WO2022104483A1 - Pérovskites d'halogénure à alliages 2d/3d : procédé pour les préparer et les utiliser dans des cellules solaires - Google Patents

Pérovskites d'halogénure à alliages 2d/3d : procédé pour les préparer et les utiliser dans des cellules solaires Download PDF

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WO2022104483A1
WO2022104483A1 PCT/CA2021/051657 CA2021051657W WO2022104483A1 WO 2022104483 A1 WO2022104483 A1 WO 2022104483A1 CA 2021051657 W CA2021051657 W CA 2021051657W WO 2022104483 A1 WO2022104483 A1 WO 2022104483A1
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alloyed
pea
perovskite
perovskites
cation
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Deepak THRITHAMARASSERY GANGADHARAN
Dangling MA
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Solaires Entreprises Inc.
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices

Definitions

  • the present invention relates generally to halide perovskites. More specifically, the present invention relates to halide perovskites comprising substantially no lead (Pb) in free form or any form that may lead to water-soluble precursors thereof.
  • the halide perovskites according to the invention have a 2D/3D structure and comprise alloys that may or may not involve lead, for example tin-lead (Sn-Pb) alloys.
  • organic-inorganic halide perovskites have stolen the show among other photovoltaic materials mainly because of a relatively simple fabrication process which involves deposition, high power conversion efficiencies (PCEs), and tunable bandgap from 1.15 to 3.06 eV obtained among others, by swapping different cations,
  • PSCs The state-of-the-art perovskite solar cells
  • Pb water-soluble lead
  • Pb halide perovskite in contact with water or humid air form water-soluble by-products of Pb, which can accumulate within the food chain and reach the human body [7]
  • Sn-based perovskites are toxicologically safe, highest-performing lead-free solar cells [10,11]. Unfortunately, Sn is more stable in the 4 + oxidation state, causing critical stability issues as well as lower photovoltaic performance for Sn-based PSCs, as a result of the formation of lattice vacancies [12], The Sn lattice vacancies enhance the background hole carrier concentration (p-doping) in Sn-based perovskites [12,13], Sn-based perovskite devices demonstrate subpar open-circuit voltage (V oc ) mainly due to severe charge carrier recombination in the solar cell triggered by p-doping [14], Different approaches including morphological control of the Sn perovskites, minimization of oxygen exposure during the device preparation, and the addition of SnF2, have been explored and found to be useful in improving PCE of Sn-based perovskite devices.
  • Zhao et al. reported one of the highest-performing Sn PSCs with an efficiency of 8.12% falling far short of Pb halide PSCs [10], On the other hand, adding Pb content into Sn perovskites can stabilize 2+ oxidation state of Sn.
  • Alloyed Pb-Sn perovskites are thus alternate strategies towards stable, less toxic solar cells without compromising the photovoltaic performance.
  • alloyed Sn-Pb perovskites exhibit broader absorption of photons extending to near-infrared spectrum (up to 1050 nm with optical bandgap of 1.18 eV).
  • MAPbl 3 , MAPbl 3 and FASnl 3 lack absorption in near-infrared spectrum; MAPbl 3 , FASnl 3 and FASnl 3 have limited optical bandgaps of 1.55 eV (up to 800 nm), 1.48 eV (up to 838 nm) and 1.30 eV (up to 950 nm), respectively [15],
  • halide perovskites which comprise substantially no lead (Pb) in free form or any form that may lead to water-soluble precursors thereof.
  • the halide perovskites according to the invention have a 2D/3D structure and comprise tin-lead (Sn-Pb) alloys.
  • the inventors have designed and prepared halide perovskites, wherein at least part of the small organic cations formamidinium (FA) and methylammonium (MA) is replaced by an organic cation having a size which is larger than the size of FA and/or MA.
  • such larger size organic cation is an ammonium or an amidinium.
  • A is an organic cation selected from ammonium cation and amidinium cation
  • FA is formamidinium
  • B is an alloy involving at least two of Sn, Pb and Ge;
  • X is a halogen atom.
  • A is an ammonium cation of general formula I below wherein Ri to R4 are each independently selected from H, alkyl, cycloalkyl, alkene, alkyne, aryl and alkylaryl.
  • R1 to R3 are each independently selected from H, alkyl, cycloalkyl, alkene, alkyne, aryl and alkylaryl;
  • L is present or absent and is a group comprising one or more of (CH 2 ) and (CH);
  • Q is present or absent and is a 5 to 12-member ring or bicycle ring, with the proviso that at least one of Q and L is present.
  • Q is present or absent and is a 5 to 12-member ring or bicycle ring; and n is an integer from 0-6.
  • Ri are each independently selected from H, alkyl, cycloalkyl, alkene, alkyne, aryl and alkylaryl; n is an integer from 1-6; and m is an integer from 0-4.
  • A is an ammonium cation of general formula V below wherein n is an integer from 1-6.
  • A is an amidinium cation of general formula I' below wherein R 5 to R 9 are each independently selected from H, alkyl, cycloalkyl, alkene, alkyne, aryl and alkylaryl.
  • Rs to Rs are each independently selected from H, alkyl, cycloalkyl, alkene, alkyne, aryl and alkylaryl;
  • L' is present or absent and is a group comprising one or more of (CH 2 ) and (CH); and Q' is a 5 to 12-member ring or bicycle ring.
  • A is an amidinium cation of general formula III' below wherein:
  • Q' is a 5 to 12-member ring or bicycle ring; and n' is an integer from 0-6.
  • R'i are each independently selected from H, alkyl, cycloalkyl, alkene, alkyne, aryl and alkylaryl; n' is an integer from 1-6; and m' is an integer from 0-4.
  • A is an organic cation selected from an ammonium cation of general formula I, II, III, IV orV and an amidinium cation of general formula I', II', III', IV' or V';
  • FA formamidinium
  • MA methylammonium
  • y 0.01-0.99
  • x 0.01-0.99
  • X is a halogen atom.
