Organic–inorganic metal halide perovskites have recently emerged as a top contender to be used as an absorber material in highly efficient, low-cost photovoltaic devices. Solution-processed ...semiconductors tend to have a high density of defect states and exhibit a large degree of electronic disorder. Perovskites appear to go against this trend, and despite relatively little knowledge of the impact of electronic defects, certified solar-to-electrical power conversion efficiencies of up to 17.9% have been achieved. Here, through treatment of the crystal surfaces with the Lewis bases thiophene and pyridine, we demonstrate significantly reduced nonradiative electron–hole recombination within the CH3NH3PbI3–x Cl x perovskite, achieving photoluminescence lifetimes which are enhanced by nearly an order of magnitude, up to 2 μs. We propose that this is due to the electronic passivation of under-coordinated Pb atoms within the crystal. Through this method of Lewis base passivation, we achieve power conversion efficiencies for solution-processed planar heterojunction solar cells enhanced from 13% for the untreated solar cells to 15.3% and 16.5% for the thiophene and pyridine-treated solar cells, respectively.
An understanding of charge-carrier recombination processes is essential for the development of hybrid metal halide perovskites for photovoltaic applications. We show that typical measurements of the ...radiative bimolecular recombination constant in CH3NH3PbI3 are strongly affected by photon reabsorption that masks a much larger intrinsic bimolecular recombination rate constant. By investigating a set of films whose thickness varies between 50 and 533 nm, we find that the bimolecular charge recombination rate appears to slow by an order of magnitude as the film thickness increases. However, by using a dynamical model that accounts for photon reabsorption and charge-carrier diffusion we determine that a single intrinsic bimolecular recombination coefficient of value 6.8 × 10–10 cm3s–1 is common to all samples irrespective of film thickness. Hence, we postulate that the wide range of literature values reported for such coefficients is partly to blame on differences in photon out-coupling between samples with crystal grains or mesoporous scaffolds of different sizes influencing light scattering, whereas thinner films or index-matched surrounding layers can reduce the possibility for photon reabsorption. We discuss the critical role of photon confinement on free charge-carrier retention in thin photovoltaic layers and highlight an approach to assess the success of such schemes from transient spectroscopic measurement.
Methylammonium tin triiodide (MASnI3) has been successfully employed in lead-free perovskite solar cells, but overall power-conversion efficiencies are still significantly lower than for lead-based ...perovskites. Here we present photoluminescence (PL) spectra and time-resolved PL from 8 to 295 K and find a marked improvement in carrier lifetime and a substantial reduction in PL line width below ∼110 K, indicating that the cause of the hindered performance is activated at the orthorhombic to tetragonal phase transition. Our measurements therefore suggest that targeted structural change may be capable of tailoring the relative energy level alignment of defects (e.g., tin vacancies) to reduce the background dopant density and improve charge extraction. In addition, we observe for the first time an above-gap emission feature that may arise from higher-lying interband transitions, raising the prospect of excess energy harvesting.
Highest reported efficiency cesium lead halide perovskite solar cells are realized by tuning the bandgap and stabilizing the black perovskite phase at lower temperatures. CsPbI2Br is employed in a ...planar architecture device resulting in 9.8% power conversion efficiency and over 5% stabilized power output. Offering substantially enhanced thermal stability over their organic based counterparts, these results show that all‐inorganic perovskites can represent a promising next step for photovoltaic materials.
We demonstrate four- and two-terminal perovskite-perovskite tandem solar cells with ideally matched band gaps. We develop an infrared-absorbing 1.2-electron volt band-gap perovskite, ...FA0.75Cs0.25Sn0.5Pb0.5I₃, that can deliver 14.8% efficiency. By combining this material with a wider-band gap FA0.83Cs0.17Pb(I0.5Br0.5)₃ material, we achieve monolithic two-terminal tandem efficiencies of 17.0% with >1.65-volt open-circuit voltage. We also make mechanically stacked four-terminal tandem cells and obtain 20.3% efficiency. Notably, we find that our infrared-absorbing perovskite cells exhibit excellent thermal and atmospheric stability, not previously achieved for Sn-based perovskites. This device architecture and materials set will enable "all-perovskite" thin-film solar cells to reach the highest efficiencies in the long term at the lowest costs.
Mixed lead–tin triiodide perovskites are promising absorber materials for low bandgap bottom cells in all‐perovskite tandem photovoltaic devices. Key structural and electronic properties of the ...FAPb1−xSnxI3 perovskite are presented here as a function of lead:tin content across the alloy series. Temperature‐dependent photoluminescence and optical absorption measurements are used to identify changes in the bandgap and phase transition temperature. The large bandgap bowing parameter, a crucial element for the attainment of low bandgaps in this system, is shown to depend on the structural phase, reaching a value of 0.84 eV in the low‐temperature phase and 0.73 eV at room temperature. The parabolic nature of the bowing at all temperatures is compatible with a mechanism arising from bond bending to accommodate the random placement of unevenly sized lead and tin ions. Charge‐carrier recombination dynamics are shown to fall into two regimes. Tin‐rich compositions exhibit fast, monoexponential recombination that is almost temperature‐independent, in accordance with high levels of electrical doping. Lead‐rich compositions show slower, stretched‐exponential charge‐carrier recombination that is strongly temperature‐dependent, in accordance with a multiphonon assisted process. These results highlight the importance of structure and composition for control of bandgap bowing and charge‐carrier recombination mechanisms in low bandgap absorbers for all‐perovskite tandem solar cells.
The bandgap and charge‐carrier recombination dynamics are investigated for FAPb1−xSnxI3 as a function of metal composition and temperature. Bandgap bowing is modified by a structural phase transition. Charge‐carrier recombination mechanisms show a substantial difference between lead‐rich and tin‐rich compositions. The results show the importance of structure and composition in controlling bandgap bowing and charge‐carrier recombination mechanisms.
Hysteresis in the current–voltage characteristics of vapor‐deposited perovskite solar cells is shown to originate from an amorphous region of CH3NH3PbI3 at the interface with the device's electron ...transport layer. Interface engineering is used to produce highly crystalline perovskite material at this interface which results in hysteresis‐free evaporated planar heterojunction solar cells.
An understanding of charge-carrier recombination processes is essential for the development of hybrid metal halide perovskites for photovoltaic applications. We show that typical measurements of the ...radiative bimolecular recombination constant in CH
NH
PbI
are strongly affected by photon reabsorption that masks a much larger intrinsic bimolecular recombination rate constant. By investigating a set of films whose thickness varies between 50 and 533 nm, we find that the bimolecular charge recombination rate appears to slow by an order of magnitude as the film thickness increases. However, by using a dynamical model that accounts for photon reabsorption and charge-carrier diffusion we determine that a single intrinsic bimolecular recombination coefficient of value 6.8 × 10
cm
s
is common to all samples irrespective of film thickness. Hence, we postulate that the wide range of literature values reported for such coefficients is partly to blame on differences in photon out-coupling between samples with crystal grains or mesoporous scaffolds of different sizes influencing light scattering, whereas thinner films or index-matched surrounding layers can reduce the possibility for photon reabsorption. We discuss the critical role of photon confinement on free charge-carrier retention in thin photovoltaic layers and highlight an approach to assess the success of such schemes from transient spectroscopic measurement.
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