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Interfacial engineering has fueled recent development of p-i-n perovskite solar cells (PSCs), with self-assembled monolayer-based hole-transport layers (SAM-HTLs) enabling almost lossless contacts for solution-processed PSCs, resulting in the highest achieved power conversion efficiency (PCE) to date. Substrate interfaces are particularly crucial for the growth and quality of co-evaporated PSCs. However, adoption of SAM-HTLs for co-evaporated perovskite absorbers is complicated by the underexplored interaction of such perovskites with phosphonic acid functional groups. In this work, we highlight how exposed phosphonic acid functional groups impact the initial phase and final bulk crystal structures of co-evaporated perovskites and their resultant PCE. The explored surface interaction is mediated by hydrogen bonding with interfacial iodine, leading to increased formamidinium iodide adsorption, persistent changes in perovskite structure, and stabilization of bulk {\alpha}-FAPbI3, hypothesized as being due to kinetic trapping. Our results highlight the potential of exploiting substrates to increase control of co-evaporated perovskite growth.

We present a simple, yet powerful analysis of Suns-photoluminescence quantum yield measurements that can be used to determine the surface saturation current densities of thin film semiconductors. We apply the method to state-of-the-art polycrystalline perovskite thin films of varying absorber thickness. We show that the non-radiative bimolecular recombination in these samples originates from the surfaces. To the best of our knowledge, this is the first study to demonstrate and quantify non-linear (bimolecular) surface recombination in perovskite thin films., Comment: arXiv admin note: text overlap with arXiv:2306.02222

We present a novel analytical model for analysing the spectral photoluminescence quantum yield of non-planar semiconductor thin films. This model considers the escape probability of luminescence and is applied to triple-cation perovskite thin films with a 1-Sun photoluminescence quantum yield approaching 25%. By using our model, we can decouple the internal radiative, external radiative, and non-radiative bi-molecular recombination coefficients. Unlike other techniques that measure these coefficients separately, our proposed method circumvents experimental uncertainties by avoiding the need for multiple photoluminescence measurement techniques. We validate our model by comparing the extracted implied open-circuit voltage, effective luminescence escape probabilities, absorptivity, and absorption coefficient with values obtained using established methods and found that our results are consistent with previous findings. Next, we compare the implied 1-Sun radiative open-circuit voltage and radiative recombination current obtained from our method with literature values. We then convert the implied open-circuit voltage and implied radiative open-circuit voltage to the injection-dependent apparent-effective and apparent-radiative carrier lifetimes, which allow us to decouple the different recombination coefficients. Using this lifetime analysis, we predict the efficiency losses due to each recombination mechanism. Our proposed analytical model provides a reliable method for analysing the spectral photoluminescence quantum yield of semiconductor thin films, which will facilitate further research into the photovoltaic properties of these materials., Comment: Main text: 10 figures, 6 tables

A direct, camera-based implied open-circuit voltage (iVOC) imaging method via the novel use of a single bandpass filter (s-BPF) is developed for large-area photovoltaic solar cells and solar cell precursors. This method images the photoluminescence (PL) emission using a narrow BPF with centre energy in the high-energy tail of the PL emission taking advantage of the close-to-unity absorptivity of typical photovoltaic devices with low variability in this energy range. As a result, the exact value of the sample's absorptivity within the BPF transmission band is not required. The use of a s-BPF enables the adaptation of a fully contactless approach to calibrate the absolute PL photon flux for camera-based spectrally-integrated imaging tools. The method eliminates the need for knowledge of the imaging system spectral response and the use of the emission and excitation spectral shapes. Through an appropriate choice of the BPF centre energy, a range of absorber compositions or a single absorber with different surface morphologies (e.g., planar vs textured) can be imaged, all without the need for additional detection optics. The feasibility of this s-BPF method is first assessed using a high-quality Cs0.05FA0.79MA0.16Pb(I0.83Br0.17)3 perovskite neat film. The error in iVOC is determined to be less than 1.5%. The efficacy of the method is then demonstrated on device stacks with two different perovskite compositions commonly used in single-junction and monolithic tandem solar cells., Comment: 23 pages, 4 figures