  • PEA y (FA x MA 1-x ) 1-y Sn x Pb 1-x l 3 (P2) wherein:
  • PEA is phenylethylammonium cation
  • FA is formamidinium
  • a method of preparing a 2D/3D alloyed halide perovskite comprising replacing at least part of the small organic cations formamidinium (FA) and methylammonium (MA) with an organic cation having a size which is larger than the size of FA and/or MA.
  • a method of preparing a 2D/3D alloyed halide perovskite comprising replacing at least part of the small organic cations formamidinium (FA) and methylammonium (MA) with a larger organic cation selected from an ammonium cation of general formula I, II, III, IV or V and an amidinium cation of general formula I', II', III', IV' or V'.
  • FA formamidinium
  • MA methylammonium
  • a method of manufacturing a solar cell device comprising replacing at least part of the small organic cations formamidinium (FA) and methylammonium (MA) with an organic cation having a size which is larger than the size of FA and/or MA.
  • a method of manufacturing a solar cell device comprising replacing at least part of the small organic cations formamidinium (FA) and methylammonium (MA) with a larger organic cation selected from an ammonium cation of general formula I, II, III, IV or V and an amidinium cation of general formula I', II', III', IV' or V'.
  • a method of manufacturing a solar cell device comprising replacing at least part of the cations formamidinium (FA) and methylammonium (MA) with phenylethylammonium (PEA) cation.
  • a method of manufacturing a solar cell device comprising preparing the 2D/3D alloyed halide perovskite as defined in any one of (1)-(25) above.
  • a method of manufacturing a solar cell device comprising using the 2D/3D alloyed halide perovskite as defined in any one of (1)-(25) above.
  • a solar cell device which comprises the 2D/3D alloyed halide perovskite as defined in any one of (1)-(25) above.
  • Figure 1 a) Absorption spectra of 3D perovskite films and comparison of absorption spectra of 3D perovskite vs. 2D/3D perovskite films; b) (PEA) y (FA 0.3 MA 0.7 ) 1-y Sn 0.3 Pb 0.7 l 3 ; c) (PEA)y (FA 0.5 MA 0.5 ) 1-y Sn 0.5 Pb 0.5 l 3 ; d) (PEA) y (FA 0.7 MA 0.3 ) 1-y Sn 0.7 Pb 0.3 l 3 .
  • Figure 3 Morphology of a) (FASnl 3 ) 0.3 (MAPbl 3 ) 0.7 ; b) (PEA) 0.05 (FA 0.3 MA 0.7 ) 0.95 Sn 0.3 Pb 0.7 l 3 ; c) (PEA) 0.1 (FA 0.3 MA 0.7 ) 0.90 Sn 0.3 Pb 0.7 l 3 ; d) (FASnl 3 ) 0.5 (MAPbl 3 ) 0.5 ; e) (PEA) 0.05 (FA 0.5 MA 0.5 ) 0.95 Sn 0.5 Pb 0.5 l 3 ; f) (PEA)o.1 (FA 0.7 MA 0.3 ) 0.90 Sn 0.5 Pb 0.5 l 3 ; g) (FASnl 3 ) 0.7 (MAPbl 3 ) 0.3 ; I 3 )
  • PEA 0.05 (FA 0.7 MA 0.3 ) 0.95 Sn 0.7 Pb 0.3 l 3 ; i) (PEA) 0.1 (FA 0.7 MA 0.3 ) 0.90 Sn 0.7 Pb 0.3 l 3 .
  • Figure 4 AFM topographical images with roughness of a) (FASnl 3 ) 0.3 (MAPbl 3 ) 0.7 ; b) (PEA) 0.05 (FA 0.3 MA 0.7 ) 0.95 Pb 0.7 Sn 0.3 l 3 ; c) (FASnl 3 ) 0.5 (MAPbl 3 ) 0.5 ; d) (PEA) 0.05 (FA 0.5 MA 0.5 ) 0.95 Pb 0.5 Sn 0.5 l 3 ; e) (FASnl 3 ) 0.7 (MAPbl 3 ) 0.3 ; f) (PEA) 0.05 (FA 0.7 MA 0.3 ) 0.95 Pb 0.3 Sn 0.7 l 3 .
  • Figure 5 SEM images and elemental mapping of Pb, Sn and I of a) (FASnl 3 ) 0.3 (MAPbl 3 ) 0.7 ; b) (FASnl 3 ) 0.5 (MAPbl 3 ) 0.5 ; c) (FASnl 3 ) 0.7 (MAPbl 3 ) 0.3 ; d) (PEA) 0.05 (FA0.3 MA 0.7 ) 0.95 Pb 0.7 Sn 0.3 l 3 ; e) (PEA) 0.05 (FA 0.5 MA 0.5 ) 0.95 Pb 0.5 Sn 0.5 l 3 ; f) (PEA) 0.05 (FA 0.7 MA 0.3 ) 0.95 Pb 0.3 Sn 0.7 I 3 .
  • Figure 6 XRD spectra of FASnl 3 and MAPbl 3 perovskite films.
  • Figure 7 Comparison of XRD spectra of different compositions of 3D perovskites and 2D/3D perovskites: a) (PEA) y (FA0.3 MA 0.7 ) 1-y Sn 0.3 Pb 0.7 l 3 , b) (PEA) y (FA 0.5 MA 0.5 ) 1-y Sn 0.5 Pb 0.5 I 3 and c) (PEA) y (FA 0.7 MA 0.3 ) 1-y Sn 0.7 Pb 0.3 I 3 ; and variation of FWHM of the (110) diffraction peak of: d) (PEA) y (FA0.3 MA 0.7 ) 1-y Sn 0.3 Pb 0.7 I 3 , e) (PEA) y (FA 0.5 MA 0.5 ) 1-y Sn 0.5 Pb 0.5 I 3 and f) (PEA) y (FA 0.7 MA 0.3 ) 1-y Sn 0.7 Pb 0.3 l 3 .
  • Figure 8 High resolution XPS spectra of Sn 3d in a) (FASnl 3 ) 0.3 (MAPbl3) 0.3 ; b) (PEA) 0.05 (FA 0.3 MA 0.7 ) 0.95 Sn 0.3 Pb 0.7 I 3 .
