arXiv subjects

Madeleine Laitz

Publications and source records attributed to Madeleine Laitz.

5 recordsLinked to original sources

arXiv2022

Reduced Recombination via Tunable Surface Fields in Perovskite Solar Cells

The ability to reduce energy loss at semiconductor surfaces through passivation or surface field engineering has become an essential step in the manufacturing of efficient photovoltaic (PV) and optoelectronic devices. Similarly, surface modification of emerging halide perovskites with quasi-2D heterostructures is now ubiquitous to achieve PV power conversion efficiencies (PCEs) > 22% and has enabled single-junction PV devices to reach 25.7%, yet a fundamental understanding to how these treatments function is still generally lacking. This has established a bottleneck for maximizing beneficial improvements as no concrete selection and design rules currently exist. Here we uncover a new type of tunable passivation strategy and mechanism found in perovskite PV devices that were the first to reach the > 25% PCE milestone, which is enabled by surface treating a bulk perovskite layer with hexylammonium bromide (HABr). We uncover the simultaneous formation of an iodide-rich 2D layer along with a Br halide gradient achieved through partial halide exchange that extends from defective surfaces and grain boundaries into the bulk layer. We demonstrate and directly visualize the tunability of both the 2D layer thickness, halide gradient, and band structure using a unique combination of depth-sensitive nanoscale characterization techniques. We show that the optimization of this interface can extend the charge carrier lifetime to values > 30 μs, which is the longest value reported for a direct bandgap semiconductor (GaAs, InP, CdTe) over the past 50 years. Importantly, this work reveals an entirely new strategy and knob for optimizing and tuning recombination and charge transport at semiconductor interfaces and will likely establish new frontiers in achieving the next set of perovskite device performance records.

physics.app-ph↗

arXiv2022

Uncovering Temperature-Dependent Exciton-Polariton Relaxation Mechanisms in Perovskites

State-of-the-art hybrid perovskites have demonstrated excellent functionality in photovoltaics and light-emitting applications, and have emerged as a promising candidate for exciton-polariton (polariton) optoelectronics. In the strong coupling regime, polariton formation and Bose-Einstein condensation (BEC) have been demonstrated at room-temperature in several perovskite formulations. Thermodynamically, low-threshold BEC requires efficient scattering to $k_{||}$ = 0, and many applications demand precise control of polariton interactions. Thus far, the primary mechanisms by which polaritons relax in perovskites remains unclear. In this work, we perform temperature-dependent measurements of polaritons in low-dimensional hybrid perovskites with high light-matter coupling strengths ($\hbar Ω_{Rabi}$ = 260$\pm$5 meV). By embedding the perovskite active layer in a wedged cavity, we are able to tune the Hopfield coefficients and decouple the primary polariton relaxation mechanisms in this material for the first time. We observe the thermal activation of a bottleneck regime, and reveal that this effect can be overcome by harnessing intrinsic scattering mechanisms arising from the interplay between the different excitonic species, such as biexciton-assisted polariton relaxation pathways, and isoenergetic intracavity pumping. We demonstrate the dependence of the bottleneck suppression on cavity detuning, and are able to achieve efficient relaxation to $k_{||}$ = 0 even at cryogenic temperatures. This new understanding contributes to the design of ultra-low-threshold BEC and condensate control by engineering polariton dispersions resonant with efficient relaxation pathways, leveraging intrinsic material scattering mechanisms for next-generation polariton optoelectronics.

cond-mat.mes-hall↗

arXiv2022

Processing Induced Distinct Charge Carrier Dynamics of Bulky Organic Halide Treated Perovskites

