Perovskite layer, manufacturing method thereof and solar cell

Abstract

The invention relates to a perovskite layer, a manufacturing method thereof and a solar cell. The present invention relates to a perovskite layer for a solar cell, the perovskite layer comprising a mixture of a halide perovskite and a sulfonyl naphthoquinone compound having the structure of formula (I) wherein: R1 is independently selected from one of OM, OR4 and NR5R6, where M is a cation, 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. A method for manufacturing said perovskite layer and a solar cell comprising a first active layer of said perovskite layer are also presented. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a perovskite layer, for example, particularly but not exclusively to a perovskite layer comprising a mixture of a halide perovskite and a sulfonyl naphthoquinone compound; and a method for making a perovskite layer. The present invention also relates to a solar cell comprising a first active layer of a perovskite layer. Background Art

[0002] Metal halide perovskite solar cells (PSCs) are promising photovoltaic (PV) technologies due to their high absorption coefficient, low exciton binding energy, high carrier mobility, long carrier diffusion length, and ambipolar charge transport. PSCs can generally be configured as single-junction solar cells and multi-junction (or tandem) solar cells (i.e., solar cells composed of two or more sub-cells). In particular, since the tandem configuration allows the combination of sub-cells with different properties (such as a combination of wide-bandgap and low-bandgap sub-cells, which can meet the needs of high-energy photons and low-energy photons during operation), it is believed that PSCs with a tandem configuration will have higher power conversion efficiency (PCE) compared to PSCs with a single-junction configuration. For example, in a PSC with a desired bandgap (E g ) of about 1.8 to 1.9 eV, the PCE can be increased from about 15% to about 24%, especially when I / Br hybrid perovskite is used ( Figure 1A ).

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

[0004] Although there are reports on suppressing halide segregation through methods such as crystallization control, defect passivation, surface modulation, and strain engineering, it is believed that none of these strategies can simultaneously address the Pb 2+ Easily reduced to Pb 0 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 that are believed to disappear quickly after taking effect. Nevertheless, it remains a challenge to make additives that can easily tune their properties to eliminate different defects and can function in a sustainable manner without introducing additional deep-level defects.

[0005] The present invention seeks to eliminate or at least mitigate these disadvantages by providing new or otherwise improved solar cell active layers, in particular enabling selective iodine (I2) reduction and metallic lead (Pb) conversion in a sustainable manner. 0 ) oxidized active perovskite layer. Summary of the invention

[0006] In a first aspect of the present invention, a perovskite layer for a solar cell is provided, which comprises a mixture of a halide perovskite and a sulfonyl naphthoquinone compound, wherein the sulfonyl naphthoquinone compound has a structure of formula (I):

[0007]

[0008] in:

[0009] 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 may form a condensed ring.

[0010] Optionally, 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 + , ammonium ion and aminum ion; 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 alkyl or phenyl; and when R2 and R3 form a fused ring, it contains a substituted or unsubstituted 6- to 14-membered ring.

[0011] In an optional embodiment, the sulfonyl naphthoquinone compound is any one of formula (II), (III), (IV), (V), (VI) or (VII):

[0012]

[0013]

[0014] wherein R1 is as defined above; and n is 1-1000.

[0015] Optionally, the sulfonyl naphthoquinone compound of formula (II) is selected from any one of formula (VIII), formula (IX) or formula (X):

[0016]

[0017]

[0018] Where M is H + , ammonium ion or aminum ion; R4 is a C1 to C4 alkyl group; R5 and R6 are independently selected from hydrogen and a C1 to C4 alkyl group.

[0019] In one embodiment of the present invention, the sulfonyl naphthoquinone compound of formula (VIII) is selected from any one of formula (VIIIa), (VIIIb) and (VIIIc):

[0020]

[0021] In an optional embodiment, the sulfonyl naphthoquinone compound comprises the structure of formula (IXa):

[0022]

[0023] In an optional embodiment, the sulfonyl naphthoquinone compound comprises a structure of formula (Xa):

[0024]

[0025] Optionally, the halide perovskite comprises [A +1 B +2 X -1 3], where A +1 is a monovalent cation at the A-site, B +2 is a divalent cation at the B-site, and X -1 It is a halide anion.

[0026] Optionally, the monovalent cation at position A is selected from the group consisting of formamidinium ions (FA + ), methylammonium ion (MA+ ), ethylammonium (EA + ), guanidine ion (GA + ), Cs + , Rb + and a combination thereof; the divalent cation at position B is selected from Pb 2+ Sn 2+ ,Ge 2+ and a combination thereof; and the halide anion is selected from the group consisting of I - Br - , Cl - and their combinations.

[0027] In an optional embodiment, 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.

[0028] Optionally, [A +1 B +2 X -1 The grain structure of 3] includes grain boundaries at which the sulfonyl naphthoquinone compounds are accommodated.

[0029] Optionally, the perovskite layer contains about 0.3 mol % to about 1 mol % of a sulfonyl naphthoquinone compound.

[0030] In an optional embodiment, the perovskite layer further comprises about 3 mol % MAPbCl 3 and 5 mol % 4-guanidinobenzoic acid.

[0031] Optionally, the perovskite layer has a thickness of about 260 nm.

[0032] In a second aspect of the present invention, there is provided a method for manufacturing a perovskite layer according to the first aspect, comprising the following steps:

[0033] 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 on a substrate; and c) annealing the spin-coated solution mixture to form a perovskite layer.

[0034] Optionally, step a) comprises the following steps: a1) providing a first reaction mixture comprising formamidine, methylammonium and cesium halide; and a2) mixing the first reaction mixture with about 0.3 mol % to about 1 mol % of a sulfonyl naphthoquinone compound to form a second reaction mixture.

[0035] In an optional embodiment, the halide includes CsI, CsBr, FAI, FABr, PbI2, and PbBr2.

[0036] Optionally, the first reaction mixture further comprises about 3 mol % MAPbCl 3 and about 5 mol % 4-guanidinobenzoic acid.

[0037] Optionally, step a) further comprises step a3) converting sodium anthraquinone-2-sulfonate into sulfonyl naphthoquinone compounds.

[0038] Optionally, step b) includes the step of bl) adding chlorobenzene anti-solvent to the center of the spin-coated solution mixture about 10 seconds before the completion of the spin-coating process.

[0039] Optionally, the spin coating is performed at about 4000 rpm to about 6500 rpm, with a ramping rate of about 1500 rpms. -1 .

[0040] In an optional embodiment, the method further comprises the following steps after step c): spin coating a surface passivation agent of piperazinium iodide (PI) on the perovskite layer; and annealing the perovskite layer coated with PI.

[0041] In a third aspect of the present invention, a solar cell is provided, comprising: a first hole transport layer; a first electron transport layer; and a first active layer of the perovskite layer according to the first aspect, which is arranged between the first hole transport layer and the first electron transport layer.

[0042] Optionally, the first active layer is in direct contact with the first hole transport layer and the first electron transport layer.

[0043] In an optional embodiment, the first hole transport layer is disposed on the transparent conductive layer, which is disposed on the transparent substrate, and the first electron transport layer is disposed on the first barrier layer, which is disposed on the first metal layer.

[0044] 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.

[0045] 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-butylene-styrene (SEBS), ethylene terephthalateco-1,4-cylclohexylenedimethyleneterephthalate (PETG), acrylonitrile-butadiene-styrene copolymer (ABS), polypropylene (PP), polyamide (PA), acrylonitrile-styrene copolymer (AS), and combinations thereof.

[0046] Optionally, the transparent conductive layer is selected from the group consisting of indium tin oxide (ITO), aluminum zinc oxide (AZO), fluorinated tin oxide (FTO), graphene, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS), silver nanowires, copper nanowires, and combinations thereof.

[0047] 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'-spirobifluorene (Spiro-OMeTAD), DC-PA, MoO x and combinations thereof.

[0048] Optionally, the first electron transport layer is selected from PC 61 BM, C 60, SnO2, PNDIT-F3N and a group consisting of their combinations.

[0049] Optionally, the first barrier layer is selected from the group consisting of bathocuproin (BCP), double C 60 (bis-C 60 )、SnO x 、Zr(acac)2、MoO x and their combinations.

[0050] Optionally, the first metal layer is selected from the group consisting of Ag, Cu, Au, Al, W, Fe, Pt and combinations thereof.

[0051] In an optional embodiment, the solar cell comprises a band gap of about 1.81 eV.

[0052] Optionally, the solar cell comprises a power conversion efficiency of about 18.98% to about 19.58%.

[0053] Optionally, the solar cell comprises a power conversion efficiency of 95% of its initial value after 500 hours of AM 1.5G illumination at about 45°C.

[0054] In an optional embodiment, the solar cell further comprises a subcell disposed on and in direct contact with the first metal layer.

[0055] Optionally, the solar cell further comprises an anti-reflection layer, and the transparent conductive layer and the transparent substrate are disposed on and in direct contact with the anti-reflection layer.

[0056] Optionally, the anti-reflective layer is selected from the group consisting of MgF2, LiF, PDMS and combinations thereof.

[0057] Optionally, the subcell comprises: 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.

[0058] In an optional embodiment, the second active layer is in direct contact with the second hole transport layer and the second electron transport layer.

[0059] 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.

[0060] Optionally, a second hole transport layer is disposed on the first metal layer, and a second electron transport layer is disposed on the second metal layer.

[0061] 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.

[0062] In an optional embodiment, 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.

[0063] 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.

[0064] In an optional embodiment, the solar cell comprises a perovskite-organic tandem solar cell.

[0065] Optionally, the perovskite-organic tandem solar cell comprises Cs 0.2 FA 0.8 Pb(I 0.6 Br 0.4 )3 first active layer and PM6:Y6:P 71 The second active layer of BM.

[0066] Optionally, the perovskite-organic tandem solar cell has a power conversion efficiency of about 24.27% to about 25.22%.