  • the red and blue curve corresponds to Sn 2+ and Sn 4+ oxidation states, respectively.
  • Figure 9 XPS survey spectra of (FASnI 3 ) 0.3 (MAPbI 3 ) 0.7 and (PEA)o.os (FA0.3 MA 0.7 ) 0.95 Pb 0.7 Sn 0.3 I 3 .
  • Figure 10 Statistical distribution of efficiency of a) (FASnl 3 ) 0.3 (MAPbl3) 0.7 ; b) (PEA) 0.05 (FA0.3 MA 0.7 ) 0.95 Sn 0.3 Pb 0.7 l 3 ; c) (PEA) 0.1 (FA0.3 MA 0.7 ) 0.95 Sn 0.3 Pb 0.7 I 3 devices.
  • Figure 11 Statistical distribution of efficiency of a) (FASnl 3 ) 0.5 (MAPbI 3 ) 0.5 ; b) (PEA) 0.05 (FA 0.5 MA 0.5 ) 0.95 Sn 0.5 Pb 0.5 I 3 ; c) (PEA) 0.1 (FA 0.5 MA 0.5 ) 0.95 Sn 0.5 Pb 0.5 I 3 devices.
  • Figure 12 Statistical distribution of efficiency of a) (FASnl 3 ) 0.7 (MAPbl3) 0.3 ; b) (PEA) 0.05 (FA 0.7 MA 0.3 ) 0.95 Sn 0.7 Pb 0.3 I 3 ; c) (PEA) 0.1 (FA 0.7 MA 0.3 ) 0.95 Sn 0.7 Pb 0.3 I 3 devices.
  • Figure 13 j. V curv es of a) (PEA) y (FA 0 .3MA 0.7 ) 1-y Sn 0.3 Pb 0.7 l3; b) (PEA) y (FA 0.5 MA 0.5 )i.
  • Figure 14 Dependence of a) J sc ; b) Voc; c) FF on the incident light intensity of the 3D PSCs and 2D/3D PSCs.
  • Figure 15 Topography and surface potential profile of a) (FASnl 3 ) 0.3 (MAPbl3) 0.7 , b) (PEA) 0.05 (FA 0.3 MA 0.7 ) 0.95 (Sn 0.3 Pb 0.7 ) I 3 , C) (FASnl 3 ) 0.5 (MAPbl 3 ) 0.5 , d) (PEA) 0.05 (FAO.5 MAO.5 ) 0.95 (Sn 0.5 Pb 0.5 ) I 3 , e) (FASnl 3 ) 0.7 (MAPbl3) 0.3 and f) (PEA) 0.05 (FA 0.7 MA0.3 ) 0.95 (Sn 0.7 Pb 0.3 ) I 3 .
  • Figure 16 J-V hysteresis of a) (FASnl 3 ) 0.3 (MAPbl 3 ) 0.7 ; b) (PEA) 0.05 (FA0.3 MA o.7 ) 0.95 Sn 0.3 Pb 0.7 I 3 devices.
  • Figure 17 Degradation of 3D perovskite devices vs. 2D/3D perovskite devices a) under 28 ⁇ 2% RH humidity in the dark; b) under N2 at 1.5G AM Sun illumination; c) under 28 ⁇ 2% RH humidity at 1.5G AM Sun illumination.
  • ammonium refers to cations having a general formula I as depicted herein.
  • aminodinium refers to cations having a general formula I' as depicted herein.
  • the words “comprising” (and any form of comprising, such as “comprise” and “comprises”), “having” (and any form of having, such as “have” and “has”), “including” (and any form of including, such as “include” and “includes”) or “containing” (and any form of containing, such as “contain” and “contains”), are inclusive or open-ended and do not exclude additional, unrecited elements or process steps.
  • alkyl represents a monovalent group derived from a straight or branched chain saturated hydrocarbon comprising, unless otherwise specified, from 1 to 15 carbon atoms and is exemplified by methyl, ethyl, n- and /so-propyl, n-, sec-, iso- and tert-butyl, neopentyl and the like and may be optionally substituted with one, two, three or, in the case of alkyl groups comprising two carbons or more, four substituents.
  • alkylene represents a saturated divalent hydrocarbon group derived from a straight or branched chain saturated hydrocarbon by the removal of two hydrogen atoms, and is exemplified by methylene, ethylene, isopropylene and the like.
  • alkenyl represents monovalent straight or branched chain groups of, unless otherwise specified, from 2 to 15 carbons, such as, for example, 2 to 6 carbon atoms or 2 to 4 carbon atoms, containing one or more carbon-carbon double bonds and is exemplified by ethenyl, 1-propenyl, 2-propenyl, 2-methyl-1-propenyl, 1-butenyl, 2- butenyl and the like and may be optionally substituted with one, two, three or four substituents.
  • alkynyl represents monovalent straight or branched chain groups of from two to six carbon atoms comprising a carbon-carbon triple bond and is exemplified by ethynyl, 1-propynyl, and the like and may be optionally substituted with one, two, three or four substituents.
  • cycloalkyl represents a monovalent saturated or unsaturated non-aromatic cyclic hydrocarbon group of three to eight carbon atoms, unless otherwise specified, and is exemplified by cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1]heptyl and the like.
  • halogen or “halo” as used interchangeably herein, represents F, Cl, Br and I.
  • the inventors have designed and prepared halide perovskites which comprise substantially no lead (Pb) in free form or any form that may lead to water-soluble precursors thereof.
  • the halide perovskites according to the invention have a 2D/3D structure and comprise tin-lead (Sn-Pb) alloys.
  • the inventors have designed and prepared halide perovskites, wherein at least part of the small organic cations formamidinium (FA) and methylammonium (MA) is replaced by an organic cation having a size which is larger than the size of FA and/or MA.
  • such larger size organic cation is an ammonium or an amidinium.
