of laser ablation, probe scribing, photolithography or mask covering.
Preferably, when the electrode B is deposited, a mask is used to block the electrode B, so that the electrode B does not need to be blocked separately. The blocked electrodes B correspond to the blocked electrodes A in a staggered mode. The size of the blocked electrode B is consistent with that of the blocked electrode A.
Preferably, after the electrode a is blocked and before the absorption layer is prepared, an electron transport layer is deposited on the electrode a, and a hole transport layer is deposited on the electrode a of another adjacent but unconnected block. The electron transport layer and the hole transport layer are alternately covered on all the blocked electrodes A. The electron transport layer and the hole transport layer may be deposited simultaneously or not.
Preferably, after the absorber layer is prepared, and before the electrode B is deposited, a hole transport layer and an electron transport layer are deposited on the absorber layer. The hole transport layers and the electron transport layers are arranged in a staggered mode, the hole transport layers deposited on the absorption layers correspond to the electron transport layers on the electrode A, and the electron transport layers deposited on the absorption layers correspond to the hole transport layers on the electrode A. The electron transport layer and the hole transport layer may be deposited simultaneously or non-simultaneously.
Preferably, the preparation method of the thin film photovoltaic tandem module comprises the following steps:
(1) Depositing an electrode A on a substrate;
(2) Blocking the electrode A;
(3) Depositing an electron transport layer on a partial area on one block of the electrode A, and depositing a hole transport layer on the rest area of the electrode A;
(4) Preparing an absorption layer on the electron transport layer and the hole transport layer in the step (3);
(5) Depositing a hole transport layer and an electron transport layer on the absorption layer in the step (4), so as to realize that the hole transport layer and the electron transport layer are arranged in a staggered manner, wherein the hole transport layer deposited on the absorption layer corresponds to the electron transport layer on the electrode A in position, and the electron transport layer deposited on the absorption layer corresponds to the hole transport layer on the electrode A in position;
(6) And depositing an electrode B, and blocking the electrode B to obtain the thin film photovoltaic series assembly. And (6) realizing that the hole transport layer and the electron transport layer are alternately positioned under the electrode B. And the hole transport layer under the electrode B corresponds to the electron transport layer on the electrode A, and the electron transport layer under the electrode B corresponds to the hole transport layer on the electrode A.
Preferably, in the step (3), an electronic transmission layer is deposited by firstly attaching an adhesive tape, then the adhesive tape is removed, a mask plate is used for shielding the electronic transmission layer from depositing the hole transmission layer, and the electrode a blocking in the step (2) can be performed after the step (3) is completed. The spacing between two adjacent but unconnected, blocked electrodes A is 5-60 μm, preferably 20-30 μm.
Preferably, in the step (4), an absorbing layer precursor solution is prepared, and then the absorbing layer precursor solution is deposited or coated on the electron transport layer and the hole transport layer in the step (3) to form the absorbing layer.
Preferably, the preparation method of the thin film photovoltaic tandem module comprises the following steps:
(1) Depositing indium-doped tin oxide (ITO) with the thickness of 300-500nm on a rectangular glass substrate through magnetron sputtering to form an electrode A;
(2) Sticking rectangular vacuum adhesive tapes at a position 0.5-1cm away from the edge of the glass substrate, wherein the vacuum adhesive tapes are parallel to the short edge of the glass substrate, and repeatedly sticking the vacuum adhesive tapes for several times, wherein the interval of each vacuum adhesive tape is 0.4-0.6cm;
(3) Preparing a tin oxide film on the electrode A to form an electron transport layer; removing the vacuum adhesive tape, covering the tin oxide film with a mask plate, and evaporating a poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] film to form a hole transport layer;
(4) The junction of part of the electron transport layer and the hole transport layer is etched by laser to block the electrode A on the glass substrate, the width of each block is 0.8-1.2cm, and the etching width is 20-60 mu m;
(5) Preparing an absorbing layer precursor solution, and then depositing or coating the absorbing layer precursor solution on the electron transport layer and the hole transport layer to form an absorbing layer;
(6) Covering all blocks of the electron transport layer with a mask plate, and evaporating C 60 And BCP (2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthroline), form electronsA transmission layer, removing the mask plate; covering all the blocks with mask plate, evaporating poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine]A thin film forming a hole transport layer;
(7) Covering the junction position of the electron transport layer and the hole transport layer and two long sides and one short side of the glass substrate with a mask plate, and evaporating silver to form an electrode B, namely preparing the thin film photovoltaic series assembly.
