Perovskite layer, method for manufacturing the same, and solar cell

Abstract

The present invention relates to a perovskite layer, a method for manufacturing thereof and a solar cell. The present invention relates to a perovskite layer for a solar cell, said perovskite layer comprising a mixture of a halide perovskite and a sulfonylnaphthoquinone compound, said sulfonylnaphthoquinone compound having the structure of formula (I), wherein: R1 is independently selected from one of OM, OR4 and NR5R6, wherein M is a cation, R4, R5 and R6 are independently selected from hydrogen and a substituent; and R2 and R3 are independently selected from hydrogen and a substituent, or R2 and R3 can form a fused ring. A method for manufacturing said perovskite layer and a solar cell comprising a first active layer of said perovskite layer are also proposed.

Description

Technical Field

[0001] This invention relates to perovskite layers, particularly but not exclusively to perovskite layers comprising a mixture of halide perovskite and sulfonylnaphthoquinone compounds; and methods for manufacturing perovskite layers. The invention also relates to solar cells comprising a first active layer of perovskite layer. Background Technology

[0002] Metal halide perovskite solar cells (PSCs) have become promising photovoltaic (PV) technologies due to their high absorption coefficient, low exciton binding energy, high carrier mobility, long carrier diffusion length, and bipolar charge transport. PSCs can typically be configured as single-junction solar cells and multi-junction (or series) solar cells (i.e., solar cells composed of two or more sub-cells). In particular, because the series configuration allows for combinations of sub-cells with different properties (such as combinations of wide-bandgap and low-bandgap sub-cells, which can meet the needs of both high-energy and low-energy photons during operation), PSCs with a series configuration are believed to have a higher power conversion efficiency (PCE) compared to PSCs with a single-junction configuration. For example, in the case of a desired bandgap (E0), PSCs with a series configuration are more likely to achieve higher PCE. g In perovskite-organic tandem solar cells (PO-TSCs) with forecells of approximately 1.8 to 1.9 eV, the PCE can be increased from approximately 15% to approximately 24%, especially when using I / Br mixed perovskites. Figure 1A ).

[0003] However, the perovskite layer of PSCs typically exhibits severe halide phase segregation during device operation. This is believed to result from halide migration from halide vacancies within the perovskite film, posing a significant obstacle to the long-term stability of perovskite-based PSCs. Furthermore, under continuous illumination and / or heating, Pb in the perovskite... 2+ The ions are also easily reduced to metallic Pb. 0 This is detrimental to device efficiency and stability.

[0004] Although there are reports of suppressing halide segregation through methods such as crystallization control, defect passivation, surface modulation, and strain engineering, it is believed that these strategies cannot simultaneously address Pb segregation. 2+ Easily reduced to Pb 0 The problems are numerous. Furthermore, the additives used in the reported strategies are either inorganic compounds whose properties are believed to be difficult to tune through synthesis, or sacrificial agents believed to disappear quickly after taking effect. Nevertheless, making it easy to tune the properties of additives to eliminate different defects and to ensure they function sustainably without introducing additional, deeper defects remains a challenge.

[0005] This invention seeks to eliminate or at least mitigate these drawbacks by providing novel or otherwise improved active layers for solar cells, particularly enabling selective iodine (I₂) reduction and metallic lead (Pb) reduction in a sustainable manner. 0 Oxidized active perovskite layer. Summary of the Invention

[0006] In a first aspect of the invention, a perovskite layer for a solar cell is provided, comprising a mixture of halide perovskite and a sulfonylnaphthoquinone compound having the structure of formula (I):

[0007]

[0008] Formula (I),

[0009] in:

[0010] R1 is independently selected from one of OM, OR4, and NR5R6, wherein M is a cation, and R4, R5, and R6 are independently selected from hydrogen and substituents; and R2 and R3 are independently selected from hydrogen and substituents, or R2 and R3 may form a fused ring.

[0011] Optionally, M can choose from the following groups: H + Na + K + Cs + 、Rb + 、Sr 2+ Ca 2+ Ni 2+ Cu 2+ Co 2+ Zn 2+ Mg 2+ Ba 2+ Li + The compounds are ammonium ions and ammonium ions; R2, R3, R4, R5 and R6 are independently selected from the group consisting of: hydrogen, substituted or unsubstituted C1 to C4 alkyl, substituted or unsubstituted C2 to C6 alkenyl, substituted or unsubstituted C2 to C6 alkynyl, halogen, substituted or unsubstituted C6 to C10 aryl, -CN, -C(=O)OH, -C(=O)H, -C(=O)R7, -OR7, -SH, -SR7, -NH2, -NHR6, -N(R7)2, -Si(R7)3, -OSi(R7)3, -S(O)OH and -P(O)(OH)2, wherein R7 is an alkyl or phenyl; and when R2 and R3 form a fused ring, it contains a substituted or unsubstituted 6- to 14-membered ring.

[0012] In an optional embodiment, the sulfonylnaphthoquinone compound is any one of formula (II), (III), (IV), (V), (VI), or (VII):

[0013]

[0014] Equation (II),

[0015]

[0016] Equation (III),

[0017]

[0018] Formula (IV),

[0019]

[0020] Equation (V),

[0021]

[0022] Formula (VI), or

[0023]

[0024] Equation (VII),

[0025] R1 is defined above; and n is 1-1000.

[0026] Optionally, the sulfonylnaphthoquinone compound of formula (II) is selected from any one of formula (VIII), formula (IX) or formula (X):

[0027]

[0028] Equation (VIII),

[0029]

[0030] Formula (IX), or

[0031]

[0032] Equation (X),

[0033] Where M is H + R4 is a C1 to C4 alkyl group; R5 and R6 are independently selected from hydrogen and C1 to C4 alkyl groups.

[0034] In one embodiment of the invention, the sulfonyl naphthoquinone compound of formula (VIII) is selected from any one of formulas (VIIIa), (VIIIb), and (VIIIc):

[0035]

[0036] Equation (VIIIa),

[0037]

[0038] Equation (VIIIb), and

[0039]

[0040] Formula (VIIIc).

[0041] In an optional embodiment, the sulfonylnaphthoquinone compound includes the structure of formula (IXa):

[0042]

[0043] Formula (IXa).

[0044] In an optional embodiment, the sulfonylnaphthoquinone compound includes the structure of formula (Xa):

[0045]

[0046] Equation (Xa).

[0047] Optionally, halide perovskites contain [A] +1 B +2 X -1 The grain structure of [3], wherein A +1 A-site monovalent cation, B +2 It is a B-site divalent cation, and X -1 It is a halide anion.

[0048] Optionally, the monovalent cation at site A is selected from the formamidinium ion (FA). + ), methylammonium ion (MA + ), Ethylammonium (EA) + ), guanidine ion (GA) + ), Cs + 、Rb + The group consisting of the group and its combination; the B-site divalent cation is selected from Pb. 2+ Sn 2+ 、Ge 2+ The group consisting of the group and its combinations; and the halide anion selected from I - ,Br - Cl - Groups composed of [them] and their combinations.

[0049] In an optional implementation, the halide perovskite is selected from CsPb. 0.5 Sn 0.5 I3, FAPbI3, MA 0.25 FA 0.75 PbI 2.2 Br 0.6 Cl 0.2 Cs 0.02 FA 0.96 MA 0.02 PbI 0.99 Cl 0.01 MAPb 0.92 Sn 0.08 I3, (FA) 0.95 MA 0.05 ) 0.95 Cs 0.05 Pb(I 0.96 Br 0.04 3. Rb 0.1 FA 0.8 GA 0.1 Pb 0.6 Ge 0.4 I3 and (FA 0.92 MA 0.08 ) 0.9 Cs 0.1 Pb(I 0.92 Br 0.08 )3 and Cs 0.2 FA 0.8 Pb(I 0.6 Br 0.4 Any one of 3.

[0050] Optional, [A +1 B +2 X -1 The grain structure of [3] includes grain boundaries where sulfonyl naphthoquinone compounds are housed.

[0051] Optionally, the perovskite layer contains about 0.3 mol% to about 1 mol% of sulfonylnaphthoquinone compounds.

[0052] In an optional embodiment, the perovskite layer also comprises about 3 mol% MAPbCl3 and 5 mol% 4-guanidinobenzoic acid.

[0053] Optionally, the perovskite layer has a thickness of approximately 260 nm.

[0054] In a second aspect of the invention, a method for manufacturing a perovskite layer according to the first aspect is provided, comprising the following steps:

[0055] a) providing a solution mixture comprising a halide perovskite precursor and a sulfonyl naphthoquinone compound according to the first aspect; b) spin-coating the solution mixture onto a substrate; and c) annealing the spin-coated solution mixture to form a perovskite layer.

[0056] Optionally, step a) includes the following steps: a1) providing a first reaction mixture comprising a halide containing formamidinium, methylammonium and cesium; and a2) mixing the first reaction mixture with about 0.3 mol% to about 1 mol% of a sulfonylnaphthoquinone compound to form a second reaction mixture.

[0057] In an optional embodiment, the halide includes CsI, CsBr, FAI, FABr, PbI2, and PbBr2.

[0058] Optionally, the first reaction mixture further comprises about 3 mol% MAPbCl3 and about 5 mol% 4-guanidinobenzoic acid.

[0059] Optionally, step a) further includes step a3) converting sodium anthraquinone-2-sulfonate into a sulfonylnaphthoquinone compound.

[0060] Optionally, step b) includes step b1) adding chlorobenzene antisolvent to the center of the spin-coated solution mixture approximately 10 seconds before the spin-coating process is completed.

[0061] Optionally, spin coating is performed at approximately 4000 rpm to approximately 6500 rpm, with a ramping rate of approximately 1500 rpm. -1 .

[0062] In an optional embodiment, the method further includes the following steps after step c): spin-coating a surface passivating agent of piperazine iodide (PI) onto the perovskite layer; and annealing the perovskite layer coated with PI.

[0063] In a third aspect of the invention, a solar cell is provided, comprising: a first hole transport layer; a first electron transport layer; and a first active layer of a perovskite layer according to the first aspect, disposed between the first hole transport layer and the first electron transport layer.

[0064] Optionally, the first active layer is in direct contact with the first hole transport layer and the first electron transport layer.

[0065] In an optional embodiment, a first hole transport layer is disposed on a transparent conductive layer disposed on a transparent substrate, and a first electron transport layer is disposed on a first barrier layer disposed on a first metal layer.

[0066] In one embodiment of the present invention, the first hole transport layer is in direct contact with the transparent conductive layer, and the first electron transport layer is in direct contact with the first blocking layer.

[0067] Optionally, the transparent substrate is selected from the group consisting of: glass, polymethyl methacrylate (PMMA), polycarbonate (PC), general-purpose polystyrene (GPPS), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polydimethylsiloxane (PDMS), styrene-ethylene-butene-styrene (SEBS), ethylene terephthalate-1,4-cyclohexanedimethyl terephthalate (PETG), acrylonitrile-butadiene-styrene copolymer (ABS), polypropylene (PP), polyamide (PA), acrylonitrile-styrene copolymer (AS), and combinations thereof.

[0068] Optionally, the transparent conductive layer is selected from the group consisting of: indium tin oxide (ITO), aluminum zinc oxide (AZO), tin oxyfluoride (FTO), graphene, poly(3,4-ethylenedioxythiophene):poly(styrene sulfonic acid) (PEDOT:PSS), silver nanowires, copper nanowires, and combinations thereof.

[0069] Optionally, the first hole transport layer is selected from the group consisting of: poly(triarylamine) (PTAA), PEDOT:PSS, NiOx, 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene (Spiro-OMeTAD), DC-PA, MoO x and their combinations.

[0070] Optionally, the first electronic transport layer is selected from PC. 61 BM, C 60 The group consists of SnO2, PNDIT-F3N and their combinations.

[0071] Optionally, the first barrier layer can be selected as Free Bath Copper Spirit (BCP) or Double C. 60 (bis-C 60 SnO x Zr(acac)2, MoO x Groups composed of its components.

[0072] Optionally, the first metal layer is selected from the group consisting of Ag, Cu, Au, Al, W, Fe, Pt and combinations thereof.

[0073] In one optional embodiment, the solar cell includes a bandgap of approximately 1.81 eV.

[0074] Optionally, the solar cell has a power conversion efficiency of about 18.98% to about 19.58%.

[0075] Optionally, the solar cell includes a power conversion efficiency of 95% of its initial value after 500 hours of AM1.5G illumination at approximately 45°C.

[0076] In an optional embodiment, the solar cell further includes a sub-cell disposed on and in direct contact with the first metal layer.

[0077] Optionally, the solar cell also includes an anti-reflective layer, a transparent conductive layer, and a transparent substrate disposed on and in direct contact with the anti-reflective layer.

[0078] Optionally, the antireflective layer is selected from the group consisting of MgF2, LiF, PDMS and combinations thereof.