  • the inventors explored different compositions of Pb- Sn alloyed perovskite by stoichiometrically mixing FASnl 3 and MAPbl 3 to utilize near-infrared photons of the solar spectrum [16]. It is known in the art that the trap states at grain boundaries (GBs) and primarily at the perovskite surface, instigate lower photovoltaic performance, current-voltage hysteresis and to some degree stability in 3D alloyed power conversion efficiencies (PSCs).
  • GBs grain boundaries
  • PSCs 3D alloyed power conversion efficiencies
  • a drawback associated to Sn-based alloyed perovskites is inferior stability under ambient environment since Sn +2 can readily oxidize to stable Sn 4+ when Sn perovskites exposed to ambient environment.
  • ion migration in the halide perovskites plays a critical role in the stability of the PSCs.
  • the passivation of iodide-rich perovskite surface reduces the ion migration in the material, improving the stability of the devices.
  • reduced ion migration in 2D/3D alloyed perovskites decreases the current-voltage hysteresis in the derived devices.
  • optical bandgaps of (FASnl 3 ) x (MAPbl3) 1-x and (PEA) y (FA X MA 1-x ) 1-y Sn x Pb 1-x I 3 were determined from diffuse reflectance measurements.
  • Figure 2 shows steady-state photoluminescence (PL) peaks of the (PEA) y (FA X MAi- x) 1-y Sn x Pb 1-x I 3 films.
  • the optical band gaps obtained from PL match with absorption onset observed in the absorption spectra indicative of direct bandgap nature in (PEA) y (FAx MA 1-x ) 1- y Sn x Pb 1-x I 3 materials ( Figure 2a).
  • Figure 2a we compare the PL intensity of 3D alloyed perovskites with 2D/3D alloyed perovskites in Figures 2b-d. A noticeable enhancement in PL intensity has observed after stoichiometrically replacing FA/MA with PEA in alloyed perovskites.
  • the FA/MA substitution with 10% PEA cations shows highest PL intensity in all alloyed perovskite compositions.
  • the increase in PL intensity in a semiconductor correlates with reduction of nonradiative recombination in a material.
  • the XRD pattern also suggests that (FASnl 3 )x (MAPbl 3 ) 1-x adopts a crystal structure type consisting of Sn and Pb atoms randomly occupying corner-sharing ([Sn 1-x Pb x l 6 ] -4 ) octahedra [21],
  • the crystal structure is unchanged after replacing a small amount of FA/MA by PEA in alloyed perovskites. But, we noticed better crystallinity for all 2D/3D compositions in comparison to 3D counterparts.
  • the intensity of the XRD peaks notably increased for alloyed perovskites with PEA, which could be from higher crystallinity of the perovskite as well as good film coverage on the substrate.
  • X-ray photoelectron spectroscopy (XPS) measurements were carried out.
  • Figure 8 shows the two XPS Sn 3d peaks (corresponding to 3d 5/2 and 3d 3/2 peaks) of (FASnl 3 ) 0.3 (MAPbl 3 ) 0.7 and (PEA) 0.05 (FA0.3 MA 0.7 ) 0.95 Sn 0.3 Pb 0.7 I 3 films.
  • Figure 9 shows the survey spectrum of alloyed perovskites.
  • 3D alloyed perovskite was highly susceptible to Sn 2+ oxidation evident from presence of peak corresponding to Sn 4+ .
  • Sn 3d 5/2 peak located at 486 eV
  • Sn 3d 5/2 peak could deconvoluted into two peaks located at 485.97 eV and 486.7 eV corresponding to Sn 2+ and Sn 4+ oxidation states.
  • Sn 3d 3/2 peak (located at 495.5 eV) comprised of two peaks located at 494.35 eV and 495.34 eV associated with Sn 2+ and Sn 4+ oxidation states [13], Also, additional peaks at 483.65 eV and 492.55 eV emerges in the XPS spectrum of 3D alloyed perovskite films which correspond to zero-valent Sn (Sn°).
  • the Sn 2+ oxidation to Sn 4+ is a strong indication of Sn vacancy formation in Sn-based perovskites [23]
  • the intrinsic defects such as Sn vacancies (through the Sn 2+ oxidation) in the 3D alloyed perovskite generate p-type conductivity in the semiconductor [24]
  • the defect formation energy of Sn vacancy is lower amongst other point defects due to the strong Sn 5s— I 5p antibonding coupling, which implies that Sn vacancy is the dominant intrinsic defect producing high hole (p-type) carrier density in Sn-based perovskites [25]
  • the high background hole carrier density within 3D alloyed perovskites stimulates predominantly monomolecular (or trap-assisted) recombination processes.
  • 2D/3D alloyed perovskite does not show any signs of Sn 2+ oxidation or metallic Sn formation.
  • the XPS studies reveal that PEA cations play a key role in inhibiting Sn 2+ oxidation and Sn formation in alloyed perovskite films.
  • First principle calculations have shown that the ionic size of organic cations plays a vital role in governing formation energy of Sn vacancies in Sn-based perovskites [14], The larger ionic size of organic cation reduces the Sn 5s— I 5p antibonding coupling, leading to lower the Sn vacancy formation energies in the Sn-based perovskites.
  • the V oc and FF strongly depend on charge carrier recombination in the solar cell and Sn-rich perovskites are likely to heavily p-doped limiting the V oc and FF of the devices.
  • the J-V curves and corresponding external quantum efficiency (EQE) graphs of solar cells are shown in Figure 13.
  • the EQE shows photoresponse of the solar cell in the NIR region.
  • the calculated J sc from EQE closely matches with J sc obtained from J-V curve except in (FASnl 3 ) 0.7 (MAPbl 3 ) 03 . This mismatch only is seen in Sn-rich 3D perovskite probably because of quicker degradation of the samples.
  • ⁇ 95
  • 2D/3D perovskite devices which implies photogenerated charge carriers in 3D alloyed perovskite device are not efficiently transported to the electrodes [26]
  • Voc versus logarithmically scaled light intensity.
  • recombination rate is proportional to the product of charge carrier densities [27].
  • the recombination rate reduces producing better FF.