Preferably, in step (7), the line width of the central line is 20 to 30 μm. The purpose of step (7) is to form a blocked electrode B.
Preferably, in the step (7), the line width of the two long sides of the glass substrate covered with the mask plate is 0.3-0.5cm, and the line width of the short side is 0.5-1cm.
Compared with the prior art, the invention has the following beneficial effects:
the thin film photovoltaic series module comprises a plurality of sub-cells (the sub-cells sequentially comprise a substrate, an electrode A, an absorption layer and an electrode B from bottom to top, wherein two unconnected electrodes B correspond to the electrode A, and two unconnected electrodes A correspond to the electrode B) which are connected in series through the electrode A and the electrode B in a staggered and corresponding mode. Further, an electron transport layer and a hole transport layer are arranged between the electrode A and the absorption layer, and a hole transport layer and an electron transport layer are arranged between the electrode B and the absorption layer. The thin film photovoltaic series module reduces the dead zone occupied power generation area to below 1%, correspondingly improves the GFF (geometric filling factor) of the thin film photovoltaic series module to above 99%, and accordingly improves the efficiency of the thin film photovoltaic series module in equal proportion; the side wall of the battery material is prevented from being exposed, and the stability is improved; high series resistance loss of the sidewalls and contact resistance loss of the back electrode (electrode B) contacting the top electrode (electrode a) are eliminated, resulting in a loss of Fill Factor (FF) and efficiency. The preparation method of the thin film photovoltaic series module reduces etching procedures and manufacturing cost.
Drawings
Fig. 1 is a schematic structural diagram of a thin film photovoltaic tandem module manufactured in example 1 of the present invention.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
The starting materials, reagents or apparatuses used in the following examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.
Example 1
A thin film photovoltaic tandem module is composed of 6 sub-cells;
the sub-battery sequentially comprises a substrate, an electrode A, an absorption layer and an electrode B from bottom to top, wherein two unconnected electrodes B correspond to the electrode A, and two unconnected electrodes A correspond to the electrode B;
an electron transport layer and a hole transport layer are also arranged between the electrode A and the absorption layer, and a hole transport layer and an electron transport layer are also arranged between the electrode B and the absorption layer. The corresponding positions of the upper side and the lower side of the absorption layer are an electron transport layer and a hole transport layer. The current can flow from the electrode B of one sub-cell, sequentially pass through the electron transport layer, the absorption layer, the hole transport layer and the electrode a below the electrode B, then flow from the electrode a into the adjacent sub-cell of the common electrode a, and the current continues to flow from the electrode a of the adjacent sub-cell of the common electrode a sequentially into the electron transport layer, the absorption layer, the hole transport layer and the electrode B. Current then flows from electrode B into the adjacent subcells of common electrode B, in such a way that the subcells are connected in series.
The substrate is glass.
The electrode A is indium-doped tin oxide (ITO).
The electron transport layer on the electrode A was composed of tin oxide, and the electron transport layer on the absorption layer was composed of C 60 And 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthroline.
The hole transport layer is composed of a poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] layer.
The electrode B is silver.
Fig. 1 is a schematic structural diagram of a thin film photovoltaic tandem module manufactured in example 1 of the present invention. As can be seen from fig. 1, from bottom to top, an electrode a is disposed on a substrate, a hole transport layer and an electron transport layer are disposed on the electrode a, an absorption layer is disposed on the hole transport layer and the electron transport layer, the electron transport layer and the hole transport layer are disposed on the absorption layer, and an electrode B is disposed on the electron transport layer and the hole transport layer. The thin film photovoltaic series module comprises a sub-cell 1, a cell 2, a cell 3, a cell 4, a cell 5 and a cell 6.