[0079] Optionally, the sub-cell includes: a second hole transport layer; a second electron transport layer; and a second active layer disposed between the second hole transport layer and the second electron transport layer.

[0080] In an optional embodiment, the second active layer is in direct contact with the second hole transport layer and the second electron transport layer.

[0081] Optionally, the second active layer is selected from the group consisting of perovskite photovoltaic materials, Si photovoltaic materials, CIGS photovoltaic materials, CdTe photovoltaic materials, organic photovoltaic materials, and combinations thereof.

[0082] Optionally, the second hole transport layer is disposed on the first metal layer, and the second electron transport layer is disposed on the second metal layer.

[0083] Optionally, the second hole transport layer is in direct contact with the first metal layer, and the second electron transport layer is in direct contact with the second metal layer.

[0084] In an optional embodiment, a second hole transport layer is disposed on a first metal layer, and a second electron transport layer is disposed on a second metal layer.

[0085] Optionally, the second hole transport layer is in direct contact with the first metal layer, and the second electron transport layer is in direct contact with the second blocking layer.

[0086] In one optional embodiment, the solar cell includes a perovskite-organic tandem solar cell.

[0087] Optionally, perovskite-organic tandem solar cells include Cs 0.2 FA 0.8 Pb(I 0.6 Br0.4 The first active layer of )3 and PM6:Y6:P 71 The second active layer of BM.

[0088] Optionally, the perovskite-organic tandem solar cell has a power conversion efficiency of about 24.27% to about 25.22%.

[0089] Optionally, the perovskite-organic tandem solar cell has a power conversion efficiency of 92% of its initial value after 500 hours of AM1.5G illumination at approximately 45°C. Attached Figure Description

[0090] The invention will now be described more specifically by way of example only with reference to the accompanying drawings, in which:

[0091] Figure 1A The theoretically achievable efficiency of a double-junction solar cell with a 2-end configuration is shown.

[0092] Figure 1B This is a schematic diagram illustrating an exemplary solar cell according to an embodiment of the present invention;

[0093] Figure 1C This is a schematic diagram illustrating an exemplary solar cell according to an embodiment of the present invention;

[0094] Figure 2A It is the synthesized AQSH (a compound of formula (VIIIa)). 1 H NMR spectrum;

[0095] Figure 2B It is the synthesized AQSH (a compound of formula (VIIIa)). 13 C NMR spectrum;

[0096] Figure 3A It is the synthesized AQSN (a compound of formula (VIIIb)). 1 H NMR spectrum;

[0097] Figure 3B It is the synthesized AQSN (a compound of formula (VIIIb)). 13 C NMR spectrum;

[0098] Figure 4A It is the synthesized AQSP (a compound of formula (VIIIc)). 1 H NMR spectrum;

[0099] Figure 4B It is the synthesized AQSP (a compound of formula (VIIIc)). 13 C NMR spectrum;

[0100] Figure 5 This shows I dispersed in a DMF / IPA mixed solvent (volume ratio 1:10) containing anthraquinone. 0 and Pb 0 Photograph of the powder (after stirring at 100°C for 60 minutes);

[0101] Figure 6A This is a schematic diagram illustrating the molecular structure of an organic redox mediator based on an AQS core with different cation substituents;

[0102] Figure 6B The cyclic voltammetry curves of AQSH are shown;

[0103] Figure 7 This is a schematic diagram illustrating the synthetic routes of AQSH, AQSP, and AQSN;

[0104] Figure 8 This is a schematic diagram illustrating the electron shuttle between the AQS core, Pb, and I;

[0105] Figure 9 Pb is shown dispersed in IPA:DMF mixed solvents (v:v = 10:1) with and without AQSH. 0 and I 0 Transmission spectrum of powder;

[0106] Figure 10A The transmission spectra of I2, FAI, and FAI+AQSH powders dissolved in DMF are shown.

[0107] Figure 10B It shows the combination of AQSH and I 0 A solution composed of powder (left) and a solution composed of AQSH and Pb 0 A photograph of a solution composed of powder (right);

[0108] Figure 11 It shows from such Figure 9 The illustration shows the powder X-ray diffraction (XRD) pattern of PbI2 and bottom precipitate obtained from a glass vial;

[0109] Figure 12 This is a schematic diagram illustrating the proposed method of using a redox mediator as an additive to sustainably eliminate metallic Pb from the perovskite layer. 0 and I 0 The mechanism of the substance and its effect on inhibiting halide segregation;

[0110] Figure 13 The time-dependent photoluminescence (tdPL) spectra of I / Br mixed perovskites with 0.5 mol% different AQS derivatives are shown.

[0111] Figure 14 Normalized PL spectra of I / Br mixed perovskite films with different redox mediators are shown (from...) after 0, 5, and 10 minutes of illumination. Figure 13 Extracted from the corresponding time-dependent PL spectrum;

[0112] Figure 15 The derived PL spectra used to analyze the phase stability of I / Br mixed perovskites with 0.5 mol% different AQS derivatives are shown.

[0113] Figure 16 Time-dependent PL spectra of I / Br mixed perovskite films doped with NH4I or PEAI as additives are shown.

[0114] Figure 17 Photographs show the aging conditions of mixed halide perovskite films with different AQS derivatives as additives, sealed in 20 mL vials (filled with N2) and illuminated for two days. The intensity of simulated AM1.5G illumination was calibrated to the equivalent intensity of 1 solar day.

[0115] Figure 18A High-resolution X-ray photoelectron spectroscopy (XPS) spectra of Pb 4f in aged perovskite films with different AQS derivatives are shown.

[0116] Figure 18B High-resolution X-ray photoelectron spectroscopy (XPS) spectra of I 3d of aged perovskite films with different AQS derivatives are shown.

[0117] Figure 18C High-resolution X-ray photoelectron spectroscopy (XPS) spectra of Br 3d in aged perovskite films with different AQS derivatives are shown.

[0118] Figure 19 The diagram shows the metallic Pb in the total Pb element of perovskite films with or without different AQS derivatives. 0 The atomic ratio;

[0119] Figure 20A The total Pb (Pb) of the original perovskite films with different AQS derivatives is shown. 2+ +Pb 0 Metallic Pb (Pb) 0 High-resolution XPS spectra;

[0120] Figure 20B The total Pb (Pb) of the original perovskite films with or without different AQS derivatives is shown. 2+ +Pb 0 Metallic Pb (Pb) 0atomic ratio;

[0121] Figure 21 The atomic ratios of I:Pb, I:Br, and (I+Br):Pb in perovskite films with or without different AQS derivatives are shown.

[0122] Figure 22 Top-view SEM images of perovskite films with or without AQS derivatives are shown.

[0123] Figure 23 Thin film XRD patterns of perovskite films with or without AQS derivatives are shown.

[0124] Figure 24 Cross-sectional SEM images and EDX elemental distributions (line scans of S, Pb, and In) of a perovskite film (prepared on an ITO substrate) with AQSH as an additive are shown.

[0125] Figure 25 The UV-vis absorption spectra of perovskite films with and without AQS derivatives are shown.

[0126] Figure 26A The optimized plate structures of original FAI-rich and defect-rich FAI (100) / (110) are shown based on density functional theory (DFT) calculations using a redox mediator / perovskite interface model.

[0127] Figure 26B The optimized plate structures of pristine PbI2-rich and defective PbI2-rich (100) / (110) are shown based on density functional theory (DFT) calculations using a redox mediator / perovskite interface model.

[0128] Figure 27A This explains the core of AQS, I 0 and Pb 0 A schematic diagram of the half-reactions between them;

[0129] Figure 27B It shows that from I 0 To I - and from Pb 0 To Pb 2+ The calculated energy barrier for the half-reaction, and the total energy barrier for redox charge shuttle;

[0130] Figure 28 The surface Pb of FAPbI3 (100) and (110) surfaces rich in PbI2 with or without AQS adsorption is shown. 2+ Binding energy;

[0131] Figure 29 NH4 was shown+ (PEA + Calculated binding energy between the original / defective FAPbI3 (100) and (110) surfaces;

[0132] Figure 30A An optimized crystal structure of the original PbI2-rich (100) with AQS adsorption is shown; optimization was performed at the GGA / PBE+vdW theoretical level.

[0133] Figure 30B An optimized crystal structure of the original PbI₂-rich (110) with AQS adsorption is shown. Optimization was performed at the GGA / PBE+vdW theoretical level;

[0134] Figure 31A It shows NH4 + and PEA + The optimized crystal structure of the original FAI-rich (100) adsorbed crystal was obtained. Optimization was performed at the GGA / PBE+vdW theoretical level.

[0135] Figure 31B It shows NH4 + and PEA + Adsorption defective FAI-rich (100)-V FA The optimized crystal structure was achieved. Optimization was performed at the theoretical level of GGA / PBE+vdW.

[0136] Figure 31C It shows NH4 + and PEA + The optimized crystal structure of the original PbI2-rich (100) adsorbed crystal was obtained. Optimization was performed at the GGA / PBE+vdW theoretical level.

[0137] Figure 31D It shows NH4 + and PEA + Adsorption defective PbI2-rich (100)-V Pb The optimized crystal structure was achieved. Optimization was performed at the theoretical level of GGA / PBE+vdW.

[0138] Figure 32A It shows NH4 + and PEA + The optimized crystal structure of the original FAI-rich (110) adsorbed crystal was obtained. Optimization was performed at the GGA / PBE+vdW theoretical level.

[0139] Figure 32B It shows NH4 + and PEA + Adsorption defective FAI-rich (110)-VFA The optimized crystal structure was achieved. Optimization was performed at the theoretical level of GGA / PBE+vdW.

[0140] Figure 32C It shows NH4 + and PEA + The optimized crystal structure of the original PbI2-rich (110) adsorbed crystal was obtained. Optimization was performed at the GGA / PBE+vdW theoretical level.

[0141] Figure 32D It shows NH4 + and PEA + Adsorption defective PbI2-rich (110)-V Pb The optimized crystal structure was achieved. Optimization was performed at the theoretical level of GGA / PBE+vdW.

[0142] Figure 33A It shows that H + Adsorption of native FAI-rich (100) and defective FAI-rich (100)-V FA Optimized crystal structure;

[0143] Figure 33B It shows that H + The adsorption of pristine PbI2-rich (100) and defective PbI2-rich (100)-V Pb Optimized crystal structure;

[0144] Figure 33C It shows that H + Adsorption of pristine FAI-rich (110) and defective FAI-rich (110)-V FA Optimized crystal structure;

[0145] Figure 33D It shows that H + Adsorption of pristine PbI2-rich (110) and defective PbI2-rich (110)-V Pb Optimized crystal structure;

[0146] Figure 34 H was shown + Calculated binding energy between the original / defective FAPbI3 (100) and (110) surfaces;

[0147] Figure 35A The time-resolved PL (trPL) spectra of perovskite films doped with different AQS derivatives are shown.

[0148] Figure 35B A table is shown, summarizing the calculations. Figure 35AThe parameter of the average carrier lifetime of I / Br mixed halide perovskites;

[0149] Figure 36A The space charge confinement current (SCLC) curves of pure hole devices with device structures of glass / ITO / DC-PA / perovskite (with and without AQS derivative / MoO3 / Ag) are shown.

[0150] Figure 36B It shows Figure 36A The corresponding calculated trap density in the perovskite film;

[0151] Figure 37A The control and target single-junction PSCs (perovskite with AQSP as an additive) are shown. JV Curves. The initial efficiencies of the control and target single-junction PSCs were 18.08% and 18.89%, respectively;

[0152] Figure 37B The single-junction PSC based on perovskite with different concentrations of AQSP is shown. JV curve;

[0153] Figure 37C A violin plot showing the photovoltaic parameters of the control and target PSCs (20 devices manufactured in different batches) is presented;

[0154] Figure 38 The target PSC is shown under reverse and forward scans. JV curve;

[0155] Figure 39A The single-junction PSC based on perovskite with different concentrations of AQSP is shown. JV curve;

[0156] Figure 39B This is a table summarizing the performance of single-junction PSC solar cells under reverse scanning (from...) Figure 39A of JV Curve extraction);

[0157] Figure 40 The external quantum efficiency (EQE) curve of the highest efficiency target PSC and the calculated actual band gap of perovskite are shown;

[0158] Figure 41 The integral J of the corresponding EQE spectrum from the highest efficiency target PSC is shown. sc ;

[0159] Figure 42A The reported V values ​​for a representative PSC with a bandgap in the range of 1.60 to 1.85 eV are shown.oc A summary of the value;

[0160] Figure 42B It is a table that summarizes the corresponding... Figure 42A The reported V of the PSC with a band gap of approximately 1.80 eV. oc value;

[0161] Figure 43 The PSC is encapsulated in an N2-filled cavity without temperature control under simulated AM1.5G illumination (100 mW cm⁻¹). -2 Continuous tracking at its maximum power point (MPP) was performed under conditions without a UV filter. The initial efficiencies of the control and target PSCs were 18.08% and 18.98%, respectively.