[0067] Optionally, the perovskite-organic tandem solar cell has a power conversion efficiency of 92% of its initial value after 500 hours of AM 1.5G illumination at about 45°C. BRIEF DESCRIPTION OF THE DRAWINGS

[0068] The invention will now be described in more detail, by way of example only, with reference to the accompanying drawings, in which:

[0069] Figure 1A The theoretically achievable efficiency of a double junction solar cell with a 2-terminal configuration is shown;

[0070] Figure 1B is a schematic diagram illustrating an exemplary solar cell according to an embodiment of the present invention;

[0071] Figure 1C is a schematic diagram illustrating an exemplary solar cell according to an embodiment of the present invention;

[0072] Figure 2A The synthesized AQSH (compound of formula (VIIIa)) 1 H NMR spectrum;

[0073] Figure 2B The synthesized AQSH (compound of formula (VIIIa)) 13 C NMR spectrum;

[0074] Figure 3A The synthesized AQSN (compound of formula (VIIIb)) 1H NMR spectrum;

[0075] Figure 3B The synthesized AQSN (compound of formula (VIIIb)) 13 C NMR spectrum;

[0076] Figure 4A The synthesized AQSP (compound of formula (VIIIc)) 1 H NMR spectrum;

[0077] Figure 4B The synthesized AQSP (compound of formula (VIIIc)) 13 C NMR spectrum;

[0078] Figure 5 Figure 1 shows I dispersed in a DMF / IPA mixed solvent (volume ratio 1:10) with anthraquinone. 0 and Pb 0 Photograph of powder (after stirring at 100°C for 60 minutes);

[0079] Fig. 6A is a schematic diagram illustrating the molecular structure of organic redox mediators based on AQS cores with different cationic substituents;

[0080] Figure 6B shows the cyclic voltammetry curve of AQSH;

[0081] Figure 7 is a schematic diagram illustrating the synthetic routes of AQSH, AQSP and AQSN;

[0082] Figure 8 is a schematic diagram illustrating the electron shuttling between the AQS core, Pb, and I;

[0083] Fig. 9 Pb dispersed in IPA:DMF mixed solvent (v:v=10:1) with and without AQSH is shown. 0 and I 0 Transmission spectrum of powder;

[0084] Fig. 10A The transmission spectra of I2, FAI, and FAI+AQSH powders dissolved in DMF are shown;

[0085] Fig. 10B Shown by AQSH and I 0 The solution composed of powder (left) and AQSH and Pb 0 Photograph of a solution composed of powders (right);

[0086] Fig.11 Shows that from Fig. 9Powder X-ray diffraction (XRD) patterns of PbI2 and bottom sediment obtained in the glass vial shown in the inset;

[0087] Fig.12 Schematic diagram showing the proposed redox mediator as an additive for sustainable elimination of metallic Pb from the perovskite layer. 0 and I 0 The mechanism of substances and their effect on inhibiting halide segregation;

[0088] Fig.13 Time-dependent photoluminescence (tdPL) spectra of I / Br mixed perovskites with 0.5 mol % of different AQS derivatives are shown;

[0089] Fig.14 The normalized PL spectra of I / Br mixed perovskite films with different redox mediators after illumination for 0, 5, and 10 min are shown (from Fig.13 The corresponding time-dependent PL spectra of are extracted from );

[0090] Fig.15 Derivatized PL spectra for analyzing the phase stability of I / Br mixed perovskites with 0.5 mol % of different AQS derivatives are shown;

[0091] Fig.16 The time-dependent PL spectra of I / Br mixed perovskite films doped with NH4I or PEAI as additives are shown;

[0092] Fig.17 Photographs showing the aging conditions of mixed halide perovskite films with different AQS derivatives as additives sealed in a 20 mL vial (filled with N2) and illuminated for two days. The intensity of the simulated AM1.5G illumination was calibrated to 1 sun equivalent intensity;

[0093] Fig.18A High-resolution X-ray photoelectron spectroscopy (XPS) spectra of Pb 4f of aged perovskite films with different AQS derivatives are shown;

[0094] Fig.18B High-resolution X-ray photoelectron spectroscopy (XPS) spectra of I 3d of aged perovskite films with different AQS derivatives are shown;

[0095] Fig.18C High-resolution X-ray photoelectron spectroscopy (XPS) spectra of Br 3d of aged perovskite films with different AQS derivatives are shown;

[0096] Fig.19 Metallic Pb in the total Pb element of perovskite films with or without different AQS derivatives is shown 0The atomic ratio of

[0097] Fig. 20A The total Pb (Pb) of the pristine perovskite films with different AQS derivatives is shown. 2+ +Pb 0 ) in the metal Pb(Pb 0 )’s high-resolution XPS spectrum;

[0098] Fig. 20B The total Pb (Pb) of the pristine perovskite films with or without different AQS derivatives is shown. 2+ +Pb 0 ) in the metal Pb(Pb 0 )’s atomic ratio;

[0099] Fig.21 The atomic ratios of I:Pb, I:Br, and (I+Br):Pb in perovskite films with or without different AQS derivatives are shown;

[0100] Fig. 22 Top-down SEM images of perovskite films with and without AQS derivatives are shown;

[0101] Fig.23 Thin film XRD patterns of perovskite films with or without AQS derivatives are shown;

[0102] Fig.24 The cross-sectional SEM image and EDX element distribution (line scan of S, Pb, and In elements) of the perovskite film (prepared on an ITO substrate) with AQSH as an additive are shown;

[0103] Fig.25 UV-vis absorption spectra of perovskite films with or without AQS derivatives are shown;

[0104] Fig.26A The optimized sheet structures of the original FAI-rich and defective FAI-rich (100) / (110) according to density functional theory (DFT) calculations based on the redox mediator / perovskite interface model are shown;

[0105] Fig.26B The optimized sheet structures of pristine PbI2-rich and defective PbI2-rich (100) / (110) according to density functional theory (DFT) calculations based on the redox mediator / perovskite interface model are shown;

[0106] Fig.27A It explains the core of AQS, I 0 and Pb 0 Schematic diagram of the half-reaction between

[0107] Fig.27B Shown from I 0 To I - and from Pb 0 To Pb 2+ Calculated energy barriers for half reactions, and the total energy barrier for redox charge shuttling;

[0108] Fig.28 Surface Pb on the PbI2-rich FAPbI3 (100) and (110) surfaces with or without AQS adsorption is shown. 2+ Binding energy;

[0109] Fig.29 Shows NH4 + (PEA + ) with the pristine / defective FAPbI3 (100) and (110) surfaces;

[0110] Fig. 30A The optimized crystal structure of the original PbI2-rich (100) with AQS adsorption is shown; the optimization was performed at the GGA / PBE+vdW level of theory;

[0111] Fig. 30B The optimized crystal structure of the original PbI2-rich (110) with AQS adsorption is shown. The optimization was performed at the GGA / PBE+vdW level of theory;

[0112] Fig.31A Shown with NH4 + and PEA + Optimized crystal structure of adsorbed pristine FAI-rich (100). Optimization was performed at the GGA / PBE+vdW level of theory;

[0113] Fig.31B Shown with NH4 + and PEA + Adsorbed defective FAI-rich (100)-V FA The optimized crystal structure was optimized at the GGA / PBE+vdW theoretical level;

[0114] Fig.31C Shown with NH4 + and PEA + Optimized crystal structure of adsorbed pristine PbI2-rich (100). Optimization was performed at the GGA / PBE+vdW level of theory;

[0115] Fig.31D Shown with NH4 + and PEA + Adsorbed defective PbI2-rich (100)-V PbThe optimized crystal structure was optimized at the GGA / PBE+vdW theoretical level;

[0116] Fig.32A Shown with NH4 + and PEA + Optimized crystal structure of adsorbed pristine FAI-rich (110). Optimization was performed at the GGA / PBE+vdW level of theory;

[0117] Fig.32B Shown with NH4 + and PEA + Adsorbed defective FAI-rich (110)-V FA The optimized crystal structure was optimized at the GGA / PBE+vdW theoretical level;

[0118] Fig.32C Shown with NH4 + and PEA + Optimized crystal structure of adsorbed pristine PbI2-rich (110). Optimization was performed at the GGA / PBE+vdW level of theory;

[0119] Fig.32D Shown with NH4 + and PEA + Adsorbed defective PbI2-rich (110)-V Pb The optimized crystal structure was optimized at the GGA / PBE+vdW theoretical level;

[0120] Fig.33A Shown with H + Adsorbed pristine FAI-rich (100) and defective FAI-rich (100)-V FA The optimized crystal structure of

[0121] Fig.33B Shown with H + Adsorbed pristine PbI2-rich (100) and defective PbI2-rich (100)-V Pb The optimized crystal structure of

[0122] Fig.33C Shown with H + Adsorbed pristine FAI-rich (110) and defective FAI-rich (110)-V FA The optimized crystal structure of

[0123] Fig.33D Shown with H + Adsorbed pristine PbI2-rich (110) and defective PbI2-rich (110)-V PbThe optimized crystal structure of

[0124] Fig.34 Shows H + Calculated binding energies with pristine / defective FAPbI3(100) and (110) surfaces;

[0125] Fig.35A Time-resolved PL (trPL) spectra of perovskite films doped with different AQS derivatives are shown;

[0126] Fig.35B shows a table summarizing the calculations used Fig.35A Parameters of the average carrier lifetime in I / Br mixed halide perovskites;

[0127] Fig.36A The space charge limited current (SCLC) curves of pure hole devices with device structure of glass / ITO / DC-PA / perovskite (with and without AQS derivative / MoO3 / Ag) are shown;

[0128] Fig.36B Shows Fig.36A The corresponding calculated trap density in the perovskite film;

[0129] Fig.37A The JV curves of the control and target single-junction PSCs (perovskite with AQSP as additive) are shown. The initial efficiencies of the control and target single-junction PSCs are 18.08% and 18.89%, respectively;

[0130] Fig.37B J-V curves of single-junction PSCs based on perovskites with different concentrations of AQSP are shown;

[0131] Fig.37C Violin plots comparing photovoltaic parameters of control and target PSCs (20 devices fabricated from different batches) are shown;

[0132] Fig.38 The JV curves of the target PSC under reverse and forward scans are shown;

[0133] Fig.39A J-V curves of single-junction PSCs based on perovskites with different concentrations of AQSP are shown;

[0134] Fig.39B is a table summarizing the solar cell performance of single junction PSCs under reverse sweep (from Fig.39A JV curve extraction);

[0135] Fig.40The external quantum efficiency (EQE) curve of the highest efficiency target PSC and the calculated actual band gap of the perovskite are shown;

[0136] Fig.41 The integral J of the corresponding EQE spectrum from the champion target PSC is shown. sc ;