To further illustrate that the thin film photovoltaic tandem module of the present invention can be formed by connecting a plurality of sub-cells in series, the sub-cells that can be further connected in series are schematically shown on the left side of the sub-cell 1 and the right side of the sub-cell 6 in fig. 1.
The current can flow from the electrode B of one sub-cell, sequentially pass through the electron transport layer, the absorption layer, the hole transport layer and the electrode A below the electrode B, then flow from the electrode A into the adjacent sub-cell of the common electrode A, and the current continues to flow from the electrode A of the adjacent sub-cell of the common electrode A into the electron transport layer, the absorption layer, the hole transport layer and the electrode B sequentially. Current then flows from electrode B into the adjacent subcells of common electrode B, in such a way that the subcells are connected in series.
A preparation method of a thin film photovoltaic series module comprises the following steps:
(1) Depositing indium-doped tin oxide (ITO) with the thickness of 500nm on a rectangular (5.6 cm in length and 5cm in width) clean glass substrate by magnetron sputtering (parameter in the deposition process: background gas pressure is 10) -6 T, the working pressure is 1.5mT, the power is 100W, the speed is 1 nm/s), an electrode A is formed, and then the electrode A is placed into a UVO chamber (an ultraviolet ozone cleaning chamber) to be cleaned for 15 minutes;
(2) Sticking a residue-free rectangular vacuum adhesive tape (the width of the vacuum adhesive tape is 0.6cm, the length of the vacuum adhesive tape exceeds 5 cm) on an electrode A at a position 0.5cm away from the edge of the glass substrate by using a sticking machine, wherein the vacuum adhesive tape is parallel to the short edge of the glass substrate, and then repeatedly sticking the vacuum adhesive tapes for 2 times, wherein the interval of each vacuum adhesive tape is 0.6cm;
(3) On the electrode APreparing tin oxide film (the method for preparing tin oxide film is conventional method, such as chemical bath and sintering method, and the specific process can be found in T. Buet al., “Lead halide-templated crystallization of methylamine-free perovskite for efficient photovoltaic modules,” Science (80).Vol. 372, no. 6548, pp. 1327-1332, 2021, doi: 10.1126/science. Abh 1035) to form an electron transport layer (vacuum tape removed before sintering); covering the tin oxide film with a mask, evaporating 5nm thick poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine]A thin film forming a hole transport layer;
(4) The electrode A on the glass substrate is blocked at the junction of the electron transport layer and the hole transport layer by laser etching (the specific parameters of the laser etching refer to P1 in the table 1), the etching width is 60 mu M so as to ensure that the two blocks are not conductive (the resistance is more than 1M omega), the two blocks are translated for 12mm along the long edge of the glass, and the step is repeated;
(5) Filling with inert nitrogen gas (water vapor) by using analytical balance<100ppm, oxygen gas<100 ppm) into a glove box, 142.8mg of FAI (formamidine iodide), 44.2mg of CsI, 461mg of PbI were weighed out 2 、27.8mg PbCl 2 、2.8mg KPF 6 Dissolved in 96. Mu.L NMP (N-methylpyrrolidone) and 500. Mu.L DMF (dimethylformamide) and shaken until completely dissolved to prepare Cs 0.17 FA 0.83 PbI 3 Coating the absorption layer precursor solution on the electron transport layer and the hole transport layer in the step (4) through slit coating deposition coating (parameters in the coating process include that the distance between a coating head and the electron transport layer and the hole transport layer is 0.2mm, the coating speed is 3.5mm/s, the solution outlet speed is 1.1 mu L/s, the distance between an air knife outlet and a coating outlet is 10cm, the distance between the air knife outlet and the electron transport layer and the hole transport layer is 3mm, the included angle between the air knife outlet and the electron transport layer and the hole transport layer is 60 degrees, the direction far away from the coating head faces, the gas is dry compressed air, the air pressure is 0.3MPa, the air outlet rate is 35mm/s, the coating environment temperature is 20 +/-2 ℃, and the relative humidity is 15 +/-5 percent) to form the absorption layer;
(6) Covering all the blocks of the electron transport layer with a maskVapor deposition (vapor deposition rate of 0.05nm/s, background gas pressure of 10) -6 T) 20nm thick C 60 And BCP (2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthroline) with the thickness of 5nm to form an electron transport layer, and removing the mask plate; then covering all the blocks where the hole transport layer is located with a mask plate, and evaporating (the evaporation rate is 0.5nm/s, the background air pressure is 10) -6 T) Poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine with a thickness of 20nm]A thin film is formed, a hole transmission layer is formed, and the mask plate is removed;
(7) Covering the center line (line width of 30 μm) position of block A along the short side direction of the glass substrate, two long sides and one short side of the glass substrate with a mask (line width of two long sides of the glass substrate covered with the mask is 0.5cm, line width of the short side is 1 cm), evaporating (evaporation rate of 0.5nm/s, background gas pressure of 10 -6 T) 100nm thick silver, and forming an electrode B, namely preparing the thin film photovoltaic series module.