[0162] Figure 44 This is a schematic diagram illustrating the structure of a monolithic (two-end) PO-TSC with a BCP / Au / MoO3 interconnect layer (ICL);

[0163] Figure 45 It shows the corresponding Figure 44 Cross-sectional scanning electron microscope (SEM) images;

[0164] Figure 46A The PO-TSC is shown in both reverse and forward scans. JV Curves. The inset shows the stable power output (SPO) of the series-connected battery;

[0165] Figure 46B This is a table that summarizes the device performance of the highest efficiency PO-TSC under both reverse and forward scans;

[0166] Figure 47 The PSC, OSC, and PO-TSC are shown. JV curve;

[0167] Figure 48 A violin plot summarizing the photovoltaic parameters of PO-TSC (25 devices manufactured in different batches) is shown;

[0168] Figure 49 The EQE spectra of perovskite and organic subcells in PO-TSC are shown. The dashed lines represent the sum of the EQE% of the front and rear subcells at different wavelengths. The dashed line 1-R represents the sum of transmission and parasitic absorption of the device, where R is the reflection of the entire device (i.e., PO-TSC), measured from the glass / ITO side in the integrating sphere;

[0169] Figure 50 The efficiency distribution of 25 individual series-connected cells (from different batches) is shown;

[0170] Figure 51 A summary of the PCEs reported for the PO-TSC is shown;

[0171] Figures 52A to 52E The certification results for the tandem solar cells, measured at SIMIT (CNAS), are shown. The certified PCE is 24.3%, and the certified aperture area is 0.0419 cm². 2 ;

[0172] Figure 53 It is a table that summarizes the device performance of the reported PO-TSC and the PO-TSC of this invention; and

[0173] Figure 54 This demonstrates the encapsulation of PO-TSC in an N2-filled cavity without temperature control under simulated AM1.5G illumination (100mW cm⁻¹). -2 Under continuous MPP tracking (without a UV filter), the initial efficiency of the series-connected cells was 24.67%. Detailed Implementation

[0174] As used herein, unless the context clearly indicates otherwise, the forms “a / kind” and “the / said” are intended to include both singular and plural forms.

[0175] The terms "example" or "exemplary" as used in this invention are intended to serve as instances, examples, or illustrations. Any aspect or design described as "exemplary" in this disclosure is not necessarily to be construed as being more preferred or advantageous than other aspects or designs. Rather, the use of the terms "example" or "exemplary" is intended to present concepts in a specific manner. As used in this application, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or." That is, unless otherwise specified or clearly indicated by the context, "X adopts A or B" is intended to mean any natural inclusive permutation. That is, "X adopts A or B" holds true if X adopts A; X adopts B; or X adopts both A and B.

[0176] As used herein, the phrase “about” is intended to refer to a value that deviates slightly from the values ​​described herein. In one instance, the expression “about 10 seconds” covers any value between 9.5 and 10.5 seconds, such as 9.5, 9.55, 9.85, 10.0, 10.02, 10.2…10.5 seconds. In another instance, the expression “about 1 mol%” covers any value between 0.8 mol% and 1.2 mol%, such as 0.8, 0.85, 0.88, 0.95…1…1.05…1.2 mol%. In yet another instance, the expression “about 0.3 mol%” covers any value between 0.28 mol% and 0.32 mol%, such as 0.28, 0.285, 0.29, 0.292…0.3…0.305, 0.31…0.32 mol%. In further examples, the expression "approximately 260 nm" covers any value from 255 nm to 265 nm, such as 255, 255.5, 256, 256.2...260...262, 263.5, 264...265 nm. In further examples, the expression "approximately 4000 rpm" covers any value from 3900 rpm to 4100 rpm, such as 3900, 3910, 3955...4000, 4005, 4050...4100 rpm.

[0177] The halide oxidation mechanism is considered one of the models that can rationalize halide segregation behavior in perovskites. Specifically, preferential iodide oxidation is believed to occur in I / Br mixed perovskites under illumination, leading to local concentration gradients of its oxidation products (e.g., I₂ and HI), which in turn drive halide migration. Furthermore, Pb in perovskites is also believed to... 2+ Ions are easily reduced to metallic Pb under continuous light irradiation. 0 This is detrimental to device efficiency and stability.

[0178] Not intending to be limited by theory, the inventors, through their own research, experiments, and design, have developed an active layer for solar cells, particularly a perovskite layer comprising a mixture of halide perovskite and sulfonylnaphthoquinone compounds (or, in other words, a perovskite layer formed by mixing halide perovskite and sulfonylnaphthoquinone compounds), which effectively suppresses halide segregation in the active layer. Specifically, in exemplary embodiments, it has been found that a power conversion efficiency (PCE) of 19.58% and an open-circuit voltage (V0.05) equipped with the perovskite layer of the present invention can be achieved in a solar cell. oc It also shows significantly improved long-term stability (T under maximum power point (MPP) tracking). 95(Approximately 500 hours). In another exemplary embodiment, a monolithic perovskite-organic tandem solar cell (PO-TSC) containing the perovskite layer of the present invention can have a PCE of 25.22% (certified as 24.27%) and retain 92% of its initial PCE after 500 hours of operation.

[0179] According to the present invention, a perovskite layer for a solar cell is provided, comprising a mixture of halide perovskite and a sulfonylnaphthoquinone compound having the structure of formula (I):

[0180]

[0181] Formula (I),

[0182] in:

[0183] R1 is independently selected from one of OM, OR4, and NR5R6, where M is a cation, and R4, R5, and R6 are independently selected from hydrogen and substituents; R2 and R3 are independently selected from hydrogen and substituents, or R2 and R3 may form a fused ring.

[0184] In one implementation, M is selected from the group consisting of: H + Na + K + Cs + 、Rb + 、Sr 2+ Ca 2+ Ni 2+ Cu 2 + Co 2+ Zn 2+ Mg 2+ Ba 2+ Li + The following are selected independently from the group consisting of: hydrogen, substituted or unsubstituted C1 to C4 alkyl, substituted or unsubstituted C2 to C6 alkenyl, substituted or unsubstituted C2 to C6 alkynyl, halogen, substituted or unsubstituted C6 to C10 aryl, -CN, -C(=O)OH, -C(=O)H, -C(=O)R7, -OR7, -SH, -SR7, -NH2, -NHR6, -N(R7)2, -Si(R7)3, -OSi(R7)3, -S(O)OH and -P(O)(OH)2, wherein R7 is an alkyl or phenyl group; and when R2 and R3 form a fused ring, it contains a substituted or unsubstituted 6- to 14-membered ring.

[0185] In one embodiment, the unsubstituted C1 to C4 alkyl groups may include methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert-butyl, n-butyl, etc. In one embodiment, the unsubstituted C2 to C6 alkenyl groups may include vinyl, 1-propenyl, 2-propenyl (allyl), isopropenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, etc. In one embodiment, the unsubstituted C2 to C6 ynyl groups may include ethynyl, propynyl, but-1-ynyl, but-2-ynyl, pent-1-ynyl, pent-2-ynyl, hex-1-ynyl, hex-2-ynyl, hex-3-ynyl, etc. In one embodiment, the unsubstituted C6 to C10 aryl groups may include unsubstituted C6 to C10 homoaryl groups, such as phenyl, naphthyl, tetrahydronaphthyl, indanyl, etc. In one embodiment, the unsubstituted C6 to C10 aryl groups may include unsubstituted C6 to C10 heteroaryl groups, such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, quinolinyl, isoquinolinyl, benzothiopheneyl, benzofuranyl, indolyl, pyridine, pyrimidone, pyrimidinone, etc.

[0186] In one embodiment, one or more hydrogen atoms of the above-mentioned substituents (i.e., C1 to C4 alkyl, C2 to C6 alkenyl, C2 to C6 alkynyl, and C6 to C10 aryl) may be substituted with one or more of the following moieties, such as halogens (e.g., F, Cl, Br), -CN, -CF3, alkenyl (e.g., -CH=CH2, -CH=C(CH3)2, etc.), alkynyl (e.g., -C≡CH, -C≡CCH3, etc.), -C(=O)OH, -C(=O)H, -C(=O)R8, -OR8, -SH, -SR8, -NH2, -NHR8, -N(R7)8, -Si(R8)3, -OSi(R8)3, -S(O)OH, and -P(O)(OH)2, wherein R8 is a C1 to C4 alkyl or phenyl as defined herein.

[0187] In one embodiment where R2 and R3 form a fused ring, it may comprise an unsubstituted 6- to 14-membered ring (such as phenyl, anthracene, tetrahydronaphthyl, indanyl, etc.) or a substituted 6- to 14-membered ring, wherein one or more hydrogens of the unsubstituted 6- to 14-membered ring are substituted with, for example, phenyl, carbonyl, primary amine, secondary amine, etc.

[0188] In one embodiment, the sulfonylnaphthoquinone compound may be any one of formula (II), (III), (IV), (V), (VI), or (VII):

[0189]

[0190] Equation (II),

[0191]

[0192] Equation (III),

[0193]

[0194] Formula (IV),

[0195]

[0196] Equation (V),

[0197]

[0198] Formula (VI), or

[0199]

[0200] Equation (VII),

[0201] R1 is defined above; and n is 1-1000.

[0202] In a particular embodiment, the sulfonylnaphthoquinone compound has the structure of formula (II), which may be selected from any one of formula (VIII), formula (IX) or formula (X):

[0203]

[0204] Equation (VIII),

[0205]

[0206] Formula (IX), or

[0207]

[0208] Equation (X),

[0209] Where M is H + The ammonium ion or ammonium ion; R4 is a C1 to C4 alkyl group; R5 and R6 are independently selected from hydrogen and C1 to C4 alkyl groups. The term "aminum ion" generally refers to a substituted ammonium ion formed by replacing one or more hydrogen atoms in the ammonium ion with one or more organic groups (such as alkyl groups (e.g., methyl, ethyl, propyl, phenethyl, tert-butyl, etc.), benzyl, phenyl, etc.). C1 to C4 alkyl groups can include straight-chain and branched aliphatic hydrocarbons having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert-butyl, n-butyl, etc.

[0210] Preferably, the sulfonyl naphthoquinone compound of formula (VIII) is selected from any one of formulas (VIIIa), (VIIIb), and (VIIIc):

[0211]

[0212] Equation (VIIIa),

[0213]

[0214] Equation (VIIIb), and

[0215]

[0216] Formula (VIIIc).

[0217] In particular, it was found that when cation M is removed from H... + Change to NH4 + and phenylamine (PEA) ions (PhCH2CH2NH3) + When sulfonyl naphthoquinone compounds are used, their passivation effect is enhanced, which in turn enhances their ability to stabilize perovskites during operation, such as exhibiting resistance to redox components of perovskites (e.g., Pb) during operation. 2+ This results in a stronger bond (e.g., a higher binding energy) to the perovskite. Therefore, it can further promote the long-term operation of perovskites. Details of the stabilizing effect of sulfonylnaphthoquinone compounds will be discussed in later sections of this disclosure.

[0218] In an optional embodiment, the sulfonylnaphthoquinone compound may contain a structure of formula (IXa):

[0219]

[0220] Formula (IXa).

[0221] In another optional embodiment, the sulfonylnaphthoquinone compound may comprise a structure of formula (Xa):

[0222]

[0223] Equation (Xa).

[0224] The halide perovskite in the perovskite layer may contain [A] +1 B +2 X -1 The grain structure of [3], wherein A +1 It is an A-site monovalent cation, B +2 It is a B-site divalent cation, and X -1 It is a halide anion.

[0225] In one implementation, the monovalent cation at the A site is selected from the formamidinium ion (FA). +), methylammonium ion (MA + ), ethylammonium ion (EA) + ), guanidine ion (GA) + ), Cs + 、Rb + The group consisting of the group and its combination; the B-site divalent cation is selected from Pb. 2+ Sn 2+ 、Ge 2 + The group consisting of the group and its combinations; and the halide anion selected from I - ,Br - Cl - Groups composed of its components.

[0226] In one particular implementation, the halide perovskite is selected from CsPb. 0.5 Sn 0.5 I3, FAPbI3, MA 0.25 FA 0.75 PbI 2.2 Br 0.6 Cl 0.2 Cs 0.02 FA 0.96 MA 0.02 PbI 0.99 Cl 0.01 MAPb 0.92 Sn 0.08 I3, (FA) 0.95 MA 0.05 ) 0.95 Cs 0.05 Pb(I 0.96 Br 0.04 3. Rb 0.1 FA 0.8 GA 0.1 Pb 0.6 Ge 0.4 I3 and (FA 0.92 MA 0.08 ) 0.9 Cs 0.1 Pb(I 0.92 Br 0.08 )3 and Cs 0.2 FA 0.8 Pb(I 0.6 Br 0.4 Any of the three. Preferably, the halide perovskite can be an I / Br mixed perovskite. As a specific embodiment, the halide perovskite can be Cs 0.2 FA 0.8 Pb(I 0.6 Br 0.4 3.