[0137] Fig.42A The reported V of representative PSCs with bandgaps ranging from 1.60 to 1.85 eV are shown. oc Summary of values;

[0138] Fig.42B is a table that summarizes the Fig.42A The reported V of PSCs with a band gap of approximately 1.80 eV oc value;

[0139] Fig.43 Figure 2 shows the encapsulated PSC under simulated AM1.5G illumination (100 mW cm) in a N2-filled cavity without temperature control. -2 , without UV filter) at its maximum power point (MPP). The initial efficiencies of the control and target PSCs were 18.08% and 18.98%, respectively;

[0140] Fig.44 is a schematic diagram illustrating the structure of a monolithic (two-terminal) PO-TSC with a BCP / Au / MoO3 interconnect layer (ICL);

[0141] Fig.45 Shows the corresponding Fig.44 Cross-sectional scanning electron microscope (SEM) image of;

[0142] Fig.46A The JV curves of PO-TSC under reverse and forward scans are shown. The inset shows the stable power output (SPO) of the tandem cell;

[0143] Fig.46B is a table that summarizes the device performance of the highest efficiency PO-TSC under reverse and forward scans;

[0144] Fig.47 JV curves of PSC, OSC and PO-TSC are shown;

[0145] Fig.48 Violin plots summarizing the photovoltaic parameters of PO-TSCs (25 devices fabricated from different batches) are shown;

[0146] Fig.49EQE spectra of the perovskite and organic subcells in a 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 the 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 an integrating sphere;

[0147] Fig.50 The efficiency distribution of 25 single series cells (from different batches) is shown;

[0148] Fig.51 A summary of the reported PCEs of PO-TSCs is shown;

[0149] Figures 52A to 52E The certified results of the tandem solar cell measured at SIMIT (CNAS) are shown. The certified PCE is 24.3% and the certified aperture area is 0.0419 cm 2 ;

[0150] Fig.53 is a table summarizing the device performance of reported PO-TSCs and PO-TSCs of the present invention; and

[0151] Fig.54 Figure 2 shows the performance of packaged PO-TSC under simulated AM1.5G illumination (100 mW cm) in a N2-filled chamber without temperature control. -2 The initial efficiency of the tandem cell was 24.67%. DETAILED DESCRIPTION

[0152] As used herein, the forms "a", "an" and "the" are intended to include both the singular and the plural forms, unless the context clearly indicates otherwise.

[0153] The words "example" or "exemplary" used in the present invention are intended to serve as examples, 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. On the contrary, the use of the words "example" or "exemplary" is intended to present concepts in a concrete way. 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 the context clearly indicates, "X employs A or B" is intended to mean any natural inclusive arrangement. That is, if X employs A; X employs B; or X employs both A and B, then "X employs A or B" is established in any of the foregoing cases.

[0154] As used herein, the phrase "about" is intended to refer to a value slightly deviating from the value described herein. In one example, the expression "about 10 seconds" covers any value from 9.5 seconds to 10.5 seconds, such as 9.5, 9.55, 9.85, 10.0, 10.02, 10.2 ... 10.5 seconds. In another example, the expression "about 1 mol%" covers any value from 0.8 mol% to 1.2 mol%, such as 0.8, 0.85, 0.88, 0.95 ... 1 ... 1.05 ... 1.2 mol%. In another example, the expression "about 0.3 mol%" covers any value from 0.28 mol% to 0.32 mol%, such as 0.28, 0.285, 0.29, 0.292 ... 0.3 ... 0.305, 0.31 ... 0.32 mol%. In a further example, the expression "about 260 nm" encompasses any value from 255 nm to 265 nm, such as 255, 255.5, 256, 256.2 ... 260 ... 262, 263.5, 264 ... 265 nm. In a further example, the expression "about 4000 rpm" encompasses any value from 3900 rpm to 4100 rpm, such as 3900, 3910, 3955 ... 4000, 4005, 4050 ... 4100 rpm.

[0155] The halide oxidation mechanism is considered to be one of the models that can rationalize the halide segregation behavior in perovskites. In particular, it is believed that under light, preferential iodide oxidation occurs in I / Br mixed perovskites, leading to local concentration gradients of their oxidation products (e.g., I2 and HI), which in turn drives halide migration. In addition, it is also believed that Pb in perovskites 2+ The ions are easily reduced to metallic Pb under continuous light. 0 , which is detrimental to device efficiency and stability.

[0156] Without intending to be limited by theory, the inventors have designed an active layer for a solar cell through their own research, tests and experiments, in particular a perovskite layer comprising a mixture of a halide perovskite and a sulfonyl naphthoquinone compound (or in other words, a perovskite layer formed by mixing a halide perovskite and a sulfonyl naphthoquinone compound), which can effectively suppress the halide segregation of the active layer. Specifically, in an example embodiment, it was found that a PSC equipped with the perovskite layer of the present invention can obtain a power conversion efficiency (PCE) of 19.58% and an open circuit voltage (V oc ), while showing significantly improved long-term stability (maximum power point (MPP) tracking under T 95In another example embodiment, a monolithic perovskite-organic tandem solar cell (PO-TSC) containing a 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.

[0157] According to the present invention, a perovskite layer for a solar cell is provided, which comprises a mixture of a halide perovskite and a sulfonyl naphthoquinone compound, wherein the sulfonyl naphthoquinone compound has a structure of formula (I):

[0158]

[0159] in:

[0160] 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; R2 and R3 are independently selected from hydrogen and a substituent, or R2 and R3 may form a condensed ring.

[0161] In one embodiment, 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 + , ammonium ion and aminum ion; 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 alkyl or phenyl; and when R2 and R3 form a fused ring, it contains a substituted or unsubstituted 6- to 14-membered ring.

[0162] In one embodiment, the unsubstituted C1 to C4 alkyl may include methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert-butyl, n-butyl, etc. In one embodiment, the unsubstituted C2 to C6 alkenyl 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 alkynyl 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 may include unsubstituted C6 to C10 homoaryl, such as phenyl, naphthyl, tetrahydronaphthyl, indanyl, etc. In one embodiment, the unsubstituted C6 to C10 aryl group may include an unsubstituted C6 to C10 heteroaryl group such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, quinolyl, isoquinolyl, benzothienyl, benzofuranyl, indolyl, pyridine, pyrimidone, pyrazinone, pyrimidinone, and the like.

[0163] In one embodiment, one or more hydrogens 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 replaced by one or more of the following moieties, such as halogen (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 C1 to C4 alkyl or phenyl as defined herein.

[0164] 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 replaced by, for example, phenyl, carbonyl, primary amine, secondary amine, etc.

[0165] In one embodiment, the sulfonyl naphthoquinone compound may be any one of formula (II), (III), (IV), (V), (VI) or (VII):

[0166]

[0167]

[0168]

[0169] wherein R1 is as defined above; and n is 1-1000.

[0170] In a specific embodiment, the sulfonyl naphthoquinone compound has a structure of formula (II), which can be selected from any one of formula (VIII), formula (IX) or formula (X):

[0171]

[0172] Where M is H + , ammonium ion or aminum ion; R4 is C1 to C4 alkyl; R5 and R6 are independently selected from hydrogen and C1 to C4 alkyl. 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 (e.g., methyl, ethyl, propyl, phenethyl, tert-butyl, etc.), benzyl, phenyl, etc.). The C1 to C4 alkyl group may 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.

[0173] Preferably, the sulfonyl naphthoquinone compound of formula (VIII) is selected from any one of formula (VIIIa), (VIIIb), (VIIIc):

[0174]

[0175] In particular, it was found that when the cation M is changed from H + Change to NH4 + and aniline (PEA) ions (PhCH2CH2NH3 + ), the passivation effect of the sulfonyl naphthoquinone compound can be enhanced, which in turn enhances the ability of the sulfonyl naphthoquinone compound to stabilize the perovskite during operation, such as exhibiting a redox effect on the perovskite component (e.g., Pb 2+ ) of the perovskite. Therefore, it can further promote the long-term operation of the perovskite. The details of the stabilizing effect of sulfonyl naphthoquinone compounds will be discussed in the later part of this disclosure.

[0176] In an optional embodiment, the sulfonyl naphthoquinone compound may comprise the structure of formula (IXa):

[0177]

[0178] In another optional embodiment, the sulfonyl naphthoquinone compound may comprise a structure of formula (Xa):

[0179]

[0180] The halide perovskite of the perovskite layer may comprise [A +1 B +2 X -1 3], where A +1 is a monovalent cation at the A-site, B +2 is a divalent cation at the B-site, and X -1 It is a halide anion.

[0181] In one embodiment, the monovalent cation at position A is selected from the group consisting of formamidinium ions (FA + ), methylammonium ion (MA + ), ethylammonium ion (EA + ), guanidine ion (GA + ), Cs + , Rb + and a combination thereof; the divalent cation at position B is selected from Pb 2+ Sn 2+ ,Ge 2 + and a combination thereof; and the halide anion is selected from the group consisting of I - Br - , Cl - and their combinations.

[0182] In a particular embodiment, 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 Cs0.1 Pb(I 0.92 Br 0.08 )3 and Cs 0.2 FA 0.8 Pb(I 0.6 Br 0.4 )3. Preferably, the halide perovskite may be an I / Br mixed perovskite. As a specific embodiment, the halide perovskite may be Cs 0.2 FA 0.8 Pb(I 0.6 Br 0.4 )3.

[0183] The term "crystal grain" (or crystallite) generally refers to small or microscopic crystals that are oriented / grown in a random or non-preferred direction, forming grain boundaries at the regions / interfaces where the crystallites meet. +1 B +2 X -1 The grain structure of the invention may include grain boundaries, the sulfonyl naphthoquinone compound is accommodated at the grain boundaries, and the sulfonyl naphthoquinone compound acts as a redox mediator at the grain boundaries, which can selectively reduce I 0 and oxidize Pb 0 .

[0184] The content / concentration of the sulfonyl naphthoquinone compound in the perovskite layer can be changed / 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 in particular about 0.3 mol% to about 0.5 mol% of the sulfonyl naphthoquinone compound.

[0185] 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 the redox mediator). Advantageously, it will be appreciated that these passivating agents may 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).

[0186] 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.