One window area is 3.6cm x 4cm (the window area is the size of the window area of the whole thin film photovoltaic tandem module, i.e. the active area plus dead zone of all 6 subcells, but not including the edge area not covered by the upper and lower electrodes), the module contains 6 0.6cm wide subcells, of which 3 subcells of conventional structure and 3 subcells of inverted structure are staggered and connected in series. The region of the perovskite absorption layer covered by both the electrode a and the electrode B is an active region, and the region not covered by both the electrodes is a dead region. GFF [ GFF = 1-dead zone width/(effective zone width + dead zone width) ] was calculated to be 99.4%.
Example 2
A preparation method of a thin film photovoltaic series module comprises the following steps:
(1) Depositing indium-doped tin oxide (ITO) with the thickness of 500nm on a rectangular (5.6 cm in length and 5cm in width) clean glass substrate by magnetron sputtering (parameter in the deposition process: background gas pressure is 10) -6 T, the working pressure is 1.5mT, the power is 100W, the speed is 1 nm/s), an electrode A is formed, and then the electrode A is placed into a UVO chamber to be cleaned for 15 minutes;
(2) Sticking a residue-free rectangular vacuum adhesive tape (the width of the vacuum adhesive tape is 0.62cm, the length of the vacuum adhesive tape exceeds 5 cm) on an electrode A at a position 0.5cm away from the edge of the glass substrate by using a sticking machine, wherein the vacuum adhesive tape is parallel to the short edge of the glass substrate, and then repeatedly sticking the vacuum adhesive tape for 2 times, wherein the interval of each vacuum adhesive tape is 0.58cm;
(3) The tin oxide film is prepared on the electrode A (the method for preparing the tin oxide film is a conventional method, for example, a method of adopting a chemical bath and sintering, and the specific process can be seen in the literature: T. Buet al., “Lead halide-templated crystallization of methylamine-free perovskite for efficient photovoltaic modules,” Science (80).Vol. 372, no. 6548, pp. 1327-1332, 2021, doi: 10.1126/science. Abh 1035) to form an electron transport layer (vacuum tape removed before sintering); covering the tin oxide film with a mask, evaporating 5nm thick poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine]A thin film forming a hole transport layer;
(4) The electrode A on the glass substrate is blocked at the junction of the electron transport layer and the hole transport layer by laser etching (the specific parameters of the laser etching are shown in P1 in Table 1), the etching width is 60 mu M so as to ensure that the two blocks are not conductive (the resistance is more than 1M omega), the two blocks are translated for 12mm along the long edge of the glass, and the step is repeated;
(5) Filling with inert nitrogen gas (water vapor) by using analytical balance<100ppm, oxygen gas<100 ppm) into a glove box, 142.8mg of FAI, 44.2mg of CsI, 461mg of PbI 2 、27.8mg PbCl 2 、2.8mg KPF 6 Dissolved in 96. Mu.L NMP (N-methylpyrrolidone) and 500. Mu.L DMF (dimethylformamide) and shaken until completely dissolved to prepare Cs 0.17 FA 0.83 PbI 3 An absorption layer precursor solution is coated by slit coating deposition (parameters in the coating process include that the distance between a coating head and an electron transport layer and a hole transport layer is 0.2mm, the coating speed is 3.5mm/s, the solution outlet speed is 1.1 mu L/s, the distance between an air knife outlet and a coating outlet is 10cm, the distance between the air knife outlet and the electron transport layer and the hole transport layer is 3mm, the included angle between the air knife outlet and the electron transport layer and the hole transport layer is 60 degrees, the gas faces to the direction far away from the coating head, is dry compressed air, the air pressure is 0.3MPa, the gas outlet rate is high, and the gas outlet rate is high35mm/s, the coating environment temperature is 20 +/-2 ℃, and the relative humidity is 15 +/-5 percent) to form an absorption layer on the electron transport layer and the hole transport layer in the step (4);