[0227] The term "crystal grain" (or crystallite) generally refers to small or microcrystalline structures that form grain boundaries at the regions / interfaces where crystallites meet, oriented / grown randomly or without a preferred direction. In one embodiment, [A] +1 B +2 X -1 The grain structure of [3] may include grain boundaries, where sulfonylnaphthoquinone compounds are housed, and these compounds act as redox mediators at the grain boundaries, enabling them to selectively reduce I through electron shuttle. 0 And oxidize Pb 0 .

[0228] The content / concentration of sulfonylnaphthoquinone compounds in the perovskite layer can be varied / adjusted according to actual needs. In one embodiment, the perovskite layer may contain about 0.3 mol% to about 1 mol%, about 0.29 mol% to about 1.1 mol%, about 0.31 mol% to about 1 mol%, about 0.3 mol% to about 0.9 mol%, about 0.3 mol% to about 0.8 mol%, about 0.32 mol% to about 0.75 mol%, about 0.3 mol% to about 0.7 mol%, about 0.31 mol% to about 0.65 mol%, about 0.3 mol% to about 0.6 mol%, about 0.31 mol% to about 0.52 mol%, or particularly about 0.3 mol% to about 0.5 mol% of sulfonylnaphthoquinone compounds.

[0229] In an additional or optional embodiment, the perovskite layer may further comprise about 3 mol% MAPbCl3 and 5 mol% 4-guanidinobenzoic acid, which specifically act as passivating agents to further passivate defects in the perovskite layer as discussed herein (in addition to the activity of redox mediators). Advantageously, it should be understood that these passivating agents can be distributed at the grain boundaries of the perovskite layer without interfering with the chemical composition of the perovskite layer (i.e., without causing significant changes in the chemical composition of the perovskite layer).

[0230] In one embodiment, the perovskite layer may have a thickness of about 200 nm to about 280 nm, about 205 nm to about 285 nm, about 210 nm to about 275 nm, about 220 nm to about 270 nm, about 220 nm to about 268 nm, about 240 nm to about 268 nm, about 255 nm to about 268 nm, about 258 nm to about 268 nm, or particularly about 260 nm.

[0231] A method for manufacturing perovskite layers as described herein is now disclosed. The method may include the following steps:

[0232] a) Provide a solution mixture comprising a halide perovskite precursor and a sulfonyl naphthoquinone compound as described herein (such as a sulfonyl naphthoquinone compound having a structure of formula (VIII), formula (IX) or formula (X);

[0233] b) Spin-coating the solution mixture onto the substrate; and

[0234] c) Anneal the spin-coated solution mixture to form a perovskite layer.

[0235] Step a) may include the following steps: a1) providing a first reaction mixture comprising a formamidinium, methylammonium and cesium; and a2) mixing the first reaction mixture with about 0.3 mol% to about 1 mol% of a sulfonylnaphthoquinone compound to form a second reaction mixture.

[0236] For example, in one embodiment, the halide may include CsI, CsBr, FAI, FABr, PbI2, and PbBr2. These halides may be dissolved in a solvent mixture (such as DMF / DMSO (e.g., volume / volume 4:1)) to form a first reaction mixture. Then, about 0.3 mol% to about 1 mol% of a sulfonylnaphthoquinone compound, such as any of sulfonylnaphthoquinone compounds having the structure of formula (VIII), formula (IX), or formula (X), may be mixed with the first reaction mixture to form a second reaction mixture. Optionally or additionally, the second reaction mixture may be stirred for at least 8 hours before performing the spin-coating step (i.e., step b) to obtain a homogeneous / consistent solution mixture.

[0237] In an additional or optional embodiment, the first reaction mixture may also contain about 3 mol% MAPbCl3 and 5 mol% 4-guanidinobenzoic acid. For example, MAPbCl3 and 4-guanidinobenzoic acid may be added to the first reaction mixture containing formamidinium, methylammonium, and cesium halides prior to step a2).

[0238] Optionally, the sulfonylnaphthoquinone compound may be commercially available or obtained synthetically. In an optional embodiment of obtaining the sulfonylnaphthoquinone compound by synthesis, the method for manufacturing the perovskite layer claimed in this invention may further include step a3), which involves converting sodium anthraquinone-2-sulfonate into the sulfonylnaphthoquinone compound as described herein.

[0239] In one embodiment, sodium anthraquinone-2-sulfonate can be converted into a sulfonylnaphthoquinone compound having the structure of formula (VIIa) by ion exchange. For example, sodium anthraquinone-2-sulfonate can be mixed with an aqueous solution of a cation exchange resin (such as Amberlite cation exchange resin (IR-120 hydrogen form)) and stirred for at least 8 hours. The mixture can then be further separated by passing it through a cation exchange column equipped with Amberlite cation exchange resin.

[0240] In another embodiment, sodium anthraquinone-2-sulfonate can be converted into sulfonylnaphthoquinone compounds having the structure of formula (VIIb) or (VIIc). For example, sodium anthraquinone-2-sulfonate can be converted into sulfonylnaphthoquinone compounds having the structure of formula (VIIa) as described above. The sulfonylnaphthoquinone compound of formula (VIIa) can then be converted into sulfonylnaphthoquinone compounds of formulas (VIIb) and (VIIc) by reacting the sulfonylnaphthoquinone compound of formula (VIIa) with a corresponding amine or ammonium salt (such as ammonium hydroxide and phenylethylamine) and stirring for at least 8 hours, followed by drying under reduced pressure (such as vacuum).

[0241] In an optional embodiment, sodium anthraquinone-2-sulfonate can be converted to anthraquinone-2-sulfonyl chloride, and then further converted to a sulfonyl naphthoquinone compound having the structure of formula (IXa) or (Xa). For example, sodium anthraquinone-2-sulfonate can be mixed with thioyl chloride in DMF to form a reaction mixture, and then crude / raw anthraquinone-2-sulfonyl chloride can be separated from the reaction mixture by precipitation and filtration. The crude / raw anthraquinone-2-sulfonyl chloride can optionally be purified by washing with a suitable solvent prior to further reactions.

[0242] To convert anthraquinone-2-sulfonyl chloride into sulfonylnaphthoquinone compounds having the structure of formula (IXa), for example, anthraquinone-2-sulfonyl chloride can be mixed with methanol in a solvent (such as DMF) and the mixture stirred at a temperature of about 50°C to about 60°C for, for example, 2 hours. The crude / crude sulfonylnaphthoquinone compound of formula (IXa) is then separated by precipitation and optional filtration, and purified by column chromatography using an elution solvent (e.g., a solution of 0.5% methanol in dichloromethane (DCM)).

[0243] On the other hand, to convert anthraquinone-2-sulfonyl chloride into a sulfonylnaphthoquinone compound having the structure of formula (Xa), butylamine can be slowly added (e.g., dropwise) to a DCM solution of anthraquinone-2-sulfonyl chloride, for example, at a reduced temperature (such as 0°C). The reaction mixture can be stirred at room temperature, for example, for 2 hours, then the crude / crude product can be washed with a suitable solvent and purified by column chromatography using an elution solvent (e.g., a 0.5% methanol solution in dichloromethane (DCM)).

[0244] In spin coating step b), the solution mixture (from step a) can be spin-coated onto a substrate at approximately 300 rpm to approximately 12000 rpm for approximately 10 seconds to approximately 140 seconds. The substrate may be a transparent substrate (e.g., glass, PDMS, PET, ITO, FTO, etc.), a hole transport layer, an electron transport layer, or a combination thereof. In one embodiment, spin coating can be performed at approximately 4000 rpm to approximately 6500 rpm, with a speed change rate of approximately 1500 rpm per second. -1 During and / or before the spin-coating process is completed, such as 3 to 35 seconds before completion, an antisolvent may be added (e.g., dropwise) to the spin-coated solution mixture. Antisolvent treatment is believed to increase the nucleation density during perovskite layer / film formation, thus favoring the production of a uniform and pinhole-free perovskite layer / film. In one embodiment, the addition of the antisolvent may begin in step b1), where a chlorobenzene antisolvent is added to the center of the spin-coated solution mixture approximately 10 seconds before the completion of the spin-coating process.

[0245] Preferably, unless otherwise specified, it should be understood that the spin coating process described herein is carried out at a controlled temperature of about 20°C in an N2-filled glove box with O2 and H2O content <5 ppm.

[0246] The method may then proceed to step c) annealing the spin-coated solution mixture to form a perovskite layer. For example, the spin-coated solution mixture (including the substrate) may be transferred to a hot plate and annealed for about 6 minutes to about 120 minutes at temperatures ranging from about 65°C to about 180°C, about 80°C to about 180°C, about 80°C to about 150°C, about 90°C to about 150°C, about 95°C to about 150°C, about 100°C to about 120°C, about 100°C to about 115°C, or about 100°C to about 110°C. It is believed that the annealing / heating process may promote perovskite crystallization and thus result in higher power conversion efficiency during (solar cell) operation. In one embodiment, the spin-coated solution mixture may be annealed at about 100°C for about 15 minutes.

[0247] In an additional or optional embodiment, the method for fabricating the perovskite layer as described herein may further include the steps of: spin-coating a surface passivating agent of piperazine iodide (PI) onto the perovskite layer; and annealing the PI-coated perovskite layer. For example, a PI solution (such as an IPA (isopropanol) solution of PI) may be spin-coated onto the perovskite layer formed in step c) at a rate of about 5000 rpm for about 30 seconds. The PI-coated perovskite layer may then be annealed / heated at a temperature of about 100°C for about 10 minutes. It is believed that the addition of PI can improve band alignment and enhance charge extraction at the interface between the perovskite layer and the electron transport layer by generating positive dipoles, which may therefore enhance the performance of the solar cell.

[0248] Another aspect of the present invention relates to solar cells, particularly solar cells comprising a perovskite layer as described herein. In one embodiment, the solar cell may include: a first hole transport layer; a first electron transport layer; and a first active layer of perovskite as described herein, disposed between the first hole transport layer and the first electron transport layer, such as... Figure 1B The example solar cell 100 is shown in the image.

[0249] As shown in the figure, the solar cell 100 has a first hole transport layer 104; a first electron transport layer 106; and a first active layer, a perovskite layer 108 as described herein, disposed between the first hole transport layer 104 and the first electron transport layer 106. In particular, the first active layer 108 is in direct contact with the first hole transport layer 104 and the first electron transport layer 106, thereby forming a layered / stacked structure.

[0250] The first hole transport layer can be disposed on a transparent conductive layer, which can be disposed on a transparent substrate, and the first electron transport layer can be disposed on a first barrier layer, which can be disposed on a first metal layer. For example, in this embodiment, the first hole transport layer 104 is in direct contact with the transport conductive layer 110 disposed on the transparent substrate 112, and the first electron transport layer 106 is in direct contact with the first barrier layer 114 disposed on the first metal layer 116. Figure 1B ).

[0251] In an alternative embodiment, the solar cell 100 may be configured such that the positions of the first hole transport layer 104 and the first electron transport layer 106 are interchanged to form the solar cell 100'. That is, in this alternative embodiment, the first electron transport layer 106 is in direct contact with the transport conductive layer 110 disposed on the transparent substrate 112, and the first hole transport layer 104 is in direct contact with the first barrier layer 114 disposed on the first metal layer 116. Figure 1B ).

[0252] As described herein, the perovskite layer of the present invention is beneficial for enhancing the efficiency and stability of devices (i.e., solar cells). For example, in one embodiment where solar cell 100 / 100' can be a perovskite solar cell (such as a single-junction perovskite solar cell), it contains, for example, a bandgap of about 1.81 eV and can contain a power conversion efficiency (PCE) of about 18.98% to about 19.58%. In another embodiment, the solar cell can contain a power conversion efficiency of 95% of its initial value after 500 hours of AM1.5G illumination at about 45°C. Detailed performance of the solar cells will be discussed in later sections of this disclosure.

[0253] In one embodiment, the solar cell 100 may further include sub-cells disposed thereon, thereby forming a series solar cell. (See reference...) Figure 1C An exemplary configuration of a series solar cell 102 is provided. As shown, the series solar cell 102 includes a solar cell 100 and a sub-cell 118 disposed on the solar cell 100, in particular in direct contact with a first metal layer 116. In other words, in this embodiment, the solar cell 100 acts as the first sub-cell 102 in the series solar cell 102. The series solar cell 102 also includes an anti-reflective layer 120, a transparent conductive layer 110, and a transparent substrate 112 disposed on and in direct contact with the anti-reflective layer.

[0254] In this embodiment, the sub-cell 118 includes a second hole transport layer 122, a second electron transport layer 124, and a second active layer 126. The second active layer is disposed between the second hole transport layer 122 and the second electron transport layer 124, and is in direct contact with them, thereby forming a layered / stacked structure. The second hole transport layer 122 may be disposed on the first metal layer 116, and the second electron transport layer 124 may be disposed on the second metal layer 128.

