Layered perovskites in solar cells: structure, optoelectronic properties, and device design

Layered hybrid perovskites (LPKs) have emerged as a viable solution to address perovskite stability concerns and enable their implementation in wide-scale energy harvesting. Yet, although more stable, the performance of devices incorporating LPKs still lags behind that of state-of-the-art, multi-cation perovskite materials. This is typically assigned to their poor charge transport, currently caused by the choice of cations used within the organic layer. On balance, a compromise between efficiency and stability is sought, involving careful control of phase purity and distribution, interfaces and energy/charge transfer processes. Further progress is hindered by the difficulty in identifying the fundamental optoelectronic processes in these materials. Here, the high exciton binding energy of LPKs lead to the formation of multiple photoexcited species, which greatly complicate measurement interpretation. In this light, this review gives an overview of how complementary measurement techniques must be used to separate the contributions from the different species in order to identify device bottlenecks, and become a useful tool to narrow down the limitless list of organic cations. A move away from making compromises to mitigate the impact of poor charge transport is required. The root of the problem must be addressed instead through rational design of the interlayer cations

Charge-Carrier Dynamics in 2D Hybrid Metal–Halide Perovskites

Hybrid metal–halide perovskites are promising new materials for use in solar cells; however, their chemical stability in the presence of moisture remains a significant drawback. Quasi two-dimensional (2D) perovskites that incorporate hydrophobic organic interlayers offer improved resistance to degradation by moisture, currently still at the cost of overall cell efficiency. To elucidate the factors affecting the optoelectronic properties of these materials, we have investigated the charge transport properties and crystallographic orientation of mixed methylammonium (MA)–phenylethylammonium (PEA) lead iodide thin films as a function of the MA-to-PEA ratio and, thus, the thickness of the “encapsulated” MA lead–halide layers. We find that monomolecular charge-carrier recombination rates first decrease with increasing PEA fraction, most likely as a result of trap passivation, but then increase significantly as excitonic effects begin to dominate for thin confined layers. Bimolecular and Auger recombination rate constants are found to be sensitive to changes in electronic confinement, which alters the density of states for electronic transitions. We demonstrate that effective charge-carrier mobilities remain remarkably high (near 10 cm2V−1s−1) for intermediate PEA content and are enhanced for preferential orientation of the conducting lead iodide layers along the probing electric field. The trade-off between trap reduction, electronic confinement, and layer orientation leads to calculated charge-carrier diffusion lengths reaching a maximum of 2.5 μm for intermediate PEA content (50%)

Raman Spectrum of the Organic-Inorganic Halide Perovskite CH3NH3PbI3 from First Principles and High-Resolution Low-Temperature Raman Measurements

We investigate the Raman spectrum of the low-temperature orthorhombic phase of the organic-inorganic halide perovskite CH3NH3PbI3, by combining first-principles calculations with high-resolution low-temperature Raman measurements. We find good agreement between theory and experiment, and successfully assign each of the Raman peaks to the underlying vibrational modes. In the low-frequency spectral range (below 60 cm1) we assign the prominent Raman signals at 26, 32, 42 and 49 cm1 to the Pb-I-Pb bending modes with either Ag or B2g symmetry, and the signal at 58 cm1 to the librational mode of the organic cation. Owing to their significant intensity, we propose that these peaks can serve as clear markers of the vibrations of the [PbI3] network and of the CH3NH+ 3 cations in this perovskite, respectively. In particular, the ratios of the intensities of these peaks might be used to monitor possible deviations from the ideal stoichiometry of CH3NH3PbI3

Perovskite-perovskite tandem photovoltaics with optimized bandgaps

We demonstrate four and two-terminal perovskite-perovskite tandem solar cells with ideally matched bandgaps. We develop an infrared absorbing 1.2eV bandgap perovskite, $FA_{0.75}Cs_{0.25}Sn_{0.5}Pb_{0.5}I_3$, that can deliver 14.8 % efficiency. By combining this material with a wider bandgap $FA_{0.83}Cs_{0.17}Pb(I_{0.5}Br_{0.5})_3$ material, we reach monolithic two terminal tandem efficiencies of 17.0 % with over 1.65 volts open-circuit voltage. We also make mechanically stacked four terminal tandem cells and obtain 20.3 % efficiency. Crucially, we find that our infrared absorbing perovskite cells exhibit excellent thermal and atmospheric stability, unprecedented 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

Untangling free carrier and exciton dynamics in layered hybrid perovskites using ultrafast optical and terahertz spectroscopy