(6) Covering all the blocks of the electron transport layer with a mask plate, and evaporating at a rate of 0.05nm/s under a background pressure of 10 -6 T) 20nm thick C 60 And BCP (2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthroline) with the thickness of 5nm to form an electron transport layer, and removing the mask plate; then covering all the blocks where the hole transport layer is located with a mask plate, and evaporating (the evaporation rate is 0.5nm/s, the background air pressure is 10) -6 T) Poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine with a thickness of 20nm]A thin film is formed, a hole transmission layer is formed, and the mask plate is removed;
(7) Covering the boundary position (line width is 30 μm) of partial electron transport layer and hole transport layer along the short side direction of the glass substrate, two long sides and one short side of the glass substrate (line width of two long sides of the glass substrate covered by the mask plate is 0.5cm, line width of the short side is 1 cm), evaporating (evaporation rate is 0.5nm/s, background air pressure is 10) -6 T) 100nm thick silver, and forming an electrode B, namely preparing the thin film photovoltaic series module.
One window area was 3.6cm x 4cm and the assembly contained 6 subcells, with 3 subcells of conventional construction, 0.58cm wide, and 3 subcells of inverted construction, 0.62cm wide, staggered, in series with each other. The region of the perovskite absorption layer covered by both the electrode a and the electrode B is an active region, and the region not covered by both the electrodes is a dead region. GFF [ GFF = 1-dead zone width/(effective zone width + dead zone width) ] was calculated to be 99.4%.
COMPARATIVE EXAMPLE 1 (conventional Structure)
A preparation method of a thin film photovoltaic series module comprises the following steps:
(1) Depositing indium-doped tin oxide (ITO) with the thickness of 500nm on a clean rectangular glass substrate (the length is 5.6cm, the width is 5 cm) by magnetron sputtering (the parameter in the deposition process is that the background air pressure is 10) -6 T, working pressure is 1.5mT, power is 100W, speed is 1 nm/s), forming electrode A, and laser etching (specific parameters of laser etching)See P1 in table 1) the ITO layer is blocked, and the blocks are not electrically conductive (resistance)>1M omega), the size is 0.6cm wide, an etching line is parallel to the short side of the glass, the etching width is 40 mu M, then the glass is placed into a UVO chamber to be cleaned for 15 minutes, and then the glass is placed into the UVO chamber to be cleaned for 15 minutes;
(2) The tin oxide film is formed on the electrode A (the method for forming the tin oxide film is a conventional method, for example, a method using a chemical bath, and the specific process is described in T. Buet al., “Lead halide-templated crystallization of methylamine-free perovskite for efficient photovoltaic modules,” Science (80).Vol. 372, no. 6548, pp. 1327-1332, 2021, doi: 10.1126/science.abh 1035) forming an electron transport layer;
(3) Filling with inert nitrogen gas (water vapor) by using an analytical balance<100ppm, oxygen gas<100 ppm) into a glove box, 142.8mg of FAI, 44.2mg of CsI, 461mg of PbI 2 、27.8mg PbCl 2 、2.8mg KPF 6 Dissolved in 96. Mu.L NMP (N-methylpyrrolidone) and 500. Mu.L DMF (dimethylformamide) and shaken until completely dissolved to prepare Cs 0.17 FA 0.83 PbI 3 Coating the absorption layer precursor solution on the electron transport layer and the hole transport layer in the step (2) through a slit coating deposition coating (parameters in the coating process include that the distance between a coating head and the electron transport