[0255] In particular, it should be understood that the second hole transport layer 122 and the second electron transport layer 124 may be configured differently depending on the configuration of the solar cell 100. For example, in this embodiment, the second hole transport layer 122 is in direct contact with the first metal layer 116, and the second electron transport layer 124 is in direct contact with the second metal layer 128.

[0256] In an alternative embodiment of the series-connected solar cell 102' comprising solar cell 100', the sub-cell may be a sub-cell 118' in which the positions of the second hole transport layer 122 and the second electron transport layer 124 are interchanged. That is, in this alternative embodiment, the second electron transport layer 124 is in direct contact with the first metal layer 116, and the second hole transport layer 122 is in direct contact with the second metal layer 128. Figure 1C ).

[0257] In an optional or additional embodiment, sub-cell 118 / 118' may further include a second barrier layer 130 disposed between the second ETL 124 / second HTL 122 and the second metal layer 128. Figure 1C Preferably, the second barrier layer 130 is in direct contact with the second ETL 124 / second HTL 122 and the second metal layer 128.

[0258] In one embodiment, the second active layer may be selected from the group consisting of perovskite photovoltaic materials, Si photovoltaic materials, CIGS photovoltaic materials, CdTe photovoltaic materials, organic photovoltaic materials, and combinations thereof.

[0259] In one example implementation, the second active layer can be made of organic photovoltaic materials such as PM6:Y6:P 71 Made by BM. In a specific instance implementation, it includes PM6:Y6:P 71 The sub-cell with the second active layer of BM can be connected to the first active layer (such as Cs) including a perovskite layer as described herein. 0.2 FA 0.8 Pb(I 0.6 Br 0.4 The solar cells are coupled together to form a perovskite organic tandem solar cell. In this particular embodiment, the tandem solar cell can have a power conversion efficiency of about 24.27% to about 25.22%, and 92% of its initial value after 500 hours of AM1.5G illumination at about 45°C. Detailed performance of the tandem solar cell will be discussed in a later part of this disclosure.

[0260] In some embodiments, the transparent substrate 112 may be flexible or rigid and may have a transmittance greater than about 80% (at 550 nm). In some specific embodiments, the transparent substrate may be selected from the group consisting of: glass, polymethyl methacrylate (PMMA), polycarbonate (PC), general-purpose polystyrene (GPPS), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polydimethylsiloxane (PDMS), styrene-ethylene-butene-styrene (SEBS), polyethylene terephthalate-1,4-cyclohexanediol (PETG), acrylonitrile-butadiene-styrene copolymer (ABS), polypropylene (PP), polyamide (PA), acrylonitrile-styrene copolymer (AS), and combinations thereof. In a more specific embodiment, the transparent substrate may be selected from glass, PET, PEN, PDMS, SEBS, PP, and combinations thereof. In a preferred embodiment, the transparent substrate may be selected from glass, PET, PEN, PDMS, and combinations thereof. As a specific embodiment, the transparent substrate may be glass.

[0261] In some embodiments, the transparent conductive layer (TCL) 110 may preferably have a strength of about 5 Ω sq. -1 Approximately 70 Ω sq -1 For example, approximately 5 Ω sq -1 Approximately 20 Ω sq -1 or approximately 5 Ω sq -1 Approximately 15 Ω sq -1 The resistance is believed to be less than approximately 5 Ωsq. -1 The resistance can affect the transparency of the conductive layer, and values ​​above approximately 70 Ω sq -1 The resistance of the device can affect charge transfer. Specifically, the TCL can be selected from the group consisting of: indium tin oxide (ITO), aluminum zinc oxide (AZO), tin oxyfluoride (FTO), graphene, poly(3,4-ethylenedioxythiophene):poly(styrene sulfonic acid) (PEDOT:PSS), silver nanowires, copper nanowires, and combinations thereof. In one embodiment, the TCL can be selected from any one of ITO, FTO, PEDOT:PSS, and combinations thereof. In another embodiment, the TCL can be selected from any one of ITO and FTO. As a specific embodiment, the TCL can be ITO.

[0262] In some implementations, the first hole transport layer (HTL) 104 and the second HTL 122 can be independently selected from the group consisting of: poly(triarylamine) (PTAA), PEDOT:PSS, NiOx, 2,2',7,7'-tetratetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene (Spiro-OMeTAD), p-type self-assembled monolayer (DC-PA), MoO x and combinations thereof. In one embodiment, the first HTL and the second HTL may be independently selected from PTAA, NiOx, Spiro-OMeTAD, DC-PA, MoO x Any of the combinations thereof.

[0263] In some implementations, the first electron transport layer (ETL) 126 and the second ETL 124 can be independently selected from the PC. 61 BM, C 60 The group consists of SnO2, PNDIT-F3N and their combinations.

[0264] In some embodiments, the first barrier layer 114 and the second barrier layer 130 can be independently selected from bath copper ether (BCP), bis-C 60 (bis-C 60 SnO x Zr(acac)2, MoO x Groups consisting of [various materials and combinations thereof]. In particular, it should be understood that when a blocking layer is placed on top of the ETL, it can be referred to as a "hole blocking layer," designed to prevent a minority of charge carriers (such as holes in this case) from reaching the cathode. The hole blocking layer can be selected from BCP, double-C [materials / materials], etc. 60 SnO x And either Zr(acac)2. Conversely, when the blocking layer is placed on top of the HTL, it can be called an "electron blocking layer," which is designed to block a minority of charge carriers (such as electrons in this case) from reaching the anode. The electron blocking layer can be MoO2. x .

[0265] In some embodiments, the antireflective layer 120 may be selected from the group consisting of MgF2, LiF, PDMS, and combinations thereof. In a specific embodiment, the antireflective layer may be selected from any one of MgF2, PDMS, and combinations thereof. As a specific embodiment, the antireflective layer may be MgF2.

[0266] In some embodiments, the first metal layer 116 and the second metal layer 128 can be independently selected from the group consisting of Ag, Cu, Au, Al, W, Fe, Pt, and combinations thereof. Specifically, the first metal layer and the second metal layer can be independently selected from any one of Ag, Cu, Au, Al, and combinations thereof. It should be understood that, depending on the location / configuration of the metal layer within the solar cell, the metal layer can be referred to as an electrode or a charge recombination layer. For example, it should be understood that when the metal layer is an intermediate layer connecting two solar cells or sub-cells (such as the first metal layer 116 in series solar cell 102), such a metal layer can be referred to as a "charge recombination layer." Conversely, when the metal layer is positioned / located / configured on the top or bottom of the solar cell (such as the first metal layer 116 in solar cell 100 and the second metal layer 128 in series solar cell 102), such a metal layer can be referred to as an "electrode."

[0267] The solar cells of the present invention can be manufactured by typical methods (such as those described below).

[0268] Typically, the manufacture of a solar cell may include the following steps: providing a substrate; depositing a substrate having a transparent conductive layer; optionally cleaning and drying the deposited substrate; spin-coating a hole transport layer onto the transparent conductive layer; spin-coating an active layer onto the hole transport layer; and thermally evaporating an electron transport layer and a metal layer.

[0269] A substrate with a deposited transparent conductive layer, such as substrate 112 with a deposited TCL 110 layer, can be cleaned by sequentially ultrasonically treating it with a cleaning agent, deionized water, acetone, and isopropanol for approximately 15 minutes to approximately 90 minutes. The substrate can then be dried in an oven at approximately 40°C to approximately 125°C for at least approximately 1 hour. The cleaned and dried substrate can be treated with oxygen plasma for approximately 10 minutes to approximately 75 minutes, and then transferred to an N2-filled glove box before the subsequent spin-coating process.

[0270] HTLs (such as first HTL 104 and second HTL 122) can be spin-coated onto the transparent conductive layer at about 1,000 rpm to about 10,000 rpm for about 5 seconds to about 90 seconds, followed by annealing at about 75°C to about 180°C for about 5 minutes to about 90 minutes. It is believed that the spin rate, time, and annealing temperature can affect the formation, thickness, and conductivity of the hole transport layer. In some embodiments, spin-coating can be performed at about 2,000 rpm to about 8,000 rpm for about 10 seconds to about 60 seconds, and the annealing temperature can be about 80°C to about 150°C.

[0271] The active layer (such as the first active layer 108 and the second active layer 126) can be spin-coated onto the HTL at approximately 300 rpm to approximately 12,000 rpm for approximately 10 seconds to approximately 140 seconds. Alternatively or alternatively, an antisolvent can be slowly dripped onto the center of the spin-coated active layer for approximately 3 seconds to approximately 35 seconds before the end of the spin-coating process. The spin-coated active layer can then be transferred to a hot plate for annealing at approximately 65°C to approximately 180°C for approximately 6 minutes to approximately 120 minutes.

[0272] ETLs (such as first ETL 106 and second ETL 124), barrier layers (such as first barrier layer 114 and second barrier layer 130), and metal layers (such as first metal layer 116 and second metal layer 130) can be passed through high vacuum (e.g., < about 5 × 10⁻⁶). -6 The deposition is achieved through thermal evaporation (using a vacuum chamber). High vacuum conditions are believed to be advantageous for achieving precise thicknesses during deposition. Preferably, the vacuum can be at least about 1 × 10⁻⁶. -5 To or smaller.

[0273] In one embodiment of the solar cell including an anti-reflective layer (such as anti-reflective layer 120), the anti-reflective layer can be deposited onto the TCL by thermal evaporation.

[0274] The present invention will now be described in more detail by way of examples, but the present invention is not limited thereto.

[0275] Example

[0276] Materials and reagents

[0277] Unless otherwise specified, the reagents and starting materials used in the synthesis of anthraquinone 2-sulfonate (AQS) derivatives are commercially available and can be used without further purification. Cesium iodide (CsI), formamidine iodide (FAI), and formamidine bromide (FABr) were purchased from Dysol (Australia). Lead iodide (PbI2, 99.999% purity), lead bromide (PbBr2, 99.9% purity), and 1-chloronaphthalene (1-CN) were purchased from TCI (Japan). Lead chloride (PbCl2), methylammonium chloride (MACl), fullerene (C60), and copper hydroxide (BCP, 99.9% purity) were purchased from Xi'an Polymer Light Technology Corporation (China). N,N-Dimethylformamide (DMF, 99.99% purity), dimethyl sulfoxide (DMSO, 99.50% purity), isopropanol (IPA, 99.50% purity), and chlorobenzene (CB, 99.90% purity) were purchased from J&K (China) and used as is. PM6 and Y6 were purchased from Solarmer Materials. PC 71BM was purchased from American Dye Source, Inc. Molybdenum oxide (MoO) x Chloroform (CF, 99.90% purity) and methanol (MeOH, 99.90% purity) were purchased from Sigma-Aldrich. Gold and silver particles used for thermal evaporation were high-purity particles from commercial sources. ((2,7-dimethoxy-9H-carbazole-9-yl)methyl)phosphonic acid (DC-PA, hole-selective self-assembled monolayer) and piperazine iodide (PI, perovskite surface passivator) were synthesized, as reported in our previous studies.

[0278] Methods and characterization

[0279] Experiments on redox mediators in solution

[0280] I 0 (25 mg, 0.1 mmol) and Pb 0 (25 mg, 0.12 mmol) powder was dispersed in 2 mL of a mixed DMF / IPA solvent (volume ratio 1:10) with or without a redox mediator (0.025 mmol), and the solution was stirred at 100 °C for 60 min. The supernatant (diluted to 1.0 × 10⁻⁶) was measured. -5 UV-vis absorption spectra of the sample and reference solutions (after 60 minutes) and XRD patterns of the bottom precipitates. Absorption spectra of representative solutions and the bottom layer, where FAI is mixed with the mediator and dissolved in DMF.

[0281] Preparation of perovskite precursors

[0282] A 1.2 M wide-bandgap perovskite precursor (CsI) was prepared by dissolving CsI (0.144 M), CsBr (0.096 M), FAI (0.576 M), FABr (0.384 M), PbI2 (0.756 M), and PbBr2 (0.48 M) in 1 mL of a DMF / DMSO (volume / volume, 4:1) mixed solvent. 0.2 FA 0.8 Pb(I 0.6 Br 0.43). It should be noted that during device fabrication, 3.0 mol% of MAPbCl3 and 0.5 mol% of 4-guanidinobenzoate are added to the perovskite precursor. These two chemicals can act as passivating agents to further passivate defects in the perovskite layer as discussed herein (in addition to the activity of the redox mediator). Advantageously, it should be understood that these passivating agents can be distributed at the grain boundaries of the perovskite layer without interfering with the chemical composition of the perovskite layer. For the target device (a solar cell containing a redox mediator as disclosed herein), 0.3 mol% of the redox mediator (i.e., AQSH, AQSN, or AQSP) is added to the perovskite precursor. The above solution is stirred overnight at room temperature and does not require filtration before use.