[0187] A method for making a perovskite layer as described herein is now disclosed. The method may include the following steps:

[0188] a) providing 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);

[0189] b) spin coating the solution mixture on a substrate; and

[0190] c) annealing the spin-coated solution mixture to form a perovskite layer.

[0191] Step a) may include the following steps: a1) providing a first reaction mixture comprising formamidine, methylammonium and cesium halide; and a2) mixing the first reaction mixture with about 0.3 mol % to about 1 mol % of a sulfonyl naphthoquinone compound to form a second reaction mixture.

[0192] 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 sulfonyl naphthoquinone compound, such as any of the sulfonyl naphthoquinone compounds of formula (VIII), formula (IX) or formula (X) structure, may be mixed with the first reaction mixture to form a second reaction mixture. Optionally or additionally, before performing the spin coating step (i.e., step b)), the second reaction mixture may be stirred for at least 8 hours to obtain a uniform / consistent solution mixture.

[0193] In an additional or optional embodiment, the first reaction mixture may further comprise 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 comprising formamidine, methylammonium and cesium halide prior to performing step a2).

[0194] Optionally, the sulfonyl naphthoquinone compound can be obtained commercially or by synthesis. In an optional embodiment of obtaining the sulfonyl naphthoquinone compound by synthesis, the method for making the perovskite layer claimed in the present invention can also include step a3), which involves converting sodium anthraquinone-2-sulfonate into a sulfonyl naphthoquinone compound as described herein.

[0195] In one embodiment, sodium anthraquinone-2-sulfonate can be converted into a sulfonyl naphthoquinone compound having the structure of formula (VIIa) by means of 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 then stirred for at least 8 hours. The mixture can be further separated by a cation exchange column having an Amberlite cation exchange resin.

[0196] In another embodiment, anthraquinone-2-sodium sulfonate can be converted into a sulfonyl naphthoquinone compound having a structure of formula (VIIb) or formula (VIIc). For example, anthraquinone-2-sodium sulfonate can be converted into a sulfonyl naphthoquinone compound having a structure of formula (VIIa) as described above. Then, the sulfonyl naphthoquinone compound of formula (VIIa) can be reacted with a corresponding amine or ammonium salt (such as ammonium hydroxide and phenylethylamine) and stirred for at least 8 hours, and then dried under reduced pressure (such as vacuum) to convert the sulfonyl naphthoquinone compound of formula (VIIa) into the sulfonyl naphthoquinone compound of formula (VIIb) and formula (VIIc).

[0197] 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 formula (Xa). For example, sodium anthraquinone-2-sulfonate can be mixed with thioyl chloride in DMF to form a reaction mixture, and then the crude anthraquinone-2-sulfonyl chloride is separated from the reaction mixture by precipitation and filtration. The crude anthraquinone-2-sulfonyl chloride can be optionally purified by washing with a suitable solvent before further reaction.

[0198] In order to convert anthraquinone-2-sulfonyl chloride into a sulfonyl naphthoquinone compound having a structure of formula (IXa), for example, anthraquinone-2-sulfonyl chloride can be first mixed with methanol in a solvent (such as DMF), and the mixture can be stirred at a temperature of about 50° C. to about 60° C. for, for example, 2 hours, and then the crude / crude sulfonyl naphthoquinone compound of formula (IXa) is isolated by precipitation and optional filtration, and purified by column chromatography using an elution solvent (e.g., 0.5% methanol in dichloromethane (DCM) solution).

[0199] On the other hand, in order to convert anthraquinone-2-sulfonyl chloride into a sulfonyl naphthoquinone compound having a structure of formula (Xa), butylamine can be slowly added (e.g., dropwise added) 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, for example, 2 hours, and the crude product is then washed with a suitable solvent and purified by column chromatography using an eluting solvent, for example, 0.5% methanol in dichloromethane (DCM) solution.

[0200] In the spin coating step b), the solution mixture (of step a)) may be spin coated onto a substrate such as a transparent substrate (e.g., glass, PDMS, PET, ITO, FTO, etc.), a hole transport layer, an electron transport layer, etc., or a combination thereof at about 300 rpm to about 12,000 rpm for about 10 seconds to about 140 seconds. In one embodiment, the spin coating may be performed at about 4,000 rpm to about 6,500 rpm, with a speed change rate of about 1,500 rpm s -1 . During the spin coating process and / or before the spin coating process is completed, such as 3 seconds to about 35 seconds before the completion, an anti-solvent can be added (e.g., dripped) to the spun solution mixture. It is believed that the anti-solvent treatment increases the nucleation density during the formation of the perovskite layer / film, thereby facilitating the production of a uniform and pinhole-free perovskite layer / film. In one embodiment, the addition of the anti-solvent can be initiated in step b1), wherein the chlorobenzene anti-solvent is added to the center of the spun solution mixture about 10 seconds before the completion of the spin coating process.

[0201] Preferably, unless specified otherwise, it is understood that the spin coating process as described herein is carried out at a controlled temperature of about 20° C. in a N 2 -filled glove box with O 2 and H 2 O content <5 ppm.

[0202] Thereafter, the method may 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 a temperature of 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 be beneficial to the crystallization of perovskite, and thus lead to a higher power conversion efficiency during operation (of the solar cell). In one embodiment, the spin-coated solution mixture may be annealed at about 100°C for about 15 minutes.

[0203] In an additional or optional embodiment, the method for making a perovskite layer as described herein may further include the steps of: spin coating a surface passivator of piperazine iodide (PI) on the perovskite layer; and annealing the perovskite layer coated with PI. For example, a PI solution (such as an IPA (isopropyl alcohol) solution of PI) can be spin coated onto the perovskite layer formed in step c) at a rate of about 5000 rpm for about 30 seconds. The perovskite layer coated with PI can 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 the band alignment and enhance the charge extraction at the interface of the perovskite layer and the electron transport layer by generating a positive dipole, which can therefore enhance the performance of the solar cell.

[0204] Another aspect of the present invention relates to solar cells, in particular 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 a perovskite layer as described herein, disposed between the first hole transport layer and the first electron transport layer, such as Figure 1B The solar cell 100 is exemplified in FIG.

[0205] As shown, the solar cell 100 has a first hole transport layer 104; a first electron transport layer 106; and a first active layer of a perovskite layer 108 as described herein, which is 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.

[0206] The first hole transport layer may be disposed on the transparent conductive layer, which may be disposed on the transparent substrate, and the first electron transport layer may be disposed on the first barrier layer, which may be disposed on the 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 ).

[0207] In an alternative embodiment, the solar cell 100 can be configured to interchange the positions of the first hole transport layer 104 and the first electron transport layer 106, thereby forming a 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 ).

[0208] As described herein, the perovskite layer of the present invention is beneficial for enhancing device (i.e., solar cell) efficiency and stability. For example, in one embodiment where the solar cell 100 / 100' can be a perovskite solar cell (such as a single junction perovskite solar cell), it comprises, for example, a band gap of about 1.81 eV, and can comprise a power conversion efficiency (PCE) of about 18.98% to about 19.58%. In another embodiment, the solar cell can comprise a power conversion efficiency of 95% of its initial value after 500 hours of AM1.5G illumination at about 45°C. The detailed performance of the solar cell will be discussed in a later section of this disclosure.

[0209] In one embodiment, the solar cell 100 may further include sub-cells disposed thereon, thereby forming a tandem solar cell. Figure 1C , an exemplary configuration of a tandem solar cell 102 is provided. As shown, the tandem solar cell 102 includes a solar cell 100 and a subcell 118 disposed on the solar cell 100, particularly in direct contact with the first metal layer 116. In other words, in this embodiment, the solar cell 100 acts as the first subcell 102 in the tandem solar cell 102. The tandem solar cell 102 also includes an anti-reflection layer 120, and the transparent conductive layer 110 and the transparent substrate 112 are disposed on the anti-reflection layer and in direct contact with it.

[0210] In this embodiment, the subcell 118 includes a second hole transport layer 122, a second electron transport layer 124, and a second active layer 126, wherein the second active layer is disposed between the second hole transport layer 122 and the second electron transport layer 124, in particular in direct contact therewith, 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.

[0211] 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.

[0212] In an alternative embodiment of the tandem solar cell 102' including the solar cell 100', the subcell can be a subcell 118' in which the position of the second hole transport layer 122 is interchanged with the position of the second electron transport layer 124. 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 ).

[0213] In an optional or additional embodiment, the subcell 118 / 118' may further include a second barrier layer 130 ( Figure 1C ). Preferably, the second barrier layer 130 is in direct contact with the second ETL 124 / the second HTL 122 and the second metal layer 128 .

[0214] 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.

[0215] In an example embodiment, the second active layer can be made of an organic photovoltaic material such as PM6:Y6:P 71 In a specific example embodiment, PM6:Y6:P 71 The subcell of the second active layer of BM can be combined with a first active layer including a perovskite layer as described herein (such as Cs 0.2 FA 0.8 Pb(I 0.6 Br 0.4 )3) of the solar cell coupling, thereby forming 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 a power conversion efficiency of 92% of its initial value after 500 hours of AM1.5G illumination at about 45°C. The detailed performance of the tandem solar cell will be discussed in the later part of this disclosure.

[0216] In some embodiments, the transparent substrate 112 may be flexible or rigid and may have a light 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-butylene-styrene (SEBS), terephthalate-1,4-cyclohexanedimethanol (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 any one of glass, PET, PEN, PDMS, SEBS, PP, and combinations thereof. In a preferred embodiment, the transparent substrate may be selected from any one of glass, PET, PEN, PDMS, and combinations thereof. As a specific embodiment, the transparent substrate may be glass.

[0217] In some embodiments, the transparent conductive layer (TCL) 110 may preferably have a dielectric constant of about 5 Ω sq -1 to about 70Ωsq -1 , for example about 5Ωsq -1 To about 20Ωsq -1 or about 5Ωsq -1 To about 15Ωsq -1 The resistance is believed to be less than about 5Ωsq -1 The resistance can affect the transparency of the conductive layer, and above about 70Ωsq -1 The resistance of the device can affect the charge transfer of the device. In particular, the TCL can be selected from the group consisting of: indium tin oxide (ITO), aluminum zinc oxide (AZO), fluorine tin oxide (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.

[0218] In some embodiments, 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'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene (Spiro-OMeTAD), p-type self-assembled monolayer (DC-PA), MoO x In one embodiment, the first HTL and the second HTL can be independently selected from PTAA, NiOx, Spiro-OMeTAD, DC-PA, MoO x and any combination thereof.