layer and the hole transport layer is 0.2mm, the coating speed is 3.5mm/s, the solution outlet speed is 1.1 mu L/s, the distance between an air knife outlet and a coating outlet is 10cm, the distance between the air knife outlet and the electron transport layer and the hole transport layer is 3mm, the included angle between the air knife outlet and the electron transport layer and the hole transport layer is 60 degrees, the direction far away from the coating head faces, the gas is dry compressed air, the air pressure is 0.3MPa, the air outlet rate is 35mm/s, the coating environment temperature is 20 +/-2 ℃, and the relative humidity is 15 +/-5 percent) to form the absorption layer;
(4) Vapor deposition (vapor deposition rate of 0.5nm/s, background pressure of 10) -6 T) Poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine with a thickness of 20nm]A thin film forming a hole transport layer;
(5) Etching a line parallel to the P1 (namely a P2 line) from the glass surface at a position 200 mu m away from the P1 line (the line formed under the P1 laser etching parameters is called as a P1 line) by using laser (the specific parameters of the laser etching are shown in the P2 in the table 1), completely removing other layers except the ITO layer, and enabling the line width to be 255 mu m;
(6) Covering two long sides (line width of 0.5 cm) and one short side (line width of 1 cm) of the glass with a mask plate, and evaporating 100nm silver layer at a rate of 0.05nm/s and a background air pressure of 10 -6 T；
(7) A line parallel to the P2 line (namely, a P3 line, the specific parameters of laser etching are shown in P3 in Table 1) is etched from the glass surface by using laser at the position of 100 mu m away from the P2 line and the side of the P2 line far away from the P1 line, all layers except the glass are completely removed, and the line width is 64 mu m.
One window area was 3.6cm x 4cm and comprised an assembly of 6 0.6cm wide subcells of conventional construction connected in series with each other. The GFF was calculated to be 91.7% by the formula.
COMPARATIVE EXAMPLE 2 (inverted structure)
A preparation method of a thin film photovoltaic series module comprises the following steps:
(1) Depositing indium-doped tin oxide (ITO) with the thickness of 500nm on a rectangular (5.6 cm in length and 5cm in width) clean glass substrate by magnetron sputtering (parameter in the deposition process: background gas pressure is 10) -6 T, working pressure is 1.5mT, power is 100W, speed is 1 nm/s), electrode A is formed, laser etching (the specific parameters of laser etching refer to P1 in Table 1) is used for blocking the ITO layer, and the blocks are not conductive (resistance)>1M omega), the size is 0.6cm wide, an etching line is parallel to the short side of the glass, the etching width is 40 mu M, then the glass is placed into a UVO chamber to be cleaned for 15 minutes, and then the glass is placed into the UVO chamber to be cleaned for 15 minutes;
(2) Vapor deposition (vapor deposition rate of 0.05nm/s, background pressure of 10) -6 T) 5nm thick poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine]A thin film forming a hole transport layer;
(3) Filling with inert nitrogen gas (water vapor) by using an analytical balance<100ppm, oxygen<100 ppm) into a glove box, 142.8mg of FAI, 44.2mg of CsI, 461mg of PbI 2 、27.8mg PbCl 2 、2.8mg KPF 6 Dissolved in 96. Mu.L of NMP (N-methyl)Pyrrolidone) and 500. Mu.L of DMF (dimethylformamide) and shaken until completely dissolved to prepare Cs 0.17 FA 0.83 PbI 3 Coating the absorption layer precursor solution on the electron transport layer and the hole transport layer in the step (2) through a slit coating deposition coating (parameters in the coating process include that the distance between a coating head and the electron transport layer and the hole transport layer is 0.2mm, the coating speed is 3.5mm/s, the solution outlet speed is 1.1 mu L/s, the distance between an air knife outlet and a coating outlet is 10cm, the distance between the air knife outlet and the electron transport layer and the hole transport layer is 3mm, the included angle between the air knife outlet and the electron transport layer and the hole transport layer is 60 degrees, the direction far away from the coating head faces, the gas is dry compressed air, the air pressure is 0.3MPa, the air outlet rate is 35mm/s, the coating environment temperature is 20 +/-2 ℃, and the relative humidity is 15 +/-5 percent) to form the absorption layer;