State-of-the-art metal halide perovskite-based photovoltaics often employ organic ammonium salts, AX, as a surface passivator, where A is a large organic cation and X is a halide. These surface treatments passivate the perovskite by forming layered perovskites (e.g., A2PbX4) or by AX itself serving as a surface passivation agent on the perovskite photoactive film. It remains unclear whether layered perovskites or AX is the ideal passivator due to an incomplete understanding of the interfacial impact and resulting photoexcited carrier dynamics of AX treatment. In the present study, we use TRPL measurements to selectively probe the different interfaces of glass/perovskite/AX to demonstrate the vastly distinct interfacial photoexcited state dynamics with the presence of A2PbX4 or AX. Coupling the TRPL results with X-ray diffraction and nanoscale microscopy measurements, we find that the presence of AX not only passivates the traps at the surface and the grain boundaries, but also induces an α/δ-FAPbI3 phase mixing that alters the carrier dynamics near the glass/perovskite interface and enhances the photoluminescence quantum yield. In contrast, the passivation with A2PbI4 is mostly localized to the surface and grain boundaries near the top surface where the availability of PbI2 directly determines the formation of A2PbI4. Such distinct mechanisms significantly impact the corresponding solar cell performance, and we find AX passivation that has not been converted to a layered perovskite allows for a much larger processing window (e.g., larger allowed variance of AX concentration which is critical for improving the eventual manufacturing yield) and more reproducible condition to realize device performance improvements, while A2PbI4 as a passivator yields a much narrower processing window. We expect these results to enable a more rational route for developing AX for perovskite.

cond-mat.mtrl-sci↗

arXiv2021

Accurate Determination of Semiconductor Diffusion Coefficient Using Optical Microscopy

Energy carrier transport and recombination in emerging semiconductors can be directly monitored with optical microscopy, leading to the measurement of the diffusion coefficient (D), a critical property for design of efficient optoelectronic devices. D is often determined by fitting a time-resolved expanding carrier profile after optical excitation using a Mean Squared Displacement (MSD) Model. Although this approach has gained widespread adoption, its utilization can significantly overestimate D due to the non-linear recombination processes that artificially broaden the carrier distribution profile. Here, we simulate diffusive processes in both excitonic and free carrier semiconductors and present revised MSD Models that take into account second-order (i.e. bimolecular) and third-order (i.e. Auger) processes to accurately recover D for various types of materials. For perovskite thin films, utilization of these models can reduce fitting error by orders of magnitude, especially for commonly deployed excitation conditions where carrier densities are > 5x10$^1$$^6$ cm$^-$$^3$. In addition, we show that commonly-deployed MSD Models are not well-suited for the study of films with microstructure, especially when boundary behavior is unknown and feature sizes are comparable to the diffusion length. Finally, we find that photon recycling only impacts energy carrier profiles on ultrashort time scales or for materials with fast radiative decay times. We present clear strategies to investigate energy transport in disordered materials for more effective design and optimization of electronic and optoelectronic devices.

physics.app-ph↗

arXiv2019

State-of-the-Art Perovskite Solar Cells Benefit from Photon Recycling at Maximum Power Point

Photon recycling is required for a solar cell to achieve an open-circuit voltage ($V_{OC}$) and power conversion efficiency (PCE) approaching the Shockley-Queisser theoretical limit. In metal halide perovskite solar cells, the achievable performance gains from photon recycling remain uncertain due to high variability in perovskite material quality and the non-radiative recombination rate ($k_{1}$). In this work, we study state-of-the-art $\textrm{Cs}_{0.05}(\textrm{MA}_{0.17}\textrm{FA}_{0.83})_{0.95}\textrm{Pb}(\textrm{I}_{0.83}\textrm{Br}_{0.17})_{3}$ films and analyze the impact of varying non-radiative recombination rates on photon recycling and device performance. Importantly, we predict the impact of photon recycling at the maximum power point (MPP), demonstrating an absolute PCE increase of up to 2.0% in the radiative limit, primarily due to a 77 mV increase in $V_{MPP}$. Even with finite non-radiative recombination, benefits from photon recycling can be achieved when non-radiative lifetimes and external LED electroluminescence efficiencies measured at open-circuit, $Q_{e}^{LED}(\textrm{V}_{OC})$, exceed 2 $μ$s and 10%, respectively. This analysis clarifies the opportunity to fully exploit photon recycling to push the real-world performance of perovskite solar cells toward theoretical limits.

physics.app-ph↗