[0219] In some embodiments, the first electron transport layer (ETL) 126 and the second ETL 124 may be independently selected from PC 61 BM, C 60 , SnO2, PNDIT-F3N and a group consisting of their combinations.

[0220] In some embodiments, the first barrier layer 114 and the second barrier layer 130 can be independently selected from bathocuproine (BCP), bis-C 60 (bis-C 60 )、SnO x 、Zr(acac)2、MoO x and combinations thereof. In particular, it is understood that when a blocking layer is disposed on top of the ETL, it may be referred to as a "hole blocking layer" which is intended to block minority charge carriers (such as holes in this case) from reaching the cathode. The hole blocking layer may be selected from BCP, bi-C 60 SnO x and Zr(acac)2. In contrast, when a blocking layer is provided on top of the HTL, it may be referred to as an "electron blocking layer" which is intended to block minority charge carriers (such as electrons in this case) from reaching the anode. The electron blocking layer may be MoO x .

[0221] In some embodiments, the anti-reflection layer 120 can be selected from the group consisting of MgF2, LiF, PDMS and combinations thereof. In a specific embodiment, the anti-reflection layer can be selected from any one of MgF2, PDMS and combinations thereof. As a specific embodiment, the anti-reflection layer can be MgF2.

[0222] 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. In particular, 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 the metal layer can be referred to as an electrode or a charge recombination layer depending on the position / configuration of the metal layer within the solar cell. 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 the tandem solar cell 102), such a metal layer can be referred to as a "charge recombination layer". On the contrary, when the metal layer is set / positioned / configured at the top or bottom of the solar cell (such as the first metal layer 116 in the solar cell 100 and the second metal layer 128 in the tandem solar cell 102), such a metal layer can be referred to as an "electrode".

[0223] The solar cell of the present invention can be manufactured by a typical method such as the method described below.

[0224] Generally, the manufacture of solar cells may include the following steps: providing a substrate; depositing a substrate with 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.

[0225] A substrate deposited with a transparent conductive layer, such as substrate 112 deposited with TCL 110, can be cleaned by ultrasonic treatment with a detergent, deionized water, acetone, and isopropyl alcohol, respectively, for about 15 minutes to about 90 minutes. The substrate can then be dried in an oven at about 40° C. to about 125° C. for at least about 1 hour. The cleaned and dried substrate can be treated with oxygen plasma for about 10 minutes to about 75 minutes and then transferred to a N2-filled glove box before a subsequent spin coating process.

[0226] The HTL (such as the first HTL 104 and the second HTL 122) can be spin coated onto the transparent conductive layer at about 1000 rpm to about 10000 rpm for 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, the spin coating can be performed at about 2000 rpm to about 8000 rpm for about 10 seconds to about 60 seconds, and the annealing temperature can be about 80° C. to about 150° C.

[0227] The active layer (such as the first active layer 108 and the second active layer 126) can be spin coated onto the HTL at about 300 rpm to about 12000 rpm for about 10 seconds to about 140 seconds. Additionally or optionally, an antisolvent can be slowly dripped onto the center of the spin-coated active layer from about 3 seconds to about 35 seconds before the end of the spin coating. The spin-coated active layer can then be transferred to a hot plate to anneal at about 65° C. to about 180° C. for about 6 minutes to about 120 minutes.

[0228] The ETL (such as the first ETL 106 and the second ETL 124), the barrier layer (such as the first barrier layer 114 and the second barrier layer 130), and the metal layer (such as the first metal layer 116 and the second metal layer 130) can be formed by high vacuum (e.g., < about 5×10 -6 It is believed that high vacuum conditions are beneficial for achieving precise thickness during deposition. Preferably, the vacuum can be at least about 1×10 -5 or smaller.

[0229] In one embodiment where the solar cell includes an anti-reflective layer, such as anti-reflective layer 120, the anti-reflective layer may be deposited onto the TCL by thermal evaporation.

[0230] Hereinafter, the present invention is described in more detail by way of examples, but the present invention is not limited thereto.

[0231] Example

[0232] Materials and reagents

[0233] If not specified, the reagents and starting materials used to synthesize anthraquinone 2-sulfonate (AQS) derivatives are commercially available and used without further purification. Cesium iodide (CsI), formamidine iodide (FAI) and formamidine bromide (FABr) were purchased from Dysol (Australia). Lead iodide (PbI2, purity 99.999%), lead bromide (PbBr2, purity 99.9%) and 1-chloronaphthalene (1-CN) were purchased from TCI (Japan). Lead chloride (PbCl2), methylammonium chloride (MACl), fullerene (C60) and bathocuproine (BCP, purity 99.9%) were purchased from Xi'an Polymer Light Technology Corporation (China). N,N-dimethylformamide (DMF, purity 99.99%), dimethyl sulfoxide (DMSO, purity 99.50%), isopropyl alcohol (IPA, purity 99.50%), and chlorobenzene (CB, purity 99.90%) were purchased from J&K (China) and used as received. PM6 and Y6 were purchased from Solarmer Materials. PC 71BM was purchased from American Dye Source, Inc. Molybdenum oxide (MoO x ), chloroform (CF, purity 99.90%), and methanol (MeOH, purity 99.90%) were purchased from Sigma-Aldrich. Gold and silver particles used for thermal evaporation were high purity particles purchased from commercial sources. ((2,7-dimethoxy-9H-carbazol-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 study.

[0234] Methods and characterization

[0235] Experiments with redox mediators in solution

[0236] I 0 (25 mg, 0.1 mmol) and Pb 0 (25 mg, 0.12 mmol) powder was dispersed in 2 mL of mixed DMF / IPA solvent (volume ratio 1:10) with or without redox mediator (0.025 mmol), and the solution was stirred at 100 °C for 60 min. The upper layer solution (diluted to 1.0 × 10 -5 M) UV-vis absorption spectra and XRD patterns of the bottom precipitate of the sample and reference solutions (after 60 min). Absorption spectra of a representative solution and bottom layer where FAI was mixed with the mediator and dissolved in DMF.

[0237] Preparation of perovskite precursors

[0238] A wide bandgap perovskite precursor (CsI) with a concentration of 1.2 M 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 mixed solvent of DMF / DMSO (vol / vol, 4:1). 0.2 FA 0.8 Pb(I 0.6 Br 0.4)3). It should be noted that 3.0 mol% MAPbCl3 and 0.5 mol% 4-guanidinobenzoic acid hydrochloride were added to the perovskite precursor during device fabrication. These two chemicals can act as passivators 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 passivators 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 (solar cell containing a redox mediator as disclosed herein), 0.3 mol% of the redox mediator (i.e., AQSH, AQSN, or AQSP) was added to the perovskite precursor. The above solution was stirred overnight at room temperature and no filtration was required before use.

[0239] Fabrication of single-junction wide-bandgap perovskite solar cells (PSCs)

[0240] Pre-patterned indium-doped tin oxide (ITO) glass substrates were cleaned by ultrasonic treatment with detergent (1:1 / vol:vol Decon 90 / deionized water), deionized water, acetone, and isopropyl alcohol (IPA) for 15 min, respectively. The cleaned ITO glass substrates were then transferred to an oven at 100 °C for 24 h and treated with O plasma for 10 min before use. DC-PA hole-selective SAM (0.75 mg mL in IPA) was added. -1 ) at 3,000rpm ((speed change rate is 2,000rpms -1 )) was spin coated onto an ITO glass substrate for 25 seconds and then annealed at 110°C for 15 minutes. After cooling, the substrate was rinsed with IPA solvent and annealed at 100°C for another 5 minutes. The perovskite film was then deposited on the DC-PA layer by a one-step spin coating method. Specifically, 50 μL of the perovskite precursor as described above (with or without a redox mediator) was spin-coated at 4,000-6,500 rpm (speed variation rate of 1,500 rpms -1 ) was spin-coated for 30 seconds. During the spin-coating process, 200 μL of chlorobenzene (CB) antisolvent was quickly 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, iodinated piperazine (PI) (0.3 mg mL in IPA) was added at 5,000 rpm. -1 ) was dynamically spin-coated onto the formed perovskite for 30 seconds, followed by annealing at 100°C for 10 minutes. All the above spin-coating processes were performed in a N2-filled glove box with O2 and H2O contents <5ppm and a controlled temperature of about 20°C. Finally, 20nm C60, 6nm BCP, and 100nm Ag were respectively coated through a metal shadow mask (aperture area: 0.0644cm 2 ) in a high vacuum chamber (<2x 10-6 100 nm of MgF2 was thermally evaporated onto the glass side of the device as an anti-reflection (AR) layer.

[0241] Preparation of organic bulk heterojunction (BHJ) layer precursors

[0242] PM6, Y6 and PC with a weight ratio of 1:0.96:0.24 71 BM was dissolved in chloroform (CF) and the concentration of PM6 was fixed at 7 mg mL -1 A solvent additive (0.5 vol%), 1-CN, was added to the above solution. The solution was then stirred at 40°C for 2 hours before use.

[0243] Fabrication of single-junction narrow-bandgap organic solar cells (OSCs)

[0244] OSC with pin configuration based on glass / ITO / MoO x / PM6:Y6:PC 71 The device structure of BM / PNDIT-F3N / Ag. First, 10nm MoO x In a high vacuum chamber (<6x 10 -7 The precipitate was thermally evaporated on a clean ITO substrate in a tray ( Then, PM6:Y6:PC 71 The BM solution was dynamically cast onto the MoO at 1,500 rpm. x layer for 40 seconds and then thermally annealed at 90°C for 10 minutes. After cooling, PNDIT-F3N (0.5 mg mL in methanol containing 0.5 vol% acetic acid) was added. -1 ) interface layer was dynamically spin-coated onto the organic BHJ layer at 1,500 rpm for 40 seconds. Finally, the interface layer was coated through a metal shadow mask (aperture area: 0.0644 cm 2 ) in a high vacuum chamber (<2x 10 -6 100 nm Ag was thermally evaporated in 4% torr.