  • the FF increases with decreasing light intensity in 2D/3D alloyed PSCs, which suggest bimolecular recombination dominate in the device.
  • FF decreases with decreasing light intensity in 3D alloyed perovskite device which indicates trap-assisted recombination dominates in these devices [27]
  • the rate of charge carriers recombining with trapped charges increases with decreasing light intensity resulting in lower FF in 3D alloyed perovskite devices. It should be noted that the number of traps does not change with lowering the light intensity.
  • the charge carrier traps such as Sn vacancies, mobile iodide ions are mainly located at GBs and on the perovskite film surface [27],
  • single crystal CsSnI 3 shows very low hole concentration ( ⁇ 10 17 cm -3 ) compared to polycrystalline perovskite films ( ⁇ 10 19 cm -3 ) due to the absence of grain boundaries [13,25],
  • the topographical images suggest that a plate-like crystal film growth for 2D/3D alloyed perovskite films which reduces the number of grain boundaries compared to their 3D analogs.
  • the mobile ions are known to be responsible for the hysteresis phenomenon in PSCs [34,35], Under an applied electric field, iodide anions can move generating ionic current in ionic crystals like halide perovskites [36,37], The inhibition of Sn vacancy formation may also lead to reduction of mobile iodide ions in 2D/3D perovskites.
  • By controlling mobile iodide ions we have also effectively tamed the J-V hysteresis in alloyed PSCs.
  • Figure 17b displays the degradation of devices under AM 1.5G illumination in an inert atmosphere.
  • Figure 17c shows that the degradation of alloyed perovskite devices is rapid in the co-presence of light and modest moisture.
  • 2D/3D perovskite devices are more resilient to the degradation, retaining 20% of initial performance after 24 hours whereas 3D perovskite devices wholly degraded.
  • Tin iodide (SnI 2 ) , tin fluoride (SnF2), dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) were purchased from Sigma Aldrich.
  • Lead iodide (PbI 3 ) was purchased from Acros Organics.
  • Phenyl-Cei-butyric acid methyl ester (PC 61 BM) and poly (3,4-ethylene dioxythiophene)-poly (styrene sulfonate) (PEDOT: PSS; CleviosTM P VP Al 4083) were obtained from 1 -Materials and Heraeus, respectively. All chemicals were used as received.
  • Example 1 - Preparation of FASnl 3 precursor solution (1.1 M): The 1.1M of FASnh precursor solution was prepared by adding equimolar FAI (189.2 mg) and SnI 2 (409.77 mg) powders and 20 mol% of SnF2 (17.3 mg) into a mixture of 1 mL of mixture of DMF: DMSO (4:1 v/v). The solution was stirred for half an hour at room temperature inside the glove box.
  • Example 3 Preparation of 3D (FASnI 3 ) 0.3 (MAPbI 3 ) 0.7 composition: The composition was obtained by stoichiometrically mixing 300 microliter of the FASnl 3 precusor solution prepared at Example 1 and 700 microliter of the MAPbl 3 precursor solution prepared at Example 2.
  • Example 4 Preparation of 3D (FASnI 3 ) 0.5 (MAPbI 3 ) 0.5 composition: The composition was obtained by stoichiometrically mixing 500 microliter of the FASnl 3 precusor solution prepared at Example 1 and 500 microliter of the MAPbl 3 precursor solution prepared at Example 2.
  • Example 5 Preparation of 3D (FASnI 3 ) 0.7 (MAPbI 3 ) 0.3 composition: The composition was obtained by stoichiometrically mixing 700 microliter of the FASnl 3 precusor solution prepared at Example 1 and 300 microliter of the MAPbl 3 precursor solution prepared at Example 2.
  • the 2D/3D alloyed perovskite precursor solutions were prepared by stoichiometrically substituting FAI/MAI with 5% and 10% PEAI in (FASnI 3 )x (MAPbl3) 1-x precursor solution.
  • Example 6 Preparation of 2D/3D (PEA) 0.05 (FA X MAI. X ) 0.95 Sn x Pb 1-x I 3 perovskite precursor solution: We first prepared PEA 0.05 FA 0.95 SnI 3 and PEA 0.05 MA 0.95 PbI 3 precursors as described above at Examples 1-2 wih suitable modifications. We replaced 5% (in weight) of MAI and FAI replaced with PEAI compared to 3D FASnl 3 and MAPbl 3 perovskite precursor solutions. The solutions were stirred for half an hour at room temperature inside the glove box.
  • Example 7 Preparation of 2D/3D (PEA) 0.1 (FA X MAI. X ) 0.90 Sn x Pb 1-x I 3 perovskite precursor solution:
  • PEA 2D/3D
  • PEA 0.1
  • FA X MAI. X 0.90
  • Sn x Pb 1-x I 3 perovskite precursor solution We first prepared PEA 0.1 FAo.9oSnh and PEA 0.1 MAogoPbh precursors as described above at Examples 1-2 wih suitable modifications.
  • the solutions were stirred for half an hour at room temperature inside the glove box.
  • Example 8 Preparation of 2D/3D (PEA) 0.05 (FA X MAI. X ) 0.95 Sn x Pb 1-x h perovskite solution: The solutions were mixed as described above for the 3D perovskite precursor solutions (Examples 3-5).
  • Example 9 Preparation of 2D/3D (PEA) 0.1 (FA X MAI. X ) 0.90 Sn x Pb 1-x I 3 perovskite solution: The solutions were mixed as described above for the 3D perovskite precursor solutions (Examples 3-5).
  • Example 10 - Solar celle fabrication Patterned ITO-coated glasses were cleaned by sonication in detergent followed by sequential washing with deionized water, acetone, and isopropanol. After drying under air flow, the substrate surface was cleaned by oxygen plasma for 10 minutes under rough vacuum.
  • the PEDOT: PSS solution was spin-coated on top of an ITO-coated glass substrate at 45000 rpm for 45 seconds; PEDOT: PSS performs as the hole transporting layer.
  • the PEDOT: PSS film was then dried in air on a hot plate (set at 170°C) for 10 minutes. After drying, the substrate is transferred to a nitrogen-filled glovebox for further use.
