Search

CN-119947554-B - Perovskite layer, manufacturing method thereof and solar cell

CN119947554BCN 119947554 BCN119947554 BCN 119947554BCN-119947554-B

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 comprising a mixture of a halide perovskite and a sulfonyl naphthoquinone compound having the structure of formula (I), wherein R 1 is independently selected from one of OM, OR 4 and NR 5 R 6 , wherein M is a cation, R 4 、R 5 and R 6 are independently selected from hydrogen and a substituent, and R 2 and R 3 are independently selected from hydrogen and a substituent, OR R 2 and R 3 may form a fused ring. A method for manufacturing the perovskite layer and a solar cell comprising a first active layer of the perovskite layer are also presented.

Inventors

  • REN GUANGYU
  • WU SHENGFAN
  • YAN YICHAO

Assignees

  • 香港城市大学

Dates

Publication Date
20260508
Application Date
20240415
Priority Date
20231101

Claims (20)

  1. 1. A perovskite layer for a solar cell, the perovskite layer comprising a mixture of mixed halide perovskite and sulfonyl naphthoquinone-based compound, the mixed halide perovskite comprising a grain structure of [ a +1 B +2 X -1 3 ], wherein a +1 is a monovalent cation at position a, B +2 is a divalent cation at position B, and X -1 is a halide anion, the monovalent cation at position a is selected from the group consisting of formamidine ion (FA + ), methyl ammonium ion (MA + ), ethyl ammonium ion (EA + ), guanidine ion (GA + )、Cs + 、Rb + ) and combinations thereof, the divalent cation at position B is selected from the group consisting of Pb 2+ 、Sn 2+ 、Ge 2+ and combinations thereof, and the halide anion is selected from the group consisting of I - 、Br - 、Cl - and combinations thereof, the sulfonyl naphthoquinone-based compound has the structure of any one of formulas (II), (III), (IV), (V), (VI) or (VII): the compound of formula (II), Formula (III), The compound of formula (IV), (V), Of formula (VI), or Formula (VII), Wherein: r 1 is independently selected from one of OM, OR 4 , and NR 5 R 6 , wherein M is a cation ：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 selected from the group consisting of; R 4 、R 5 and R 6 are independently selected from the group consisting of hydrogen, substituted or unsubstituted C1 to C4 alkyl, substituted or unsubstituted C2 to C6 alkenyl, substituted or unsubstituted C2 to C6 alkynyl, halogen, unsubstituted C6 to C10 aryl 、-CN、-C(=O)OH、-C(=O)H、-C(=O)R 7 、-OR 7 、-SH、-SR 7 、-NH 2 、-NHR 6 、-N(R 7 ) 2 、-Si(R 7 ) 3 、-OSi(R 7 ) 3 、-S(O)OH, and-P (O) (OH) 2 , wherein R 7 is alkyl or phenyl, and n is 1-1000; wherein the sulfonyl naphthoquinone compound does not include a porphyrin and is configured to inhibit halide segregation in the mixed halide perovskite.
  2. 2. The perovskite layer of claim 1, wherein the sulfonyl naphthoquinone compound of formula (II) is selected from any one of formula (VIII), formula (IX) or formula (X): The compound of formula (VIII), Of formula (IX), or A process for preparing (X), Wherein M is H + , ammonium ion or aminum ion, R 4 is C1 to C4 alkyl, R 5 and R 6 are independently selected from hydrogen and C1 to C4 alkyl.
  3. 3. The perovskite layer of claim 2, wherein the sulfonyl naphthoquinone compound of formula (VIII) is selected from any one of formulas (VIIIa), (VIIIb), and (VIIIc): formula (VIIIa), Of formula (VIIIb), and Formula (VIIIc).
  4. 4. The perovskite layer of claim 2, wherein the sulfonyl naphthoquinone compound comprises a structure of formula (IXa): Formula (IXa).
  5. 5. The perovskite layer of claim 2, wherein the sulfonyl naphthoquinone compound comprises a structure of formula (Xa): Formula (Xa).
  6. 6. The perovskite layer of claim 1, wherein the mixed halide perovskite is selected from any one of CsPb 0.5 Sn 0.5 I 3 、FAPbI 3 、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 I 3 、(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 I 3 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 ) 3 ).
  7. 7. The perovskite layer of claim 1, wherein the grain structure of [ a +1 B +2 X -1 3 ] includes grain boundaries at which the sulfonyl naphthoquinone compound is contained.
  8. 8. The perovskite layer of claim 1, comprising 0.3 mol% to 1 mol% of the sulfonyl naphthoquinone compound.
  9. 9. The perovskite layer of claim 1, further comprising 3 mol% MAPbCl 3 and 5% mol% 4-guanidinobenzoic acid.
  10. 10. The perovskite layer of claim 1, having a thickness of 260 nm a.
  11. 11. A solar cell, comprising: a first hole transport layer; a first electron transport layer, and The first active layer of the perovskite layer of claim 1, disposed between the first hole transport layer and the first electron transport layer.
  12. 12. The solar cell of claim 11, wherein the first active layer is in direct contact with the first hole transport layer and the first electron transport layer.
  13. 13. The solar cell of claim 12, 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 barrier layer disposed on a first metal layer.
  14. 14. The solar cell of claim 13, wherein the first hole transport layer is in direct contact with the transparent conductive layer and the first electron transport layer is in direct contact with the first blocking layer.
  15. 15. The solar cell of claim 13, wherein the transparent substrate is selected from the group consisting of glass, polymethyl methacrylate (PMMA), polycarbonate (PC), general Purpose Polystyrene (GPPS), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polydimethylsiloxane (PDMS), styrene-ethylene-butylene-styrene (SEBS), ethylene terephthalate-1, 4-cyclohexanedimethanol ester (PETG), acrylonitrile-butadiene-styrene copolymer (ABS), polypropylene (PP), polyamide (PA), acrylonitrile-styrene copolymer (AS), and combinations thereof.
  16. 16. The solar cell of claim 13, wherein the transparent conductive layer is selected from the group consisting of Indium Tin Oxide (ITO), zinc aluminum oxide (AZO), tin oxyfluoride (FTO), graphene, poly (3, 4-ethylenedioxythiophene) poly (styrenesulfonic acid) (PEDOT: PSS), silver nanowires, copper nanowires, and combinations thereof.
  17. 17. The solar cell of claim 13 wherein the first hole transport layer is selected from the group consisting of poly (triarylamine) (PTAA), PEDOT PSS, niOx, 2', 7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene (spiro-ome tad), DC-PA, moO x , and combinations thereof.
  18. 18. The solar cell of claim 13, wherein the first electron transport layer is selected from the group consisting of PC 61 BM、C 60 、SnO 2 , PNDIT-F3N, and combinations thereof.
  19. 19. The solar cell of claim 13, wherein the first barrier layer is selected from the group consisting of Bathocuproine (BCP), bic 60 、SnO x 、Zr(acac) 2 、MoO x , and combinations thereof.
  20. 20. The solar cell of claim 13, wherein the first metal layer is selected from the group consisting of Ag, cu, au, al, W, fe, pt and combinations thereof.