Layered hybrid perovskites (LPKs) are promising as alternatives or additives to 3D metal halide perovskites for optoelectronic applications including photovoltaic cells, LEDs and lasers due to their increased stability. However, high exciton binding energies in these materials mean that excitons are the majority species under the operating conditions of many devices. Although the efficiency of devices that incorporate LPKs has been increasing, much is still unknown about the interplay of excitons and free charge-carriers in these materials, which is vital information for understanding how optoelectronic properties dictate device efficiency. In this work, we employ optical pump/THz probe spectroscopy (OPTP) and visible transient absorption spectroscopy (TAS) to analyse the optoelectronic properties and charge-carrier dynamics of phenylethylammonium lead iodide (PEA)2PbI4. By combining these techniques, we are able to disentangle the contributions from excitons and free charge-carriers. We observe fast cooling of free charge-carriers and exciton formation on a timescale of ∼400 fs followed by slower bimolecular recombination of residual free charge-carriers with a rate constant k 2 ∼ 109 cm3s−1. Excitons recombine via two monomolecular processes with lifetimes t 1 ∼ 11 ps and t2 ∼ 83 ps. Furthermore, we detect signatures of exciton–phonon coupling in the transient absorption kinetic traces. These findings provide new insight into the interplay between free charge-carriers and excitons as well as a possible mechanism to further understand the charge-carrier dynamics in LPKs

Biomarkers of stroke recovery: consensus-based core recommendations from the Stroke Recovery and Rehabilitation Roundtable

The most difficult clinical questions in stroke rehabilitation are ‘‘What is this patient’s potential for recovery?’’ and ‘‘What is the best rehabilitation strategy for this person, given her/his clinical profile?’’ Without answers to these questions, clinicians struggle to make decisions regarding the content and focus of therapy, and researchers design studies that inadvertently mix participants who have a high likelihood of responding with those who do not. Developing and implementing biomarkers that distinguish patient subgroups will help address these issues and unravel the factors important to the recovery process. The goal of the present paper is to provide a consensus statement regarding the current state of the evidence for stroke recovery biomarkers. Biomarkers of motor, somatosensory, cognitive and language domains across the recovery timeline post-stroke are considered; with focus on brain structure and function, and exclusion of blood markers and genetics. We provide evidence for biomarkers that are considered ready to be included in clinical trials, as well as others that are promising but not ready and so represent a developmental priority. We conclude with an example that illustrates the utility of biomarkers in recovery and rehabilitation research, demonstrating how the inclusion of a biomarker may enhance future clinical trials. In this way, we propose a way forward for when and where we can include biomarkers to advance the efficacy of the practice of, and research into, rehabilitation and recovery after stroke

Charge-carrier dynamics in mixed lead-tin 2D/3D metal halide perovskites

Halide perovskite thin films with mixtures of both standard 3D perovskites and quasi-2D or layered perovskites are promising materials for devices due to their increased stability. Optical-pump/THz probe studies combined with visible transient absorption measurements reveal the complex charge-carrier dynamics in these mixed materials

Efficient Terahertz Generation via Optical Rectification in Halide Perovskites

THz emission from the all-organic, halide perovskite N-methyl-1,4-diazabicyclo [2.2.2] octan-1-ium (methyl-DABCO) ammonium iodide (MDNI) has been demonstrated for the first time. The generation mechanism was shown to be optical rectification, and a peak field strength of up to 0.8 kV/cm was achieved, demonstrating the promise of this class of materials as efficient THz emitter

YG200604171857_1

The photoluminescence, transmittance, charge‐carrier recombination dynamics, mobility, and diffusion length of CH3NH3PbI3 are investigated in the temperature range from 8 to 370 K. Profound changes in the optoelectronic properties of this prototypical photovoltaic material are observed across the two structural phase transitions occurring at 160 and 310 K. Drude‐like terahertz photoconductivity spectra at all temperatures above 80 K suggest that charge localization effects are absent in this range. The monomolecular charge‐carrier recombination rate generally increases with rising temperature, indicating a mechanism dominated by ionized impurity mediated recombination. Deduced activation energies Ea associated with ionization are found to increase markedly from the room‐temperature tetragonal (Ea ≈ 20 meV) to the higher‐temperature cubic (Ea ≈ 200 meV) phase adopted above 310 K. Conversely, the bimolecular rate constant decreases with rising temperature as charge‐carrier mobility declines, while the Auger rate constant is highly phase specific, suggesting a strong dependence on electronic band structure. The charge‐carrier diffusion length gradually decreases with rising temperature from about 3 μm at −93 °C to 1.2 μm at 67 °C but remains well above the optical absorption depth in the visible spectrum. These results demonstrate that there are no fundamental obstacles to the operation of cells based on CH3NH3PbI3 under typical field conditions