  • the 3D and 2D/3D alloyed perovskite absorber layer was spin-coated on the PEDOT : PSS film at 5,000 rpm for 60 seconds. Diethyl ether was dropped onto the spinning substrate. Then the PCeiBM solution (20 mg/mL in chlorobenzene) was spin-coated on top of the perovskite film at 1000 rpm for 45 seconds to form a 20 nm thick electron transporting layer. Finally, the film was transferred to a thermal evaporation chamber inside the nitrogen filled glove box. The chamber was pumped down to 1 x 10" 6 Torr for silver deposition. The 100 nm thick silver top electrode was deposited through a shadow mask that defines the active device area as 0.06 cm 2 for the solar cells.
  • Example 11 - Perovskite Film Characterization Topography of perovskite film surface was obtained by using Bruker MultiMode8 AFM. The absorption spectra were collected by using a Lambda 750, UV-Visible-NIR spectrometer (Perkin Elmer). Steady-state PL spectra were obtained from a Fluorolog®-3 system (Horiba Jobin Yvon). XRD measurements were carried out using a Panalytical X-Pert PRO MRD X-Ray diffractometer. The oxidation of Tin element probed by XPS (ESCALAB 220I-XL spectrometer) equipped with an Al Ka (1486.6 eV) monochromatic source.
  • XPS XPS
  • Al Ka 1486.6 eV
  • KPFM measurements were done using Lift mode in Bruker MultiMode8 AFM under ambient conditions. KPFM measurements were performed using a Pt/lrtip (Bruker, SCM-PIT) with a lift height of 20 nm by applying AC voltage of 1V.
  • Example 12 - Solar cell characterization Solar cell performance was measured using a class ABA LED solar simulator which was calibrated to deliver simulated AM 1.5 sunlight at an irradiance of 100 mW/cm 2 (The irradiance was calibrated using an NREL- calibrated KG5 filtered silicon reference cell). Current-voltage curves were recorded using a source meter (Keithley 2400, USA). External quantum efficiency (EQE) measurement was conducted by using an IQE200B system (Newport Corporation).
  • EQE External quantum efficiency
  • Example 13 - Device stability tests The stability of devices were tested in the same device configuration without any encapsulation.
  • the 2D and 3D perovskite devices were placed inside a desiccator.
  • the relative humidity (28 ⁇ 2% RH humidity) was measured with a digital humidity sensor.
  • the perovskite devices were placed under constant AM1.5G illumination inside the N2 filled glovebox. Devices are also tested under constant AM1.5G illumination at 28 ⁇ 2% RH humidity.
  • Suitable large organic cations equivalent to the methylammonium (MA) cation and different from phenylethylammonium (PEA), ammonium cations may also be used to replace methylammonium (MA) and formamidinium (FA) in the halide perovskite according to the invention.
  • Such organic cations include for example those depicted in general formulae I, II, III, IV and V as depicted herein.
  • iodine may be replaced by chorine (Cl) or bromine (Br).
  • the alloy in the halide perovskite of the invention may include any suitable metals.
  • Such metals may be for example tin (Sn), lead (Pb), germanium (Ge).
  • alloys in the perovskite according to the invention may be for example Sn-Pb, Sn-Ge or Ge- Pb. In embodiments of the invention, the alloy is Sn-Pb.
  • Keywords lead-free perovskite solar cells, alloyed perovskites, Sn oxidation, trap-assisted recombination, stability
  • PES bulkier phenylethylammonium
  • halide perovskites mainly the hybrid organic- inorganic perovskites 2 but also the all-inorganic perovskites, 3,4 have attracted the major research interest in the photovoltaic community mainly because of their simple solution deposition fabrication process, rapidly increasing and high power conversion efficiencies (PCEs) and spectacular optical and electronic properties, including tunable bandgap from 1.15 to 3.06 eV by swapping different cations and halides in the perovskite structure. 5 7
  • Pb perovskite solar cells involve water-soluble Pb species, which hamper the commercialization of this technology. 8 Once in contact with water or moisture, Pb perovskites quickly form water-soluble by-products of Pb, which can accumulate within the food chain and so human body. 9 It is thus highly necessary to restrict the use of Pb by replacing it partially or entirely with less toxic or, even better, non-toxic metals. Most likely, appropriate candidates for Pb replacement without compromising too much photovoltaic properties are elements in the same group (group 4) as Pb. The immediate candidates then appear as Sn and Ge, both of which can be more easily oxidized from the 2 + to 4 + oxidation states than Pb.
  • Sn-based PSCs thus demonstrate subpar open-circuit voltage (V oc ) mainly due to severe trap- assisted recombination triggered by Sn vacancy-mediated unintentional doping/defects.
  • V oc subpar open-circuit voltage
  • Different approaches including morphological control of the Sn perovskites, minimization of oxygen exposure during the device preparation, and the addition of Sn salts, have been explored and found to be useful in improving the performance of Sn-based PSCs.
  • Wang et al. reported one of the Sn PSCs with an efficiency of 9.41% by employing quasi-two-dimensional (2D) Sn perovskites, which is still falling far short of Pb PSCs.
  • alloying Pb with Sn perovskites seems to be a promising, balanced strategy towards achieving stable, less toxic solar cells without much compromising the photovoltaic performance.
  • alloyed Sn-Pb perovskites bring an added advantage, extended absorption of photons to the near-infrared (NIR) spectral range (up to 1050 nm with an optical bandgap of 1.18 eV).
  • typical hybrid organic-inorganic halide perovskites such as MAPbI 3 , FASnl 3 .
  • the trap-assisted recombination coefficient which is defined as a specific rate at which oppositely charged ions combine at traps, is ⁇ 70 times higher than those in Pb-based ones. 23 It suggests a prospect of improving the performance of Sn-Pb alloyed PSCs by reducing the defects associated with oxidation of Sn 2+ to Sn 4+ and/or Sn vacancy formation.