[0245] Fabrication of Perovskite-Organic Tandem Solar Cells (PO-TSC)

[0246] For the monolithic (2-terminal) PO-TSC in this study, the narrow bandgap organic subcell is integrated on top of the perovskite subcell. Briefly, after thermal evaporation of the BCP in the wide bandgap subcell, 0.5 nm Au (in rate) and 10nm MoO x Then, the organic BHJ layer and the interfacial layer (i.e., ICL) were sequentially spin-coated on the MoOx PNDIT-F3N was dynamically spin-coated on the organic BHJ layer at 1,500 rpm for 40 seconds. Finally, a metal shadow mask (aperture area: 0.0644 cm 2 ) Thermal evaporation of 100 nm Ag.

[0247] Characterization

[0248] 1 H NMR and 13 C NMR spectra were measured on Bruker AVANCE III 300MHz and 400MHz spectrometers. Solution UV-vis absorption spectra were obtained from Agient8454 spectrophotometer. Cyclic voltammetry (CV) measurements were performed on a CHI660D electrochemical workstation. CV experiments were performed at room temperature using a conventional three-electrode system, using 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, 0.1M) was used as the supporting electrolyte, and the scan rate was 0.1V s -1 Elemental analysis was obtained by Elemantar: Vario UNICUBE. Transmission and absorption spectra were performed on a UV-visible (UV-vis) spectrometer (PE Lamda 750).

[0249] Time-dependent photoluminescence (tdPL) spectra were collected by a homemade device, in which the excitation laser (450 nm) was introduced into the sample through an optical fiber, and the PL spectrum was detected by using a detector connected to 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 UV light with an energy of 21.21 eV.

[0250] The top view morphology of the thin film samples, the cross-sectional profile of the tandem cells and the cross-sectional energy dispersive spectroscopy (EDX, line scan) were analyzed by 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 ) radiation is carried out.

[0251] Time-resolved photoluminescence spectra (trPL) were recorded by a FLS980 spectrofluorimeter (Edinburgh) with a 480 nm pulsed excitation laser. The current density-voltage (JV) characteristics of the devices were measured at room temperature in a N2-filled glove box under simulated sunlight from a solar simulator (EnliTech, SS-F5, Taiwan Province, China) using a Keithley 2400 Source Meter. AM1.5G (100 mW cm) was obtained using a silicon solar cell calibrated by the National Renewable Energy Laboratory (NREL) with a KG-2 filter. -2 ) Light intensity of the solar simulator. The perovskite solar cell is covered with an aperture area of ​​0.0419 cm 2 A light shield is used to ensure the accuracy of the current density of the JV curve.

[0252] The J-V measurements were performed in swept mode using reverse and forward scans with a scan rate of 10 mV s -1 , and the step size is 0.02 V. The EQE curve was measured by an EQE measurement system (EnliTech, QE-R, Taiwan Province, China). For perovskite organic tandem solar cells, the wide E g EQE of the perovskite subcell while saturating the corresponding organic subcell. Similarly, the narrow E g EQE of the organic subcell while saturating the corresponding perovskite subcell. No bias voltage was applied during all EQE measurements.

[0253] Long-term device stability measurements

[0254] The long-term device stability of the packaged devices was tested by an in-situ stability measurement system (CRYSCO) equipped with multiple sample chambers (without UV filters and temperature control) and automatic data collection elements. The maximum power point (MPP) of the solar cell was tracked under a simulated AM 1.5G spectrum (1 sun equivalent intensity). The light source was a SLED lamp with a wavelength range of 400 to 1,000nm. A silicon photoelectric probe was equipped to monitor light intensity changes, and the intensity was automatically adjusted under host control. The sample chamber was placed in air with a continuous N2 flow during the test.

[0255] Density functional theory (DFT) calculations

[0256] The DFT calculations were performed using the projected augmented wave (PAW) method implemented in the Vienna As-is Computational Simulation Package (VASP) code. The generalized gradient approximation (GGA) and Perdew–Burke–Ernzerhof (PBE) exchange-correlation functionals were applied. The van der Waals (vdW) interactions were also included in the calculations using Grimme’s zero-damped DFT-D3 method. A uniform mesh of 6 × 6 × 6 k-mesh in the Brillouin zone was used to optimize the crystal structure of the cubic phase FAPbI3 in the bulk, 4 × 4 × 1 k-mesh for the FAPbI3 slab, and 2 × 2 × 1 k-mesh for the molecule / FAPbI3 interface. The energy cutoffs of the wave functions for the bulk were set to 500 eV and those for the slabs and interfaces were 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 with different terminations (FAI-rich and PbI2-rich) and surface defects (V FA and V Pb ). The plate replicas are separated by approx. Each structure is optimized until the forces on a single atom are less than and elimination of Pb 0 and I 0 The energy barrier of the relevant half-reaction is calculated as E(Pb 0 Elimination) = E(AQS 2- +Pb 2+ )–E(AQS)+E(Pb 0 ) and E(I 0 Elimination) = E(AQS - +I - )–E(AQS 2- )+E(I 0 The binding energy was calculated as E(binding) = E(interface) – E(FAPbI3) – E(molecule), where E(interface) is the total energy of FAPbI3 upon molecular adsorption, and E(FAPbI3) and E(molecule) are the total energy of FAPbI3 and PEA separated. + [H + or NH4 + ]’s energy.

[0257] Example 1A

[0258] Synthesis of AQSH

[0259] Anthraquinone-2-sodium sulfonate (300mg, 0.97mmol) and 3mL Amberlite cation exchange resin (IR-120 hydrogen form) are added to 5mL deionized water. The mixture is stirred overnight, and the anthraquinone compound dissolves. The solution is then rinsed through a cation exchange column with an Amberlite cation exchange resin again. The sulfonic acid obtained is evaporated, and the compound is vacuum dried overnight. The product is obtained as a light yellow powder with an output of 216mg (yield: 77%). 1 HNMR(400MHz,D2O)δ8.07(s,1H),7.97(d,J=8.2Hz,1H),7.88(d,J=8.2Hz,1H),7.74–7.64(m,2H),7.58–7.50(m,2H)( Figure 2A ). 13 CNMR (101MHz, D2O)δ182.46,182.36,148.04,135.15,135.10,133.38,132.32,131.57,131.18,127.81,126.72,123.74.(Two peaks overlap)( Figure 2B ).

[0260] Example 1B

[0261] Synthesis of AQSN

[0262] A 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 into an ammonium salt. Water was evaporated and the compound was dried in vacuo overnight. The product was obtained as a pale yellow powder in a yield of 278 mg (yield: 94%). 1 H NMR(400MHz,D2O)δ8.28(s,1H),8.14–8.04(m,2H),8.02–7.87(m,2H),7.76–7.61(m,2H)( Figure 3A ). 13 C NMR (101 MHz, 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%, S10.50%; measured values: C 54.52%, H 3.63%, N 4.57%, S10.94%.

[0263] Example 1C

[0264] Synthesis of AQSP

[0265] A 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 into an ammonium salt. Water was evaporated and the compound was dried in vacuo overnight. The product was obtained as a pale yellow powder in a yield of 311 mg (yield: 76%). 1 H NMR(400MHz,DMSO-d6)δ8.40(d,J=1.7Hz,1H),8.29–8.16(m,3H),8.09(dd,J=8.1,1.7Hz,1H),7.94(dq,J=7.3 ,4.0Hz,2H),7.75(s,3H),7.40–7.29(m,2H),7.29–7.19(m,3H),3.04(t,J=9.6Hz,2H),2.84(t,J=9.6Hz,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 19 NO5S analysis calculated value: C 64.53%, H 4.68%, N 3.42%, S7.83%; measured value: C 64.60%, H 4.68%, N 3.29%, S 8.18%.

[0266] Example 2

[0267] Synthesis of AQS esters

[0268] Anthraquinone-2-sodium sulfonate (2.5g, 8mmol) is first converted into the corresponding sulfonyl chloride by reaction with thionyl chloride (10mL, 137mmol) and DMF (0.5mL). The reaction mixture is poured into ice water. The precipitate is filtered and vacuum dried to obtain a yellow solid (2.4g, 98%). Pyridine (0.06mL) is added to a mixture of sulfonyl chloride (1mmol) and methanol (1mmol) in DMF (3mL) and the mixture is stirred at 50-60°C for 2 hours. The solution is cooled to room temperature and poured into water (20mL). The obtained precipitate is filtered, washed with water and purified by column chromatography (0.5% MeOH in DCM solution) to obtain 195mg of light yellow solid (yield: 65%).

[0269] Example 3

[0270] Synthesis of AQ amide

[0271] 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 allowed to warm 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) to give 105 mg of a light yellow solid (yield: 92%).

[0272] Example 4

[0273] Design and Characterization

[0274] Although anthraquinone (AQ) is believed to be able to serve as a redox skeleton, the inventors have revealed through their own research and experiments that AQ cannot actually be used by Pb 0 with I 0 The electron shuttling between the two promotes the formation of PbI2, which may be attributed to its relatively low redox potential compared with Pb, making it unable to oxidize metallic Pb 0 ( Figure 5 ). To solve this problem, the inventors designed that the AQ skeleton can be made of strong electron-withdrawing SO3 - The groups were functionalized to tune its redox potential to -0.21 V vs. NHE, thereby enabling suitable redox shuttling between Pb (-0.365 V vs. NHE) and I2 (0.536 V vs. NHE). This modification also increased its solubility in polar organic solvents (i.e., DMF and DMSO) for better processibility and provided additional synthetic tunability to its properties ( Fig. 6A and 6B In addition, it was found that by replacing the -H in the cationic part of AQS with -NH4 and -PEA ( Figure 7), which can impart molecular defect passivation capabilities.

[0275] The proposed redox shuttle Figure 8 As shown in Figure 2, the AQS core controls the redox ability of the molecule. 0 and I 0 The powder was dissolved in a DMF:IPA mixed solvent (volume ratio 1:10) to test for Pb 0 with I 0 The feasibility of electron transfer between the raw material powder and the formed PbI2 precipitate is to provide a good balance between the solubility of the raw material powder and the formed PbI2 precipitate ( Fig. 9 ).like Fig. 9 As shown in the inset, the control sample (without AQSH) exhibited the least yellow solid product and remained dark brown. In contrast, the target sample containing AQSH became colorless and formed a lot of yellow precipitate, which indicated that Pb 0 and I 0 The transmission spectrum of the supernatant solution (taken from the sample) further confirmed the presence of I only in the control solution. 0 substance, because two characteristic peaks at about 290 nm and about 360 nm were recorded.