Description

Perovskite layer, manufacturing method thereof and solar cell Technical Field The present invention relates to perovskite layers, such as particularly but not exclusively perovskite layers comprising a mixture of halide perovskite and sulfonyl naphthoquinone compounds, and to methods for manufacturing perovskite layers. The invention also relates to a solar cell comprising a first active layer of a perovskite layer. Background Metal halide Perovskite Solar Cells (PSC) are promising Photovoltaic (PV) technologies due to their high absorption coefficient, low exciton binding energy, high carrier mobility, long carrier diffusion length, and bipolar charge transport. PSCs can generally be configured as single junction solar cells and multi-junction (or tandem) solar cells (i.e., solar cells composed of two or more subcells). In particular, since the series configuration allows combinations of subcells with different properties, such as combinations of wide bandgap and low bandgap subcells, which can meet the needs of high and low energy photons at run-time, it is believed that PSCs with a series configuration will have higher Power Conversion Efficiency (PCE) than PSCs with a single junction configuration. For example, in a perovskite-organic tandem solar cell (PO-TSC) with a precursor subcell having a desired band gap (E g) of about 1.8 to 1.9 eV, its PCE may be increased from about 15% to about 24%, particularly when an I/Br mixed perovskite is employed (fig. 1A). However, perovskite layers of PSCs typically experience severe halide phase segregation during device operation, which is believed to be a result of halide migration through halide vacancies within the perovskite film, constituting a significant barrier to the long term stability of perovskite-based PSCs. In addition, under continuous illumination and/or heating, pb 2+ ions in the perovskite are also easily reduced to metal Pb 0, which is detrimental to device efficiency and stability. Although there are reports of suppression of halide segregation by, for example, crystallization control, defect passivation, surface modulation, and strain engineering, none of these strategies is believed to simultaneously solve the problem of easy reduction of Pb 2+ to Pb 0. Furthermore, the additives used in the reported strategies are either inorganic compounds, which are believed to be difficult to tailor their properties synthetically, or sacrificial agents, which are believed to disappear soon after validation. Nevertheless, it remains a challenge to have an additive whose properties can be easily tuned to eliminate different defects and which can function in a sustainable manner without introducing additional deep defects. The present invention seeks to obviate or at least mitigate these disadvantages by providing a new or otherwise improved solar cell active layer, in particular an active perovskite layer capable of achieving selective iodine (I 2) reduction and metallic lead (Pb 0) oxidation in a sustainable manner. Disclosure of Invention In a first aspect of the invention there is provided a perovskite layer for a solar cell comprising a mixture of a halide perovskite and a sulfonyl naphthoquinone compound having the structure of formula (I): The compound of formula (I), Wherein: R 1 is independently selected from one of OM, OR 4 and NR 5R6, wherein M is a cation, R 4、R5 and R 6 are independently selected from hydrogen and substituents, and R 2 and R 3 are independently selected from hydrogen and substituents, OR R 2 and R 3 may form a fused ring. Optionally, M is selected from the group ：H+、Na+、K+、Cs+、Rb+、Sr2+、Ca2+、Ni2+、Cu2+、Co2+、Zn2+、Mg2+、Ba2+、Li+、 ammonium ion (amminium ion) and aminum ion, R 2、R3、R4、R5 and R 6 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 R 7 is alkyl or phenyl, and when R 2 and R 3 form a fused ring, it comprises a substituted or unsubstituted 6-to 14-membered ring. In an optional embodiment, the sulfonyl naphthoquinone compound is any of formulas (II), (III), (IV), (V), (VI), or (VII): the compound of formula (II), Formula (III), The compound of formula (IV), (V), Of formula (VI), or Formula (VII), Wherein R 1 is as defined above and n is 1 to 1000. Optionally, the sulfonyl naphthoquinone compound of formula (II) is selected from any of formula (VIII), formula (IX) or formula (X): The compound of formula (VIII), Of formula (IX), or A process for preparing (X), Wherein M is H +, ammonium ion or aminum ion, R 4 is C1 to C4 alkyl, R 5 and R 6 are independently selected from hydrogen and C1 to C4 alkyl. In one embodiment of the present invention, the sulfonyl naphthoquinone compound of formula (VIII) is selected f