  • the defects formed in the course of perovskite film preparation can be detrimental to the stability of the PSCs. So, minimizing the defects in Sn-Pb perovskites improves stability. The defects also play a detrimental role in current density-voltage (J-V) curve hysteresis in PSCs through defect migration at grain boundaries (GBs) and perovskite film interfaces.
  • J-V current density-voltage
  • the peak close to the optical absorption edge is ascribed to the bound excitonic state due to the Columbic attraction of electrons and holes (the hydrogenic absorption peak).
  • the peak is located (at 1.85 eV) significantly distant from the absorption onsets (at 1.18 eV, 1.22 eV, 1.26 eV), which basically excludes the hydrogenic absorption origin of the peak.
  • GIWAXS Grazing-incidence wide-angle X-ray scattering
  • the Sn 3d 5/2 peak (located at 495.41 eV) comprises two peaks located at 494.27 eV and 494.71 eV, associated with Sn 2+ and Sn 4+ oxidation states. 17
  • the (PEA) 0.05 (FA0.3 MA 0.7 ) 0.95 Sn 0.3 Pb 0.7 I 3 only shows two sharp, non- deconvolutable peaks, with no Sn 4+ peaks.
  • the XPS spectra of (PEA) 0.05 (FA 0.7 MA 0.3 ) 0.95 Sn 0.7 Pb 0.3 I 3 perovskites also showed similar behavior compared to their control samples ( Figure S7).
  • the resultant defects can stimulate non-radiative (or trap-assisted) recombination processes, which is detrimental to photovoltaic performance.
  • the PEA-FA/MA alloyed perovskites do not show any detectable signals of Sn 4+ , enhanced photovoltaic performance and stability are thus expected.
  • PEA bulkier organic cations
  • V oc and fill factor (FF) reduced as the Sn content increased (Table 1), with Sn-rich ((FASnl 3 ) 0.7 (MAPb 13)0.3) showing the lowest V oc and FF amongst all the compositions.
  • Sn-rich perovskites are highly likely to contain a higher number of defects limiting the V oc and FF of their devices. Specifically, the defects in the bandgap would attract electrons/holes and act as non-radiative recombination centers, which primarily impacts the V oc of corresponding solar cells.
  • V oc was significantly improved.
  • the V oc of (FASnl 3 ) 0.3 (MAPbl 3 ) 0.7 PSCs was boosted from 0.72 V to 0.80 V.
  • the highest V oc enhancement (of 0.23V) was observed for (PEA) 0.1 (F Ao. ?M A 0.3 )0.90 Sn 0.7 Pb 0.3 I 3 , followed by (PEA) 0.1 (FA 0.5 MA 0.5 )o.9o Sn 0.5 Pb 0.5 I 3 (with an improvement of 0.15 V).
  • J sc there is no clear trend of variation with incorporating PEA among various alloyed perovskite compositions. But in a particular alloyed perovskite compositional group, the J sc in the devices follows a similar trend as observed in XRD data, especially in Sn-rich perovskites, where reduction of crystallinity with higher amount of PEA lowered the J sc .
  • the PSCs employing Sn-Pb alloyed perovskites with 5% bulkier PEA cations produced the highest PCE. We hypothesis this is due to a trade-off between local lattice strain or/and crystallinity and the number of defects in the alloyed perovskites.
  • Figures S8-S10 shows the statistical distribution of efficiency of 20-30 devices in each compositional group.
  • J-V curves and corresponding external quantum efficiency (EQE) spectra of solar cells are shown in Figures 6 and SI 1. It can be seen from the EQE measurements that the photoresponse of all the solar cells reaches up to the near-infrared (NIR) region.
  • NIR near-infrared
  • the calculated J sc values from EQE basically matched with those obtained from the J-V curves, except for (FASnl 3 ) 0.7
  • Figure 7a shows the dependence of J sc on incident light intensity by fitting to a power law (I).
  • t 1/2 as a time for the PCE of the device to drop to 50% of its initial value for standardizing the comparison between different devices.
  • Figure S13a shows the degradation of devices under a modest moisture environment (28 ⁇ 2% RH humidity) in the dark. The degradation was significantly slowed down by substituting FA/MA with 5% of PEA in (FASnl 3 ) 0.3 (MAPbl 3 ) 0.7 .
  • Figure SI 3b displays the degradation of devices under AM1.5G illumination in an inert atmosphere.
  • Figure S13c shows that the degradation of alloyed perovskite devices became faster in the co-presence of light and modest moisture.
  • PEA-FA/MA perovskite devices were still more resistant to the degradation, retaining 20% of initial performance after 24h, whereas FA/MA perovskite devices were wholly degraded during the same period.
  • the defects in Sn-Pb perovskites induced by Sn vacancies not only play a key role in determining photovoltaic performance (PCE and J-V hysteresis) but also the stability of the devices.
  • the defects in perovskites are vulnerable to oxygen or moisture filtration and accelerate the degradation of devices under ambient conditions.
  • 49 Reduced defects (see DFT calculations and PL discussion) and enhanced crystallinity (see XRD and GIWAXS discussion) with the incorporation of 5% PEA in Sn-Pb perovskites contribute to enhanced stability of the PEA-FA/MA Sn-Pb PSCs.
  • Figure 8 a) Height topography and b-c) surface potential profile of (FASnl 3 ) 0.3 (MAPbl 3 ) 0.7 , d) topography and e-f) surface potential profile of (PEA) 0.05 (FA0.3 MA 0.7 ) 0.95 (Sn 0.3 Pb 0.7 ) I 3 .
  • the average CPD calculated using Gwyddion software is also provided at the bottom of each Figure.
  • CPD contact potential difference
  • KPFM Kelvin probe force microscopy
  • the charge-separation process in the complete device is mimicked using the AFM probe in the KPFM measurement, and SPV represents the V oc or internal electric field in the solar cell.
  • the SPV increased from 0.059 V to 0.077 V with 5% PEA in alloyed perovskite film, indicating an increase in the internal electric field in PEA-FA/MA perovskite devices; therefore, we can reasonably conclude that photogenerated carriers are more efficiently separated in the PEA-FA/MA perovskite film than FA/MA perovskite film.