[0283] Fabrication of single-junction wide-bandgap perovskite solar cells (PSCs)

[0284] Prepatterned indium-doped tin oxide (ITO) glass substrates were cleaned sequentially by ultrasonic treatment for 15 minutes each with a detergent (1:1 volume:volume of Decon 90 / deionized water), deionized water, acetone, and isopropanol (IPA). The cleaned ITO glass substrates were then transferred to an oven at 100°C for 24 hours and treated with O2 plasma for 10 minutes before use. DC-PA hole-selective SAM (0.75 mg / mL in IPA) was then applied. -1 At 3,000 rpm (with a speed change rate of 2,000 rpm / s) -1 Spin-coating was performed onto an ITO glass substrate for 25 seconds, followed by annealing at 110°C for 15 minutes. After cooling, the substrate was rinsed with IPA solvent and annealed again at 100°C for 5 minutes. A perovskite film was then deposited on the DC-PA layer using a one-step spin-coating method. Specifically, 50 μL of the perovskite precursor (with or without a redox mediator) as described above was applied at 4,000-6,500 rpm (rate of change 1,500 rpm s). -1 Spin-coating for 30 seconds. During the spin-coating process, 200 μL of chlorobenzene (CB) antisolvent was rapidly dropped onto the center of the perovskite film 10 seconds before the end of the process, and then annealed at 100 °C for 15 minutes. Next, piperazine iodide (PI) (0.3 mg / mL in IPA) was added at 5,000 rpm. -1 Dynamic spin-coating was applied to the formed perovskite for 30 seconds, followed by annealing at 100°C for 10 minutes. All spin-coating processes were performed in an N2-filled glove box with O2 and H2O content <5 ppm and a controlled temperature of approximately 20°C. Finally, 20 nm C60, 6 nm BCP, and 100 nm Ag were respectively applied through a metal shadow mask (pore area: 0.0644 cm²).2 In a high vacuum chamber (<2 x 10⁻⁶) -6 Thermal evaporation. 100 nm of MgF2 was thermally evaporated onto the glass side of the device as an anti-reflective (AR) layer.

[0285] Preparation of organic heterojunction (BHJ) layer precursor

[0286] PM6, Y6, and PC were mixed in a weight ratio of 1:0.96:0.24. 71 BM was dissolved in chloroform (CF), while the concentration of PM6 was fixed at 7 mg / mL. -1 Add solvent additive (0.5 vol%), i.e., 1-CN, to the above solution. Then, stir the solution at 40°C for 2 hours before use.

[0287] Fabrication of single-junction narrow-bandgap organic solar cells (OSC)

[0288] OSC with pin configuration based on glass / ITO / MoO x / PM6:Y6:PC 71 The device structure of BM / PNDIT-F3N / Ag. First, 10 nm MoO x In a high vacuum chamber (<6 x 10⁻⁶) -7 Thermal evaporation (at 0.05 Ås) on a clean ITO substrate in a [missing information - likely a specific process or method]. -1 (rate). Then, PM6:Y6:PC 71 BM solution was dynamically cast into MoO at 1,500 rpm. x Apply the solution to the substrate for 40 seconds, then heat-anneal at 90°C for 10 minutes. After cooling, add 0.5 mg / mL of PNDIT-F3N (containing 0.5% vol% acetic acid in methanol). -1 The interface layer was dynamically spin-coated onto the organic BHJ layer at 1,500 rpm for 40 seconds. Finally, it was coated with a metal shadow mask (pore area: 0.0644 cm²). 2 In a high vacuum chamber (<2 x 10⁻⁶) -6 100 nm Ag was evaporated by thermal evaporation in Torr.

[0289] Fabrication of perovskite-organic tandem solar cells (PO-TSC)

[0290] For the monolithic (two-terminal) PO-TSC in this study, a narrow bandgap organic sub-cell is integrated on top of the perovskite sub-cell. In short, after thermally evaporating the BCP in the wide bandgap sub-cell, 0.5 nm Au (at 0.05 Å s⁻¹) was thermally evaporated on top of the BCP. -1 (rate) and 10 nm MoOx To form an ICL structure for a series battery, an organic BHJ layer and an interface layer (i.e., ICL) are then sequentially spin-coated onto MoO. x Top. PNDIT-F3N was dynamically spin-coated onto the organic BHJ layer at 1,500 rpm for 40 seconds. Finally, it was passed through a metal shadow mask (pore area: 0.0644 cm²). 2 ) Thermal evaporation of 100 nm Ag.

[0291] Characterization

[0292] 1 H NMR and 13 C10 NMR spectra were measured on a Bruker AVANCE III 300 MHz and 400 MHz spectrometer. Solution UV-vis absorption spectra were obtained from an Agient 8454 spectrophotometer. Cyclic voltammetry (CV) measurements were performed on a CHI 660D electrochemical workstation. CV experiments were performed at room temperature using a standard three-electrode system with a glassy carbon electrode as the working electrode, a Pt wire as the counter electrode, and Ag / AgCl (saturated KCl) as the reference electrode. An aqueous solution of ammonium chloride (NH4Cl, 0.1 M) was used as the supporting electrolyte, and the scan rate was 0.1 V / s. -1 Elemental analysis was obtained using the Elemantar: Vario UNICUBE. Transmission and absorption spectra were performed on a UV-Vis spectrometer (PE Lamda 750).

[0293] Time-dependent photoluminescence (tdPL) spectra were collected using a self-made device in which an excitation laser (450 nm) was introduced into the sample via an optical fiber, and the PL spectra were detected using a detector connected to an Ocean Optics USB2000. X-ray photoelectron spectroscopy (XPS) was performed on a Thermo Fisher ESCALAB XI+ X-ray photoelectron spectrometer. Non-monochromatic He I was used as the UV light at an energy of 21.21 eV.

[0294] The top-view morphology, cross-sectional profile of the tandem cells, and cross-sectional energy-dispersive X-ray spectroscopy (EDX, line scan) of the thin film samples were analyzed using scanning electron microscopy (SEM, QUATTRO S). Powder and thin film X-ray diffraction (XRD) characterization was performed on a D2 Phaser instrument using Cu Kα (wavelength 1.5418 Å) radiation.

[0295] Time-resolved photoluminescence (trPL) spectra were recorded using an FLS980 spectrophotometer (Edinburgh) with a 480 nm pulsed laser excitation. The device's current density-voltage ratio was measured at room temperature in an N2-filled glove box using a Keithley 2400 SourceMeter under simulated sunlight from a solar simulator (EnliTech, SS-F5, Taiwan). J- V) Characteristics. AM 1.5G (100 mW cm⁻¹) was achieved using silicon solar cells (with KG-2 filters) calibrated by the National Renewable Energy Laboratory (NREL). -2 The light intensity of the solar simulator. The perovskite solar cell is covered with a pore area of ​​0.0419 cm². 2 A sunshade to ensure JV The accuracy of the current density curve.

[0296] Use reverse and forward scans in frequency sweep mode. JV Measurement, scan rate 10 mV s -1 The step size was 0.02 V. EQE curves were obtained using an EQE measurement system (EnliTech, QE-R, Taiwan). For perovskite organic tandem solar cells, the width of the EQE curve was measured by applying bias illumination using an 800 nm long-pass filter. g The EQE of the perovskite sub-cell was simultaneously saturated with that of the corresponding organic sub-cell. Similarly, the narrow EE was measured by applying bias illumination using a 500 nm short-pass filter. g The EQE of the organic sub-cell was measured, while simultaneously saturating the corresponding perovskite sub-cell. No bias voltage was applied during all EQE measurements.

[0297] Long-term device stability measurement

[0298] Long-term device stability of the packaged devices was tested using an in-situ stability measurement system (CRYSCO) equipped with multiple sample chambers (without UV filters and temperature control) and automated data collection elements. The maximum power point (MPP) of the solar cells was tracked under simulated AM 1.5G spectrum (1 solar equivalent intensity). The light source was an SLED lamp with a wavelength range of 400 to 1,000 nm. A silicon photodetector was equipped to monitor light intensity variations and automatically adjust the intensity under host control. During testing, the sample chambers were placed in air with a continuous flow of N2.

[0299] Density functional theory (DFT) calculations

[0300] The DFT calculations were performed using the Projected Added Wave (PAW) method implemented in the Vienna Universal Simulation Package (VASP) code. The Generalized Gradient Approximation (GGA) and the Perdew-Burke-Ernzerhof (PBE) exchange-correlated functionals were applied. Van der Waals (vdW) interactions were also included in the calculations using the zero-damped DFT-D3 method with Grimme. A 6×6×6 kilomesh uniform grid in the Brillouin zone was used to optimize the crystal structure of the cubic phase FAPbI3 in the bulk, with 4×4×1 kilomesh for the FAPbI3 plates and 2×2×1 kilomesh for the molecule / FAPbI3 interface. The energy cutoff for the wavefunction of the bulk was set to 500 eV, and the energy cutoff for the wavefunctions of the plates and interfaces was set to 450 eV. The unit cell has a (2 × 2) lateral periodicity and contains four or five FAPbI3 octahedral layers with exposed (100) and (110) surfaces having different ends (FAI-rich and PbI2-rich) and surface defects (V). FA and V Pb The plate replicas were separated by a vacuum of approximately 20 Å. Each structure was optimized until the force on a single atom was less than 0.015 eV Å. -1 With the elimination of Pb 0 and I 0 The energy barrier for the relevant half-reaction is calculated as follows: E (Pb 0 Eliminate) = E (AQS 2- + Pb 2+ ) – E (AQS) + E (Pb 0 )and E (I 0 Eliminate) = E (AQS - + I - )– E (AQS 2- ) + E (I 0 The binding energy is calculated as follows: E (combination) = E (interface) - E (FAPbI3) – E (molecule), in which E (Interface) is the total FAPbI3 energy during molecular adsorption, and E (FAPbI3) and E (Molecules) are separated FAPbI3 and PEA + [H + or NH4 + [Energy].

[0301] Example 1A

[0302] AQSH Synthesis

[0303] Sodium anthraquinone-2-sulfonate (300 mg, 0.97 mmol) and 3 mL of Amberlite cation exchange resin (IR-120 hydrogen form) were added to 5 mL of deionized water. The mixture was stirred overnight, during which time the anthraquinone compound dissolved. The solution was then rinsed again through a cation exchange column with Amberlite cation exchange resin. The resulting sulfonic acid was evaporated, and the compound was dried under vacuum overnight. The product was obtained as a pale yellow powder in a yield of 216 mg (yield: 77%). 1 H NMR (400 MHz,D2O) δ 8.07 (s, 1H), 7.97 (d, J = 8.2 Hz, 1H), 7.88 (d, J = 8.2 Hz, 1H), 7.74– 7.64 (m, 2H), 7.58 – 7.50 (m, 2H) ( Figure 2A ). 13 C NMR (101 MHz, D2O) δ 182.46, 182.36, 148.04, 135.15, 135.10, 133.38, 132.32, 131.57, 131.18, 127.81, 126.72, 123.74. (Two peaks overlap) Figure 2B ).

[0304] Example 1B

[0305] AQSN Synthesis

[0306] An aqueous solution of AQSH (0.97 mmol) obtained as described in Example 1A was cooled to 0°C, and then 0.5 mL of 30% ammonium hydroxide was added to convert the acid to an ammonium salt. The water was evaporated and the compound was vacuum dried overnight. The product was obtained as a pale yellow powder in a yield of 278 mg (yield: 94%). 1 H NMR (400 MHz, D2O) δ 8.28 (s, 1H), 8.14 –8.04 (m, 2H), 8.02 – 7.87 (m, 2H), 7.76 – 7.61 (m, 2H) ( Figure 3A ). 13C NMR (101MHz, D2O) δ 182.36, 182.22, 148.06, 135.16, 135.11, 133.25, 132.22, 131.48, 131.46, 131.19, 127.78, 126.69, 123.70. (One peak overlaps) Figure 3B C 14 H 11 NO5S analysis calculated values: C 55.08%, H 3.63%, N 4.59%, S 10.50%; measured values: C 54.52%, H 3.63%, N 4.57%, S 10.94%.

[0307] Example 1C

[0308] AQSP Synthesis

[0309] An aqueous solution of AQSH (0.97 mmol) obtained as described in Example 1A above was cooled to 0°C, and then 1.2 equivalents of phenethylamine were added to convert the acid to an ammonium salt. The water was evaporated and the compound was vacuum dried overnight. The product was obtained as a pale yellow powder in a yield of 311 mg (yield: 76%). 1 H NMR (400 MHz, DMSO-d6) δ 8.40 (d, J =1.7 Hz, 1H), 8.29 – 8.16 (m, 3H), 8.09 (dd, J = 8.1, 1.7 Hz, 1H), 7.94 (dq, J= 7.3, 4.0 Hz, 2H), 7.75 (s, 3H), 7.40 – 7.29 (m, 2H), 7.29 – 7.19 (m, 3H), 3.04 (t, J = 9.6 Hz, 2H), 2.84 (t, J = 9.6 Hz, 2H) ( Figure 4A ). 13 C NMR (101 MHz, DMSO-d6) δ 182.37, 182.16, 153.58, 137.23, 134.61, 134.56, 133.21, 133.18, 132.95, 132.89, 131.23, 128.70, 128.66, 127.09, 126.86, 126.83, 126.82, 123.72, 33.09. (One peak overlaps) Figure 4B C 22 H 19NO5S analysis and calculation values: C 64.53%, H 4.68%, N 3.42%, S 7.83%; measured values: C 64.60%, H 4.68%, N 3.29%, S 8.18%.