[0276] In order to exclude the possibility that AQSH oxidizes iodide, another set of DMF solutions consisting of pure I2, pure AQSH, and FAI:AQSH were prepared respectively ( Fig. 10A ). The transparent FAI:AQSH solution showed no 0 The peak of the substance, which means Pb 0 Instead of I - The selective oxidation of Pb by AQSH and 0 or I 0 To further verify this selective redox process ( Fig. 10B By performing powder X-ray diffraction (XRD), based on the presence of characteristic diffraction peaks at 12.7°, 26.0°, and 38.7° ( Fig.11 ), most of the yellow precipitate ( Fig. 9 The inset of Figure 1 was verified to be PbI2. Therefore, it is speculated that the AQS derivatives will act as effective redox mediators of perovskites, thereby achieving I 0 Selective reduction of Pb 0 The simultaneous elimination of these defects should help suppress halide segregation in mixed halide perovskites (e.g. Fig.12 shown).

[0277] Example 5

[0278] Suppression of halide segregation in mixed halide perovskites

[0279] Preferential oxidation of halides with relatively low oxidation potentials (I - <Br - <Cl - ) is a key step in halide mass transport, which ultimately triggers phase segregation in perovskites. Therefore, time-dependent PL (tdPL) was first performed to investigate the effect of AQS-based redox mediators on halide segregation ( Fig.13 ). AQS derivatives, namely AQSH, AQSN, and AQSP, were incorporated as additives to I / Br hybrid perovskite films, respectively. The initial PL peak at about 700 nm was assigned to the pristine perovskite. After continuous irradiation, the PL of the AQS-based perovskite film remained stable, showing only a slight red shift of 3-5 nm ( Fig.14 ). In contrast, the double peak shape, a signature of halide segregation, gradually appears in the PL spectrum of the control sample within a few minutes.

[0280] For the segregated I / Br mixed perovskite, the photogenerated charge carriers will flow into the I-rich regions due to their lower band gap than the surrounding non-segregated domains. In this case, a new PL peak with lower photon energy (about 1.64 eV) is observed in the unstable control perovskite. To visually investigate the extent of halide segregation, the residual spectrum deduced by subtracting the initial PL from the final spectrum is used, as shown in Fig.15 As shown. The AQS-based perovskite exhibits only a small and symmetrical valley shape in its residual PL spectrum, while the control sample exhibits a significantly larger and asymmetrical valley shape in its residual PL spectrum. These significant changes in peak position and shape imply severe segregation of halides. In addition, to exclude the effect of cation substitution on phase stability, tdPL measurements of perovskite films were performed with NH4I or PEAI as additives, which showed negligible effects on alleviating phase segregation ( Fig.16 ).

[0281] High-resolution X-ray photoelectron spectroscopy (XPS) was then used to investigate the -2 Surface properties of aged perovskite films under Fig.17 ). In order to verify whether the AQS-based redox mediator helps to inhibit Pb 0 and I 0 The formation of Pb, I and Br elements ( Figures 18A to 18C ). The binding energies (BE) of approximately 138.1 eV and 142.9 eV were assigned to the Pb 4f 7 / 2 and Pb 4f 5 / 2 In contrast, for the control sample, Pb 4f 7 / 2 and Pb 4f5 / 2 The BE of α is slightly shifted to 138.5 eV and 143.3 eV. In addition, the Pb-derived ions are observed in the control perovskite (the main decomposition product of the perovskite under illumination). 0 There are two different shoulders (i.e., 136.7 eV and 141.6 eV) of

[0282] For metallic Pb in total Pb 0 The atomic ratios of Fig.19 , 20A and 20B. The control sample shows that the metal Pb 0 The ratio of Pb is as high as 11.58%, while that of AQS-based perovskites is 2.64-3.11%. 0 This significant decrease in Pb may be attributed to the oxidation of Pb to Pb mediated by AQS derivatives. 2+ ,like Figures 8 to 12 The previous results shown in .

[0283] Regarding halide elements, two peaks were observed in the control perovskite with BE of 619.3 eV and 630.8 eV, which originated from I 3d 5 / 2 and I 3d 3 / 2 ( Fig.18B Given the volatility of the iodine product, relative atomic ratios were used to study the halide distribution on the illuminated perovskite surface ( Fig.21 ). It is noted that the I / Pb atomic ratio (2.12-2.18) of the AQS based perovskite film is slightly higher than the stoichiometric ratio (indicated by the dashed line), while the (I+Br) / Pb atomic ratio is close to the stoichiometric ratio (3.09). This compositional heterogeneity may be attributed to the different nucleation / crystallization kinetics of I and Br based perovskites. However, a loss of halide species in the control perovskite was found as the atomic ratio of (I+Br) / Pb (2.48) was much lower than its stoichiometric ratio of 3.09. Considering its I / Pb atomic ratio of 1.80, this loss of halide content is attributed to iodine species as they have a lower oxidation potential than bromide (1.065 V). Meanwhile, the increased I / Br ratio of 2.67 in the control sample suggests that Br - Migrate faster along the direction of incident light, as reported.

[0284] Example 6

[0285] Structural properties and density functional theory (DFT) calculations

[0286] The structural properties of the perovskite films were investigated using scanning electron microscopy (SEM) and XRD, and the results Fig. 22 and 23All XRD patterns revealed two prominent diffraction peaks at 14.4° and 20.4° 2θ, corresponding to the (100) and (110) crystal planes of the perovskite. For the AQSN and AQSP based perovskites, lower intensities of the diffraction peaks from PbI2 were observed, which may be attributed to the regulatory effect of the substituted cations on the perovskite growth. Top-down SEM images did not show obvious differences in the morphology of the samples. The distribution of AQS derivatives within the perovskite layer was depicted by cross-sectional SEM-energy dispersive spectroscopy (SEM-EDX), which showed a uniform distribution ( Fig.24 ). The optical band gap of the perovskite film was also determined to be approximately 1.79 eV by UV-vis absorption spectroscopy. Fig.25 shown.

[0287] Based on the above structural analysis, density functional theory (DFT) calculations were performed on the redox mediator / perovskite interface model to gain insight into the role of AQS derivatives in promoting the overall redox reaction and passivating the perovskite, as well as to estimate their interactions. Two representative perovskite surfaces were considered, each with different terminations (FAI-rich and PbI2-rich) and surface defects (V FA and V Pb ),like Fig.26A and 26B As shown. First calculate the 0 and I 0 The energy barrier of the elimination-related half-reaction ( Fig.27A and 27B ). The results show that from Pb 0 To Pb 2+ The half-reaction presents a considerable energy barrier (11.6 eV), while 0 to I - The reduction of is thermodynamically more favorable to the pristine perovskite (-5.0 eV). After introducing the AQS derivatives to the perovskite surface, the energy barriers of both half reactions were lowered. The overall energy barrier of the redox reaction was reduced by more than three times (from 1.76 eV to 0.49 eV), verifying the ability of these molecules to promote electron shuttling within the perovskite.

[0288] As discussed in Example 4, the AQS core controls the redox capability, while the -H substitution by -NH4 and -PEA provides additional defect passivation effects to the molecule. - With Pb 2+ The binding energies between them are calculated to be 7.50 eV and 3.75 eV, respectively, which are higher than the binding energy of the control perovskite ( Fig.28 ). and Pb 2+ The stronger binding of NH4 is essential for stabilizing the perovskite.+ / PEA + The binding energy between the perovskite surface ( Fig.29 ). The optimized crystal structure of redox mediator-modified perovskite Figures 30A-30B , Figures 31A-31D , Figures 32A-32D , Figures 33A-33D and Fig.34 The results show that regardless of the crystal plane and surface properties, PEA + The cations are higher than NH4 + Provides a stronger defect passivation effect as it consistently exhibits higher binding energy with the perovskite surface.

[0289] Time-resolved PL (trPL) measurements of perovskite films to investigate the defect passivation effect of AQS derivatives ( Fig.35A ). The average carrier lifetime of the control perovskite (τ avg ) is calculated to be 0.91 μs, and slightly increased to 1.07 μs for the AQSH-based perovskite ( Fig.35B ). Notably, carrier lifetimes of 1.40 μs and 1.50 μs are obtained for AQSN- and AQSP-based perovskites, respectively. Since an extended carrier lifetime generally indicates enhanced radiative recombination, the space charge limited current (SCLC) method is used to quantify the trap density (N) in the perovskite. 陷阱 )( Fig.36A ). First, the trap filling limit voltage (V TFL ), and then the N of the control, AQSH-based perovskite, AQSN-based perovskite, and AQSP-based perovskite were calculated. 陷阱 The values ​​are 2.68×10 16 , 2.51×10 16 , 1.61×10 16 and 1.13×10 16 cm -3 ( Fig.36B ).

[0290] Example 7

[0291] Photovoltaic performance of PSC and PO-TSC

[0292] To further investigate the suppressed phase segregation and non-radiative recombination properties conferred by the AQSP additive, a single junction wide E gPSCs, where ITO is indium tin oxide and DC-PA represents a p-type self-assembled monolayer (SAM). The characteristics of devices based on perovskites without and with AQSP (denoted as control and target, respectively) are discussed as follows. The control device exhibits a decent PCE of 18.68%, while the optimized target device achieves an efficiency of 19.58%, which is mainly due to the V oc Increased from 1.309V to 1.351V ( Figures 37A to 37C ). The target device also shows negligible hysteresis as a PCE of 19.14% can be obtained under the forward scanning direction ( Fig.38 The photovoltaic performance of devices based on perovskites with different AQS derivatives is shown in Fig.39A Provided in and Fig.39B In summary.

[0293] By differentiating the external quantum efficiency (EQE) spectrum of the target device, it is determined that the band gap of the target device is 1.81 eV, and the spectrum shows an inflection point at 685 nm ( Fig.40 ). EQE integrated short-circuit current density (J sc ) matches closely with the values ​​extracted from the JV curve ( Fig.41 ). The target device’s V oc Defects (E g –qV oc ) is calculated to be 0.459 V, which is the highest E reported so far. g The lowest value of PSC is about 1.80 eV ( Fig.42A and 42B In addition, we significantly improved the long-term stability of the target cell (initial efficiency = 18.98%), which retained 95% of its initial PCE after 500 hours of operation under 1 sun illumination at maximum power point (MPP) ( Fig.43 ). In contrast, the efficiency of the control cell (initial efficiency = 18.08%) dropped rapidly (>20%) within 300 hours of operation.