  • the KPFM measurements essentially suggest reduced recombination events for the devices employing PEA-FA/MA perovskite film compared to their control samples.
  • Methylammonium iodide (CH 3 NH 3 I), Formamidinium iodide (CH(NH2)2l) and phenylethylammonium iodide ( C 6 H 5 (CH 2 ) 2 NH 3 I) were purchased from Dyesol.
  • Tin iodide (SnE), tin fluoride (SnF2), dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) were purchased from Sigma Aldrich.
  • Lead iodide (Pb I 2 ) was bought from Acros Organics.
  • Phenyl- C61-butyric acid methyl ester (PC 61 BM) and poly (3, 4-ethylene dioxythiophene)-poly (styrene sulfonate) (PEDOT: PSS; CleviosTM P VP Al 4083) were obtained from 1-Materials and Heraeus, respectively. All chemicals were used as received. Alloyed perovskite precursor solution: FASnI 3 precursor solution (1.1 M) was prepared by adding equimolar FAI and SnI 2 powders and 20 mol% of SnF 2 into a mixture of DMF: DMSO (4: 1 v/v).
  • MAPbI 3 precursor solution (1.1 M) was prepared by adding MAI and PbI 2 in a mixture of DMF: DMSO (4: 1 v/v).
  • (FASnl 3 ) x (MAPbl 3 ) 1-x (x 0.3, 0.5, 0.7) solutions were prepared by stoichiometrically mixing FASnI 3 and MAPbE solutions.
  • the PEA-FA/MA alloyed perovskite precursor solutions were prepared by stoichiometrically substituting FAI/MAI with 5% and 10% PEAI in (FASnI 3 ) x (MAPbl 3 ) 1-x precursor solution.
  • the FA/MA and PEA-FA/MA alloyed perovskite absorber layer were spin-coated on the PEDOT : PSS film at 5000 rpm for 60 s. Diethyl ether was dropped onto the spinning substrate. The spin-coated films were annealed at 60°C for 5 minutes. Then the PC 61 BM solution (20 mg/mL in chlorobenzene) was spin-coated on top of the perovskite film at 2000 rpm for 60 s to form a 20 nm thick electron transporting layer. Finally, the film was transferred to a thermal evaporation chamber inside the nitrogen-filled glove box. The chamber was pumped down to 1 x 10 -6 Torr for silver deposition.
  • Perovskite Film Characterization Topography of perovskite film surface was obtained by using a Bruker MultiMode8 AFM. Absorption spectra were collected by using a UV-Visible- NIR spectrometer Lambda 750 (Perkin Elmer). Steady-state PL spectra were obtained from a Fluorolog®-3 system (Horiba Jobin Yvon) using a 444 nm laser. XRD measurements were carried out using a Panalytical X-Pert PRO MRD X-Ray diffractometer.
  • the oxidation of the tin element was probed by an XPS spectrometer (ESCALAB 220I-X L) equipped with an Al K ⁇ (1486.6 eV) monochromatic source.
  • the grazing incidence wide-angle X-ray scattering (GIWAXS) measurements were done at the BL14B1 beamline of the Shanghai Synchrotron Radiation Facility (SSRF).
  • the GIWAXS patterns were collected by a MarCCD detector, which is mounted vertically at around 194 mm from the sample. The exposure time was less than 50 s, and a grazing incidence angle with respect to the surface plane is 1°.
  • KPFM measurements were done using the tapping mode in a Cypher AFM (Model: Cypher S) under ambient conditions. KPFM measurements were performed using a Platinum-coated Silicon tip. A white LED lamp was used to carry out KPFM measurements under illumination.
  • Solar cell characterization Solar cell performance was measured using a class ABA LED solar simulator, which was calibrated to deliver simulated AM 1.5 sunlight irradiance of 100 mW/cm 2 . The irradiance was calibrated using an NREL-calibrated KG5 filtered silicon reference cell. Current density -voltage (J-V) curves were recorded using a source meter (Keithley 2400, USA). External quantum efficiency (EQE) measurements were conducted by using an IQE200B system (Newport Corporation).
  • Device stability tests The stability of devices was tested without any device encapsulation.
  • the PEA-FA/MA and FA/MA perovskite devices were placed inside a desiccator under an ambient environment.
  • the relative humidity 28 ⁇ 2% RH humidity
  • the relative humidity 28 ⁇ 2% RH humidity
  • the perovskite devices were placed under constant AM1.5G illumination inside an N2 filled glovebox. Devices were also tested under constant AM1.5G illumination at 28 ⁇ 2% RH humidity.
  • a 1 x4x4 F-centered Appoint sampling of the Brillouin Zone (BZ) was used for the structural optimizations of both the 8x 1 x 1 bare FASnI 3 and mixed (PEA 4 FA 10 )Sn 12 I 38 supercells.
  • E form E tot ( Vsn q ) - E tot + ⁇ Sn + q( ⁇ VBM +E F ), (2)
  • the chemical potentials of FASnI 3 constituents were estimated by imposing the thermodynamic equilibrium of FASnI 3 with the SnE phase. We thus apply the following two constraints:
  • BSSE Basis Set Superposition Error

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Abstract

L'invention concerne des pérovskites d'halogénure qui ne comprennent pratiquement pas de plomb (Pb) sous forme libre ou sous une forme quelconque pouvant conduire à des précurseurs de celui-ci solubles dans l'eau. Les pérovskites d'halogénure selon l'invention ont une structure 2D/3D et comprennent des alliages qui peuvent ou non comporter du plomb, par exemple des alliages étain-plomb (Sn-Pb).
PCT/CA2021/051657 2020-11-23 2021-11-22 Pérovskites d'halogénure à alliages 2d/3d : procédé pour les préparer et les utiliser dans des cellules solaires WO2022104483A1 (fr)

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US20160075881A1 (en) * 2013-11-26 2016-03-17 Hunt Energy Enterprises, L.L.C. Bi- and Tri- Layer Interfacial Layers in Perovskite Material Devices
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