[0310] Example 2

[0311] Synthesis of AQS ester

[0312] First, sodium anthraquinone-2-sulfonate (2.5 g, 8 mmol) was converted to the corresponding sulfonyl chloride by reaction with thionyl chloride (10 mL, 137 mmol) and DMF (0.5 mL). The reaction mixture was poured into ice water. The precipitate was filtered and dried under vacuum to give a yellow solid (2.4 g, 98%). Pyridine (0.06 mL) was added to a mixture of sulfonyl chloride (1 mmol) and methanol (1 mmol) in DMF (3 mL), and the mixture was stirred at 50–60 °C for 2 hours. The solution was cooled to room temperature and poured into water (20 mL). The resulting precipitate was filtered, washed with water, and purified by column chromatography (0.5% MeOH in DCM solution) to give 195 mg of a pale yellow solid (yield: 65%).

[0313] Example 3

[0314] Synthesis of AQ amide

[0315] Butylamine (0.16 mL, 1.6 mmol) was added dropwise to a solution of sulfonyl chloride (100 mg, 0.33 mmol) in DCM (5 mL) at 0 °C. The reaction mixture was warmed to room temperature and stirred for 2 hours. The reaction mixture was washed with water and purified by column chromatography (0.5% MeOH in DCM solution) to give 105 mg of a pale yellow solid (yield: 92%).

[0316] Example 4

[0317] Design and characterization

[0318] Although anthraquinone (AQ) is believed to serve as a redox framework, the inventors have revealed through their own research and experiments that AQ cannot actually be converted to redox structures by Pb. 0 with I 0 Electron shuttle between them promotes the formation of PbI2, which may be attributed to its relatively low redox potential compared to Pb, making it unable to oxidize metallic Pb. 0 ( Figure 5 To solve this problem, the inventors designed an AQ framework that could use strongly electron-withdrawing SO3. -The functional group was modified to adjust its redox potential to -0.21 V with NHE, thereby achieving a suitable redox shuttle between Pb (-0.365 V with NHE) and I2 (0.536 V with NHE). This modification also increased its solubility in polar organic solvents (i.e., DMF and DMSO) for better processability and provided additional synthetic tunability to its properties. Figure 6A and 6B Furthermore, it was found that replacing the -H in the cation moiety of AQS with -NH4 and -PEA ( Figure 7 It can impart the ability to passivate molecular defects.

[0319] The proposed redox shuttle Figure 8 The diagram shows the redox capabilities of the AQS core control molecule. Firstly, by combining AQSH and Pb... 0 and I 0 Pb was tested by dissolving powder in a DMF:IPA mixed solvent (volume ratio 1:10). 0 with I 0 The feasibility of electron transfer between the raw material powder and the resulting PbI2 precipitate was investigated to provide a good balance between the solubility of the raw material powder and the formation of the precipitate. Figure 9 ).like Figure 9 As shown in the illustration, the control sample (without AQSH) exhibited minimal yellow solid product and remained dark brown. Conversely, the target sample containing AQSH turned colorless and formed numerous yellow precipitates, indicating that Pb... 0 and I 0 The electron shuttle efficiently converts the material into solid PbI₂. The transmission spectrum of the supernatant solution (taken from the sample) further confirms that I₂ is present only in the control solution. 0 The substance was found to have two characteristic peaks at approximately 290 nm and 360 nm.

[0320] To rule out the possibility of AQSH oxidizing iodides, another set of DMF solutions composed of pure I₂, pure AQSH, and FAI:AQSH were prepared. Figure 10A Clear FAI: AQSH solution did not show origin from I. 0 The peak of the substance, which means Pb 0 Instead of I - Selective oxidation of [a substance] was also tested using AQSH and Pb. 0 Or I 0 The solution was designed to further verify this selective redox process. Figure 10B By performing powder X-ray diffraction (XRD), the presence of characteristic diffraction peaks at 12.7°, 26.0°, and 38.7° was observed. Figure 11 Most of the yellow precipitate ( Figure 9 The illustration (shown in the image) was verified to be PbI2. Therefore, it is speculated that the AQS derivative will act as an effective redox mediator for perovskite, thereby achieving I... 0 Selective reduction and Pb 0 Selective oxidation. Simultaneously eliminating these defects should help suppress halide segregation (e.g., in mixed halide perovskites). Figure 12 (As shown).

[0321] Example 5

[0322] Suppression of halide segregation in mixed halide perovskites

[0323] Preferential oxidation of halides with relatively low oxidation potential (I - <Br - <Cl - This is a key step in halide mass transport, ultimately leading to phase segregation in perovskites. Therefore, time-dependent PL (tdPL) was first performed to investigate the effect of AQS-based redox mediators on halide segregation. Figure 13 AQS derivatives, namely AQSH, AQSN, and AQSP, were incorporated as additives into I / Br mixed perovskite films. The initial PL peak at approximately 700 nm was identified as the original perovskite. After continuous irradiation, the PL of the AQS-based perovskite film remained stable, exhibiting only a slight redshift of 3-5 nm. Figure 14 Conversely, the bimodal shape, a hallmark of halide segregation, gradually appeared in the PL spectrum of the control sample within minutes.

[0324] For segregated I / Br mixed perovskites, photogenerated charge carriers will flow into the I-rich region due to their lower band gap compared to the surrounding unsegregated domain. In this case, a new PL peak with a lower photon energy (approximately 1.64 eV) is observed in the unstable control perovskite. To visually investigate the degree of halide segregation, the residual spectrum derived by subtracting the initial PL from the final spectrum is used, such as... Figure 15 As shown, the perovskite based on AQS exhibits only small and symmetrical valley peak shapes in its residual PL spectrum, while the control sample shows significantly larger and asymmetrical peak-valley shapes. These significant changes in peak position and shape indicate severe halide segregation. Furthermore, to eliminate the influence of cation substitution on phase stability, tdPL measurements of the perovskite film were performed using NH4I or PEAI as additives, which showed negligible effects on mitigating phase segregation. Figure 16 ).

[0325] Then, high-resolution X-ray photoelectron spectroscopy (XPS) was used to study the effects under continuous illumination (AM 1.5G, 100 mW cm⁻¹). -2Surface properties of perovskite films aged under ) Figure 17 To verify whether AQS-based redox mediators help inhibit Pb 0 and I 0 The formation of [the substance] focuses on the elements Pb, I, and Br. Figures 18A to 18C The binding energies (BE) of approximately 138.1 eV and 142.9 eV are assigned as the values ​​of Pb 4f in the AQS-based perovskite film, respectively. 7 / 2 and Pb 4f 5 / 2 In contrast, for the control sample, Pb4f 7 / 2 and Pb 4f 5 / 2 The BE values ​​shifted slightly to 138.5 eV and 143.3 eV. Furthermore, Pb-derived metals were observed in the control perovskite (the major decomposition product of perovskite under illumination). 0 The two distinct abutments (i.e., 136.7 eV and 141.6 eV).

[0326] Metallic Pb in total Pb 0 The atomic ratio was quantified, and the results were in Figure 19 , 20A As shown in 20B. The control sample shows metallic Pb. 0 The proportion of Pb is a high 11.58%, while that of AQS-based perovskites is 2.64-3.11%. 0 This significant reduction may be attributed to the oxidation to Pb mediated by AQS derivatives. 2+ ,like Figures 8 to 12 The previous results are shown in the figure.

[0327] Regarding halide elements, two peaks were observed in the reference perovskite, with BE values ​​of 619.3 eV and 630.8 eV, originating from I 3d, respectively. 5 / 2 and I 3d 3 / 2 ( Figure 18B Given the volatility of iodine products, relative atomic ratios were used to study the distribution of halides on the illuminated perovskite surface. Figure 21It is noted that the I / Pb atomic ratio (2.12–2.18) of the AQS-based perovskite films is slightly higher than the stoichiometry (indicated by the dashed line), while the (I+Br) / Pb atomic ratio is close to the stoichiometry (3.09). This compositional inhomogeneity may be attributed to the different nucleation / crystallization kinetics of I- and Br-based perovskites. However, a loss of halide content was found in the control perovskite because the (I+Br) / Pb (2.48) atomic ratio is much lower than its stoichiometry of 3.09. Considering its I / Pb atomic ratio of 1.80, this loss of halide content is attributed to iodine content, as its oxidation potential is lower than that of bromides (1.065 V). Meanwhile, the increased I / Br ratio of 2.67 in the control samples indicates that Br - It migrates faster along the direction of the incident light, as reported.

[0328] Example 6

[0329] Structural properties and density functional theory (DFT) calculations

[0330] The structural properties of the perovskite film were investigated using scanning electron microscopy (SEM) and XRD, and the results... Figure 22 and 23 The XRD patterns all revealed two prominent diffraction peaks at 2θ at 14.4° and 20.4°, corresponding to the (100) and (110) crystal planes of the perovskite. For AQSN- and AQSP-based perovskites, lower intensities of the diffraction peaks from PbI2 were observed, which may be attributed to the moderating effect of the substituted cations on perovskite growth. Top-view SEM images showed no significant differences in the morphology of the samples. The distribution of the AQS derivatives within the perovskite layer was depicted by cross-sectional SEM-energy dispersive spectroscopy (SEM-EDX), which showed a uniform distribution. Figure 24 Furthermore, the optical band gap of the perovskite film was determined to be approximately 1.79 eV using UV-vis absorption spectroscopy. Figure 25 As shown.

[0331] Based on the above structural analysis, density functional theory (DFT) calculations were performed on the redox mediator / perovskite interface model to gain a deeper understanding of the role of AQS derivatives in promoting the overall redox reaction and passivating the perovskite, and to estimate their interactions. Two representative perovskite surfaces were considered, each with different ends (FAI-rich and PbI2-rich) and surface defects (V0.05). FA and V Pb ),like Figure 26A and 26B As shown. First, calculate the relationship with Pb. 0 and I 0 The energy barrier for eliminating the associated half-reaction ( Figure 27A and27B The results show that from Pb 0 To Pb 2+ The half-reaction exhibits a fairly large energy barrier (11.6 eV), while from I 0 to I - The reduction of the AQS derivative is thermodynamically more favorable to the original perovskite (-5.0 eV). Introducing the AQS derivative onto the perovskite surface lowered the energy barriers of both half-reactions. The overall energy barrier of the redox reaction decreased by more than three times (from 1.76 eV to 0.49 eV), validating the ability of these molecules to promote electron shuttle within the perovskite.

[0332] As discussed in Example 4, the AQS core controls redox capabilities, while the substitution of -H with -NH4 and -PEA provides additional defect passivation effects to the molecule. AQS on PbI2--rich (100) and (110) surfaces... - With Pb 2+ The calculated binding energies between them are 7.50 eV and 3.75 eV, respectively, which are higher than the binding energies of the control perovskite. Figure 28 ). with Pb 2+ Stronger bonding is crucial for stabilizing perovskites. Furthermore, the calculation of NH4... + / PEA + The binding energy between the perovskite and the surface ( Figure 29 ) Optimized crystal structure of perovskite modified by redox mediator in Figures 30A-30B , Figures 31A-31D , Figures 32A-32D , Figures 33A-33D and Figure 34 The results show that, regardless of crystal planes and surface properties, PEA... + The cations are all greater than NH4 + It provides a stronger defect passivation effect because it consistently exhibits a higher binding energy with the perovskite surface.

[0333] Time-resolved photoplethysmography (trPL) measurements were performed on perovskite films to investigate the defect passivation effect of AQS derivatives. Figure 35A ). Comparison with the average carrier lifetime of perovskites ( The value is calculated to be 0.91. μ s, and the AQSH-based perovskite slightly increased to 1.07. μ s ( Figure 35B It is worth noting that for perovskites based on AQSN and AQSP, 1.40 were obtained respectively. μ s and 1.50 μ s-carrier lifetime. Since extended carrier lifetime typically indicates enhanced radiative recombination, the space charge confinement current (SCLC) method is used to quantify the trap density in perovskites.N 陷阱 ) ( Figure 36A First, through fitting... JV Curve extraction trap filling limit voltage (V) TFL Then, the values ​​of the control, AQSH-based perovskite, AQSN-based perovskite, and AQSP-based perovskite were calculated. N 陷阱 The values ​​are 2.68 × 10 16 2.51 × 10 16 1.61 × 10 16 and 1.13 × 10 16 cm -3 ( Figure 36B ).