(4) Vapor deposition (vapor deposition rate of 0.05nm/s, background pressure of 10) -6 T) 20nm thick C 60 And BCP (2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthroline) with a thickness of 5nm to form an electron transport layer;
(5) Etching a line (namely a P2 line) parallel to the P1 line (a line formed by etching under the laser parameter of the P1 is called as a P1 line) from the glass surface at a distance of 190 mu m from the P1 line (the line formed by etching under the laser parameter of the P1 is called as the P1 line) by using laser (the laser parameter refers to P2 in the table 1), completely removing other layers except the ITO layer, and enabling the line width to be 238 mu m;
(6) Covering two long sides (line width of 0.5 cm) and one short side (line width of 1 cm) of the glass with a mask plate, and evaporating 100nm silver layer at a rate of 0.05nm/s and a background air pressure of 10 -6 T；
(7) A line parallel to the P2 line (namely, a P3 line, the specific parameters of laser etching are shown in P3 in Table 1) is etched from the glass surface by using laser at the position 110 mu m away from the P2 line on the side of the P2 line far away from the P1 line, all layers except the glass are completely removed, and the line width is 88 mu m.
One window area was 3.6cm x 4cm and contained 6 modules of 0.6cm wide subcells in an inverted configuration in series with each other. The GFF was calculated to be 91.6% by the formula.
Table 1: laser etching process parameters
Pulse of light Wavelength of light Energy density Scanning speed Frequency of
P1 400ps 1064nm 7.33J/cm 2 400mm/s 300kHz
P2 800fs 532nm 1.5J/cm 2 400mm/s 300kHz
P3 400ps 532nm 3.04J/cm 2 5000mm/s 300kHz
Product effectiveness testing
The thin film photovoltaic series modules prepared in the examples and the comparative examples are tested under the conditions of sunlight intensity, light source AAA level and window area of 14.4cm 2 (in the test, sunlight was incident from the bottom surface of the substrate). The scan range is from 7V to-0.1V, and the scan rate is 1V/s. The test results are shown in Table 2.
Table 2: thin film photovoltaic tandem module efficiency and parameter results
14.4cm 2 (6 sub-batteries) Voc（V） J SC (mA/cm 2 ) FF（%） GFF（%） PCE（%）
Example 1 6.50 3.4 77.1 99.4 16.9
Example 2 6.51 3.51 77.2 99.4 17.53
Comparative example 1 6.52 3.6 72 91.7 15.4
Comparative example 2 6.4 3.4 70.1 91.6 13.97
Voc in table 2 represents an open circuit voltage, jsc represents a short circuit current density, FF represents a fill factor, GFF represents a geometric fill factor, and PCE represents energy conversion efficiency.
As can be seen from table 2, the geometric fill factor and energy conversion efficiency of the thin film photovoltaic tandem modules of examples 1-2 are significantly higher than those of comparative examples 1-2.

Claims (10)

1. A thin film photovoltaic tandem module, characterized in that it is composed of a plurality of sub-cells;
the sub-battery sequentially comprises a substrate, an electrode A, an absorption layer and an electrode B from bottom to top, wherein the electrode A corresponds to the two unconnected electrodes B, and the electrode B corresponds to the two unconnected electrodes A.
2. The thin-film photovoltaic tandem module of claim 1 wherein an electron transport layer and a hole transport layer are further disposed between said electrode a and the absorber layer.