[0294] The width E g Perovskite integrated with organic semiconductors to construct monolithic PO-TSC. PM6:Y6:PC 71 BM ternary blends are used as narrow E g The bulk heterojunction layer in the rear subcell. The device structure of PO-TSC is as follows Fig.44 As shown, BCP / Au / MoO xActing as interconnect layer (ICL). In order to obtain a good balance between transparency and electrical properties, 0.5 nm thick Au was used as the composite layer. The thickness of the perovskite and organic BHJ layers were optimized to about 260 nm and about 150 nm, respectively, to ensure efficient photon utilization and current matching between the two subcells ( Fig.45 ).

[0295] Strikingly, the tandem solar cell achieves an impressive PCE of 25.22% and a high V oc 、14.36mA cm -2 J sc and a fill factor (FF) of 81.65%, exhibiting negligible hysteresis and a steady power output (SPO) of 25.00%. Fig.46A and Fig.46B This high efficiency can be attributed to the low voltage losses of the perovskite subcell and ICL ( Fig.47 and Fig.48 The tandem cells in this study also showed good current matching, with 14.84 mA cm -2 and 14.38 mA cm -2 J sc Integrate the EQE spectra of the perovskite and organic subcells, respectively ( Fig.49 ).

[0296] An average PCE of 24.33% was calculated from 25 independent tandem cells manufactured from different batches, as Fig.50 The packaged tandem cells (with fixed masks) were also sent to the Independent Photovoltaic Calibration Institute (SIMIT) for certification, achieving a certified efficiency of 24.27%. This value is believed to represent the highest certified PCE reported for PO-TSCs ( Fig.51 , Figures 52A-52E and Fig.53 The packaged tandem cells retained 92% of the initial PCE after 500 hours of continuous operation at about 45°C under 1-sun illumination (AM 1.5G spectrum, no UV filter) in a N2-filled chamber ( Fig.54 ).

[0297] The present invention is presented by way of example only, and various other modifications and / or alterations to the described embodiments may be made by those skilled in the art without departing from the scope of the present invention as specified in the appended claims.

Claims

1. A perovskite layer for a solar cell, the perovskite layer comprising a mixture of a halide perovskite and a sulfonyl naphthoquinone compound, wherein the sulfonyl naphthoquinone compound has a structure of formula (I): in: 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 may form a condensed ring.

2. The perovskite layer of claim 1, wherein: 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 + , ammonium ions and aminum 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 alkyl or phenyl; When R2 and R3 form a fused ring, it comprises a substituted or unsubstituted 6- to 14-membered ring.

3. The perovskite layer of claim 2, wherein the sulfonyl naphthoquinone compound is any one of formula (II), (III), (IV), (V), (VI) or (VII): wherein R1 is as defined above; and n is 1-1000.

4. The perovskite layer according to claim 3, wherein the sulfonyl naphthoquinone compound of formula (II) is selected from any one of formula (VIII), formula (IX) or formula (X): Where M is H + , ammonium ion or aminum ion; R4 is a C1 to C4 alkyl group; R5 and R6 are independently selected from hydrogen and a C1 to C4 alkyl group.

5. The perovskite layer according to claim 4, wherein the sulfonyl naphthoquinone compound of formula (VIII) is selected from any one of formulas (VIIIa), (VIIIb) and (VIIIc):

6. The perovskite layer of claim 4, wherein the sulfonyl naphthoquinone compound comprises a structure of formula (IXa):

7. The perovskite layer of claim 4, wherein the sulfonyl naphthoquinone compound comprises a structure of formula (Xa):

8. The perovskite layer of claim 1, wherein the halide perovskite comprises [A +1 B +2 X -1 3], where A +1 A is a monovalent cation, B +2 is a divalent cation at position B, and X -1 It is a halide anion.

9. The perovskite layer of claim 8, wherein the monovalent cation at the A position is selected from the group consisting of formamidinium ion, methylammonium ion, ethylammonium ion, guanidine ion, Cs + , Rb + and a group consisting of a combination thereof; the B-position divalent cation is selected from Pb 2+ Sn 2+ ,Ge 2+ and a combination thereof; and the halide anion is selected from I - Br - , Cl - and their combinations.

10. The perovskite layer of claim 9, wherein 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.

11. The perovskite layer of claim 8, wherein the [A +1 B +2 X -1 3] includes a grain structure where the sulfonyl naphthoquinone compound is accommodated. 12 . The perovskite layer according to claim 1 , comprising 0.3 mol % to 1 mol % of the sulfonyl naphthoquinone compound.

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

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

15. A method for producing a perovskite layer as claimed in claim 1, comprising the following steps: a) providing a solution mixture, wherein the solution mixture comprises a halide perovskite precursor and the sulfonyl naphthoquinone compound according to claim 4; b) spin coating the solution mixture on a substrate; as well as c) annealing the spin-coated solution mixture to form the perovskite layer.

16. The method of claim 15, wherein step a) comprises the following steps: a1) providing a first reaction mixture comprising formamidine, methylammonium and a cesium halide; and a2) mixing the first reaction mixture with 0.3 mol % to 1 mol % of the sulfonyl naphthoquinone compound to form a second reaction mixture.

17. The method of claim 16, wherein the halide comprises CsI, CsBr, FAI, FABr, PbI2, and PbBr2.

18. The method of claim 16, wherein the first reaction mixture further comprises 3 mol% MAPbCl3 and 5 mol% 4-guanidinobenzoic acid.

19. The method according to claim 15, wherein step a) further comprises step a3) converting sodium anthraquinone-2-sulfonate into the sulfonyl naphthoquinone compound.

20. The method of claim 15, wherein step b) comprises step bl) adding chlorobenzene anti-solvent to the center of the spin-coated solution mixture about 10 seconds before completing the spin-coating process.

21. The method of claim 15, wherein the spin coating is performed at 4000 rpm to 6500 rpm, with a ramp rate of about 1500 rpm s -1 .

22. The method according to claim 15, further comprising the following steps after step c): Spin coating a piperazine iodide (PI) surface passivator on the perovskite layer; and The PI-coated perovskite layer is annealed.

23. A solar cell comprising: a first hole transport layer; a first electron transport layer; and The first active layer of the perovskite layer according to claim 1, which is arranged between the first hole transport layer and the first electron transport layer. 24 . The solar cell of claim 23 , wherein the first active layer is in direct contact with the first hole transport layer and the first electron transport layer. 25 . The solar cell of claim 24 , wherein the first hole transport layer is disposed on a transparent conductive layer disposed on a transparent substrate, and the first electron transport layer is disposed on a first blocking layer disposed on a first metal layer. 26 . The solar cell of claim 25 , 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.

27. The solar cell of claim 25, wherein the transparent substrate is selected from the group consisting of glass, polymethyl methacrylate, polycarbonate, general-purpose polystyrene, polyethylene terephthalate, polyethylene naphthalate, polydimethylsiloxane, styrene-ethylene-butylene-styrene, ethylene terephthalate-1,4-cyclohexanedimethanol ester, acrylonitrile-butadiene-styrene copolymer, polypropylene, polyamide, acrylonitrile-styrene copolymer, and combinations thereof.

28. The solar cell of claim 25, wherein the transparent conductive layer is selected from the group consisting of indium tin oxide, aluminum zinc oxide, tin oxide fluoride, graphene, poly(3,4-ethylenedioxythiophene):poly(styrene sulfonic acid), silver nanowires, copper nanowires, and combinations thereof.

29. The solar cell of claim 25, wherein the first hole transport layer is selected from the group consisting of poly(triarylamine), PEDOT:PSS, NiOx, 2,2',7,7'-tetrakis[N,N-bis(4-methoxyphenyl)amino]-9,9'-spirobifluorene, DC-PA, MoO x and combinations thereof.

30. The solar cell according to claim 25, wherein the first electron transport layer is selected from PC 61 BM, C 60 , SnO2, PNDIT-F3N and a group consisting of their combinations.

31. The solar cell of claim 25, wherein the first barrier layer is selected from the group consisting of bathocuproin (BCP), double C 60 SnO x 、Zr(acac)2、MoO x and their combinations.

32. The solar cell of claim 25, wherein the first metal layer is selected from the group consisting of Ag, Cu, Au, Al, W, Fe, Pt, and combinations thereof.

33. The solar cell of claim 23 comprising a bandgap of 1.81 eV.

34. The solar cell of claim 23, comprising a power conversion efficiency of 18.98% to 19.58%.

35. The solar cell of claim 23, comprising a power conversion efficiency of 95% of its initial value after 500 hours of AM 1.5G illumination at 45°C.

36. The solar cell of claim 25, further comprising a subcell disposed on and in direct contact with the first metal layer. 37 . The solar cell according to claim 36 , further comprising an anti-reflection layer, wherein the transparent conductive layer and the transparent substrate are disposed on and in direct contact with the anti-reflection layer.

38. The solar cell of claim 36, wherein the anti-reflective layer is selected from the group consisting of MgF2, LiF, PDMS, and combinations thereof.

39. The solar cell of claim 36, wherein the subcell comprises: a second hole transport layer; a second electron transport layer; and The second active layer is disposed between the second hole transport layer and the second electron transport layer.

40. The solar cell of claim 39, wherein the second active layer is in direct contact with the second hole transport layer and the second electron transport layer.

41. The solar cell of claim 39, 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.

42. The solar cell of claim 40, 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.

43. The solar cell of claim 39, 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.

44. The solar cell of claim 40, 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.

45. The solar cell of claim 39, 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.

46. ​​The solar cell of claim 42 comprising a perovskite organic tandem solar cell.

47. The solar cell of claim 46, wherein the perovskite organic tandem solar cell comprises Cs 0.2 FA 0.8 Pb(I 0.6 Br 0.4 )3 of the first active layer and PM6:Y6:P 71 The second active layer of BM.

48. The solar cell of claim 46, wherein the perovskite organic tandem solar cell has a power conversion efficiency of 24.27% to 25.22%.

49. The solar cell of claim 46, wherein the perovskite organic tandem solar cell has a power conversion efficiency of 92% of its initial value after 500 hours of AM 1.5G illumination at about 45°C.

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