[0334] Example 7

[0335] Photovoltaic performance of PSC and PO-TSC

[0336] To further investigate the suppressed phase segregation and nonradiative recombination properties imparted by the AQSP additive, a single-junction with a width of E was fabricated based on a glass / ITO / DC-PA / perovskite / C60 / BCP / Ag structure. g PSC, where ITO is indium tin oxide and DC-PA represents p-type self-assembled monolayer (SAM). The characteristics of perovskite devices with and without AQSP (denoted as control and target, respectively) are discussed below. The control device exhibits a good PCE of 18.68%, while the optimized target device achieves an efficiency of 19.58%, primarily due to V... oc Increased from 1.309 V to 1.351 V ( Figures 37A to 37C The target device also exhibits negligible hysteresis, as a PCE of 19.14% can be obtained in the forward scan direction. Figure 38 Photovoltaic performance of devices based on perovskites with different AQS derivatives. Figure 39A Provided in Figure 39B Summary.

[0337] The band gap of the target device was determined to be 1.81 eV by differentiating its external quantum efficiency (EQE) spectrum, and the spectrum exhibited an inflection point at 685 nm. Figure 40 The integral short-circuit current density of EQE (J) sc ) and from JV The values ​​extracted from the curve are a very good match ( Figure 41 V of the target device oc Defect (E) g – q V ocThe calculated value is 0.459 V, which is the highest reported value to date. g The lowest value of PSC is approximately 1.80 eV. Figure 42A and 42B Furthermore, we significantly improved the long-term stability of the target cell (initial efficiency = 18.98%), retaining 95% of its initial PCE after 500 hours of operation at maximum power point (MPP) under 1 solar illumination. Figure 43 In contrast, the efficiency of the control battery (initial efficiency = 18.08%) dropped rapidly (>20%) after 300 hours of operation.

[0338] The above width E g Perovskite and organic semiconductors are integrated to construct monolithic PO-TSCs. PM6:Y6:PC 71 BM ternary blends are used as narrow E g The bulk heterojunction layer in the secondary cell. The device structure of PO-TSC is as follows. Figure 44 As shown, BCP / Au / MoO x It serves as an interconnect layer (ICL). To achieve a good balance between transparency and electrical properties, a 0.5 nm thick Au layer was used as a composite layer. The thicknesses of the perovskite and organic BHJ layers were optimized to approximately 260 nm and 150 nm, respectively, to ensure efficient photon utilization and current matching between the two sub-cells. Figure 45 ).

[0339] Notably, the tandem solar cells achieved an impressive PCE of 25.22% and a high VT of 2.151 V. oc 14.36 mA cm -2 J sc With a fill factor of 81.65%, it exhibits negligible hysteresis and a steady-state power output (SPO) of 25.00%. Figure 46A and Figure 46B This high efficiency can be attributed to the low voltage loss of the perovskite sub-cell and the ICL (internal galvanic cell). Figure 47 and Figure 48 The series-connected cells in this study also exhibited good current matching, with a current of 14.84 mA cm⁻¹. -2 and 14.38 mA cm -2 J sc Integrating from the EQE spectra of perovskite and organic sub-cells respectively ( Figure 49 ).

[0340] An average PCE of 24.33% was calculated based on 25 independently connected cells manufactured in different batches. Figure 50As shown. The packaged series cells (with a fixed mask) were also sent to the independent photovoltaic calibration organization (SIMIT) for certification, achieving a certified efficiency of 24.27%. This value is believed to represent the highest certified PCE reported by PO-TSC. Figure 51 , Figures 52A-52E and Figure 53 The encapsulated series cells, exposed to 1 solar illumination (AM 1.5G spectrum, no UV filter) in an N2-filled chamber, retained 92% of their initial PCE after 500 hours of continuous operation at approximately 45°C. Figure 54 ).

[0341] The invention is given by way of example only, and various other modifications and / or alterations may be made to the described embodiments by those skilled in the art without departing from the scope of the invention as specified in the appended claims.

Claims

1. A perovskite layer for a solar cell, the perovskite layer comprising a mixture of mixed halide perovskite and sulfonylnaphthoquinone compounds, the mixed halide perovskite comprising [A +1 B +2 X -1 The grain structure of [3], wherein A +1 It is a monovalent cation at site A, B +2 It is a divalent cation at the B site, and X -1 It is a halide anion; the monovalent cation at the A site is selected from formamidinium ion (FA). + ), methylammonium ion (MA + ), ethylammonium ion (EA) + ), guanidine ion (GA) + ), Cs + 、Rb + The group consisting of the group and its combinations; the B-site divalent cation is selected from Pb. 2+ Sn 2+ 、Ge 2+ The group consisting of the group and its combinations; and the halide anion selected from I - ,Br - Cl - The group consisting of the sulfonyl naphthoquinones and their combinations; the sulfonyl naphthoquinones having the structure of any one of formulas (II), (III), (IV), (V), (VI) or (VII): Equation (II), Equation (III), Formula (IV), Equation (V), Formula (VI), or Equation (VII), in: R1 is independently selected from one of OM, OR4, and NR5R6, where M is a cation selected from the group consisting of: H + Na + K + Cs + 、Rb + 、Sr 2+ Ca 2+ Ni 2+ Cu 2+ Co 2+ Zn 2+ Mg 2+ Ba 2+ Li + ammonium ions and amium ions; R4, R5, and R6 are independently selected from the group consisting of: hydrogen, substituted or unsubstituted C1 to C4 alkyl, substituted or unsubstituted C2 to C6 alkenyl, substituted or unsubstituted C2 to C6 alkynyl, halogen, unsubstituted C6 to C10 aryl, -CN, -C(=O)OH, -C(=O)H, -C(=O)R7, -OR7, -SH, -SR7, -NH2, -NHR6, -N(R7)2, -Si(R7)3, -OSi(R7)3, -S(O)OH, and -P(O)(OH)2, wherein R7 is an alkyl or phenyl group, and n is 1-1000; The sulfonylnaphthoquinone compounds mentioned herein do not include porphyrins and are configured to suppress halide segregation in the mixed halide perovskite.

2. The perovskite layer of claim 1, wherein the sulfonylnaphthoquinone compound of formula (II) is selected from any one of formula (VIII), formula (IX) or formula (X): Equation (VIII), Formula (IX), or Equation (X), Where M is H + R4 is a C1 to C4 alkyl group; R5 and R6 are independently selected from hydrogen and C1 to C4 alkyl groups.

3. The perovskite layer of claim 2, wherein the sulfonylnaphthoquinone compound of formula (VIII) is selected from any one of formulas (VIIIa), (VIIIb), and (VIIIc): Equation (VIIIa), Equation (VIIIb), and Formula (VIIIc).

4. The perovskite layer of claim 2, wherein the sulfonylnaphthoquinone compound comprises the structure of formula (IXa): Formula (IXa).

5. The perovskite layer of claim 2, wherein the sulfonylnaphthoquinone compound comprises the structure of formula (Xa): Equation (Xa).

6. The perovskite layer of claim 1, wherein the mixed halide perovskite is selected from CsPb. 0.5 Sn 0.5 I3, FAPbI3, MA 0.25 FA 0.75 PbI 2.2 Br 0.6 Cl 0.2 Cs 0.02 FA 0.96 MA 0.02 PbI 0.99 Cl 0.01 MAPb 0.92 Sn 0.08 I3, (FA) 0.95 MA 0.05 ) 0.95 Cs 0.05 Pb(I 0.96 Br 0.04 3. Rb 0.1 FA 0.8 GA 0.1 Pb 0.6 Ge 0.4 I3 and (FA 0.92 MA 0.08 ) 0.9 Cs 0.1 Pb(I 0.92 Br 0.08 )3 and Cs 0.2 FA 0.8 Pb(I 0.6 Br 0.4 Any one of 3.

7. The perovskite layer of claim 1, wherein [A] +1 B +2 X -1 The grain structure of [3] includes the grain boundaries where the sulfonyl naphthoquinone compound is located.

8. The perovskite layer of claim 1, wherein the perovskite layer contains 0.3 mol% to 1 mol% of the sulfonylnaphthoquinone compound.

9. The perovskite layer of claim 1, further comprising 3 mol% MAPbCl3 and 5 mol% 4-guanidinobenzoic acid.

10. The perovskite layer of claim 1, having a thickness of 260 nm.

11. A solar cell comprising: First hole transport layer; First electron transport layer; and The first active layer of the perovskite layer as described in claim 1 is disposed between the first hole transport layer and the first electron transport layer.

12. The solar cell of claim 11, wherein the first active layer is in direct contact with the first hole transport layer and the first electron transport layer.

13. The solar cell of claim 12, wherein the first hole transport layer is disposed on the transparent conductive layer, the transparent conductive layer is disposed on the transparent substrate, and the first electron transport layer is disposed on the first barrier layer, the first barrier layer being disposed on the first metal layer.

14. The solar cell of claim 13, wherein the first hole transport layer is in direct contact with the transparent conductive layer, and the first electron transport layer is in direct contact with the first blocking layer.

15. The solar cell of claim 13, wherein the transparent substrate is selected from the group consisting of: glass, polymethyl methacrylate (PMMA), polycarbonate (PC), general-purpose polystyrene (GPPS), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polydimethylsiloxane (PDMS), styrene-ethylene-butene-styrene (SEBS), polyethylene terephthalate-1,4-cyclohexanedimethyl terephthalate (PETG), acrylonitrile-butadiene-styrene copolymer (ABS), polypropylene (PP), polyamide (PA), acrylonitrile-styrene copolymer (AS), and combinations thereof.

16. The solar cell of claim 13, wherein the transparent conductive layer is selected from the group consisting of: indium tin oxide (ITO), aluminum zinc oxide (AZO), tin oxyfluoride (FTO), graphene, poly(3,4-ethylenedioxythiophene):poly(styrene sulfonic acid) (PEDOT:PSS), silver nanowires, copper nanowires, and combinations thereof.

17. The solar cell of claim 13, wherein the first hole transport layer is selected from the group consisting of: poly(triarylamine) (PTAA), PEDOT:PSS, NiOx, 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene (spiro-OMeTAD), DC-PA, MoO x and their combinations.

18. The solar cell of claim 13, wherein the first electron transport layer is selected from PC. 61 BM, C 60 The group consists of SnO2, PNDIT-F3N and their combinations.

19. The solar cell of claim 13, wherein the first barrier layer is selected from copper bath (BCP) and double C. 60 SnO x Zr(acac)2, MoO x Groups composed of its components.

20. The solar cell of claim 13, wherein the first metal layer is selected from the group consisting of Ag, Cu, Au, Al, W, Fe, Pt and combinations thereof.

21. The solar cell of claim 11, comprising a band gap of 1.81 eV.

22. The solar cell of claim 11, wherein it has a power conversion efficiency of 18.98% to 19.58%.

23. The solar cell of claim 11, wherein the solar cell has a power conversion efficiency of 95% of its initial value after 500 hours of AM1.5G illumination at 45°C.

24. The solar cell of claim 13, further comprising a sub-cell disposed on the first metal layer and in direct contact with the first metal layer.

25. The solar cell of claim 24, further comprising an anti-reflective layer, wherein the transparent conductive layer and the transparent substrate are disposed on and in direct contact with the anti-reflective layer.

26. The solar cell of claim 25, wherein the antireflective layer is selected from the group consisting of MgF2, LiF, PDMS, and combinations thereof.

27. The solar cell of claim 24, wherein the sub-cell comprises: Second hole transport layer; Second electron transport layer; and The second active layer is disposed between the second hole transport layer and the second electron transport layer.

28. The solar cell of claim 27, wherein the second active layer is in direct contact with the second hole transport layer and the second electron transport layer.

29. The solar cell of claim 27, wherein the second active layer is selected from the group consisting of perovskite photovoltaic materials, Si photovoltaic materials, CIGS photovoltaic materials, CdTe photovoltaic materials, organic photovoltaic materials, and combinations thereof.

30. The solar cell of claim 28, wherein the second hole transport layer is disposed on the first metal layer, and the second electron transport layer is disposed on the second metal layer.

31. The solar cell of claim 27, wherein the second hole transport layer is in direct contact with the first metal layer, and the second electron transport layer is in direct contact with the second metal layer.

32. The solar cell of claim 27, wherein the second hole transport layer is in direct contact with the first metal layer, and the second electron transport layer is in direct contact with the second blocking layer.

33. The solar cell of claim 30, comprising a perovskite organic tandem solar cell.

34. The solar cell of claim 33, wherein the perovskite organic tandem solar cell comprises Cs 0.2 FA 0.8 Pb(I 0.6 Br 0.4 The first active layer of )3 and PM6:Y6:P 71 The second active layer of BM.

35. The solar cell of claim 33, wherein the perovskite organic tandem solar cell has a power conversion efficiency of 24.27% to 25.22%.

36. The solar cell of claim 33, wherein the perovskite organic tandem solar cell has a power conversion efficiency of 92% of its initial value after 500 hours of AM1.5G illumination at 45°C.

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