3. The thin film photovoltaic tandem module according to claim 1, wherein a hole transport layer and an electron transport layer are further provided between the electrode B and the absorber layer.
4. The thin film photovoltaic tandem module according to claim 1, wherein an electron transport layer and a hole transport layer are further disposed between the electrode a and the absorber layer, and a hole transport layer and an electron transport layer are further disposed between the electrode B and the absorber layer.
5. The thin film photovoltaic tandem module of claim 1 wherein said thin film photovoltaic tandem module is a solar cell module, said solar cell module comprising at least one of a perovskite solar cell module, an organic solar cell module, a polymer solar cell module, a cadmium telluride solar cell module.
6. The thin film photovoltaic tandem module of claim 5 wherein said electron transport layer comprises tin oxide, C 60 And 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthroline; the hole transport layer comprises poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine]At least one of poly (3-hexylthiophene-2, 5-diyl) and nickel oxide; the absorption layer is at least one of a perovskite absorption layer, an organic matter absorption layer, a polymer absorption layer and a cadmium telluride absorption layer.
7. A method of making a thin film photovoltaic tandem module as claimed in any of claims 1 to 6 comprising the steps of:
depositing an electrode A on a substrate;
blocking the electrode A;
preparing an absorption layer;
depositing an electrode B;
and blocking the electrode B to obtain the film photovoltaic series assembly.
8. The preparation method according to claim 7, characterized in that when the electrode A is deposited, a mask plate shielding method is adopted to form a blocked electrode A, and the electrode A does not need to be blocked independently; when the electrode B is deposited, a mask plate shielding method is adopted to form the blocked electrode B, and the electrode B does not need to be blocked independently; the blocked electrodes B correspond to the blocked electrodes A in a staggered mode.
9. The method of claim 7, comprising the steps of:
(1) Depositing an electrode A on a substrate;
(2) Blocking the electrode A;
(3) Depositing an electron transport layer on a partial area on one block of the electrode A, and depositing a hole transport layer on the rest area of the electrode A;
(4) Preparing an absorption layer on the electron transport layer and the hole transport layer in the step (3);
(5) Depositing a hole transport layer and an electron transport layer on the absorption layer in the step (4) to realize staggered arrangement of the hole transport layer and the electron transport layer, wherein the hole transport layer deposited on the absorption layer corresponds to the electron transport layer on the electrode A, and the electron transport layer deposited on the absorption layer corresponds to the hole transport layer on the electrode A;
(6) And depositing an electrode B, and blocking the electrode B to obtain the thin film photovoltaic series assembly.
10. The method of claim 7, comprising the steps of:
(1) Depositing indium-doped tin oxide with the thickness of 300-500nm on a rectangular glass substrate by magnetron sputtering to form an electrode A;
(2) Sticking rectangular vacuum adhesive tapes at a position 0.5-1cm away from the edge of the glass substrate, wherein the vacuum adhesive tapes are parallel to the short edge of the glass substrate, and repeatedly sticking the vacuum adhesive tapes for several times, wherein the interval of each vacuum adhesive tape is 0.4-0.6cm;
(3) Preparing a tin oxide film on the electrode A to form an electron transport layer; removing the vacuum adhesive tape, covering the tin oxide film by using a mask plate, and evaporating a poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] film to form a hole transport layer;
(4) The junction of part of the electron transport layer and the hole transport layer is etched by laser to block the electrode A on the glass substrate, the width of each block is 0.8-1.2cm, and the etching width is 20-60 mu m;
(5) Preparing an absorbing layer precursor solution, and then depositing or coating the absorbing layer precursor solution on the electron transport layer and the hole transport layer to form an absorbing layer;
(6) Covering all blocks of the electron transport layer with a mask plate, and evaporating C 60 And 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthroline to form an electron transport layer, and removing the mask plate; covering all the blocks with mask plate, evaporating poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine]A thin film forming a hole transport layer;
(7) Covering the junction position of the electron transport layer and the hole transport layer and two long sides and one short side of the glass substrate with a mask plate, and evaporating silver to form an electrode B, namely preparing the thin film photovoltaic series assembly.
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