We propose a framework for the configuration and operation of expensive-to-evaluate advanced manufacturing methods, based on Bayesian optimization. The framework unifies a tailored acquisition function, a parallel acquisition procedure, and the integration of process information providing context to the optimization procedure. \cmtb{The novel acquisition function is demonstrated, analyzed and compared on state-of-the-art benchmarking problems. We apply the optimization approach to atmospheric plasma spraying and fused deposition modeling.} Our results demonstrate that the proposed framework can efficiently find input parameters that produce the desired outcome and minimize the process cost., Comment: Accepted for IEEE RA-L. 8 pages, 6 figures. arXiv admin note: text overlap with arXiv:2103.13881

Recent work has shown constrained Bayesian optimization to be a powerful technique for the optimization of industrial processes. In complex manufacturing processes, the possibility to run extensive sequences of experiments with the goal of finding good process parameters is severely limited by the time required for quality evaluation of the produced parts. To accelerate the process parameter optimization, we introduce a parallel acquisition procedure tailored on the process characteristics. We further propose an algorithm that adapts to equipment status to improve run-to-run reproducibility. We validate our optimization method numerically and experimentally, and demonstrate that it can efficiently find input parameters that produce the desired outcome and minimize the process cost., Comment: Accepted for IEEE CASE 2021

The internal luminescence quantum efficiency ($Q_\mathrm{i}^\mathrm{lum}$) provides an excellent assessment of the optoelectronic quality of semiconductors. To determine $Q_\mathrm{i}^\mathrm{lum}$ of perovskite films from the experimentally accessible external luminescence quantum efficiency ($Q_\mathrm{e}^\mathrm{lum}$) it is essential to account for photon recycling, and this requires knowledge of the photon escape probability ($p_\mathrm{e}$). Here, we establish an analysis procedure based on a curve fitting model that accurately determines $p_\mathrm{e}$ of perovskite films from photoluminescence (PL) spectra measured with a confocal microscope and an integrating sphere setup. We show that scattering-induced outcoupling of initially-trapped PL explains commonly observed red-shifted and broadened PL spectral shapes and leads to $p_\mathrm{e}$ being more than 10% higher in absolute terms compared to earlier assumptions. Applying our model to CH$_3$NH$_3$PbI$_3$ films with exceptionally high $Q_\mathrm{e}^\mathrm{lum}$ up to 47.4% sets a real benchmark for $Q_\mathrm{i}^\mathrm{lum}$ at $78.0 \pm 0.5\%$, revealing there is beyond a factor of two more scope for reducing non-radiative recombination than previously thought.

The wide band gap methylammonium lead bromide perovskite is promising for applications in tandem solar cells and light-emitting diodes. Despite its utility, there is only a limited understanding of its reproducibility and stability. Herein, the dependence of the properties, performance, and shelf storage of thin films and devices on minute changes to the precursor solution stoichiometry is examined in detail. Although photovoltaic cells based on these solution changes exhibit similar initial performance, the shelf-storage depends strongly on the precursor solution stoichiometry. While all devices exhibit some degree of healing, the bromide-deficient films show a remarkable improvement, more than doubling in their photoconversion efficiency. Photoluminescence spectroscopy experiments performed under different atmospheres suggest that this increase is due in part to a trap healing mechanism that occurs upon exposure to the environment. Our results highlight the importance of understanding and manipulating defects in lead halide perovskites to produce long-lasting, stable devices.

The last five years have witnessed a remarkable progress in the field of lead halide perovskite materials and devices. Examining the existing body of literature reveals staggering inconsistencies in the reported results among different research groups with a particularly wide spread in the photovoltaic performance and stability of devices. In this work we demonstrate that fractional, quite possibly unintentional, deviations in the precursor solution stoichiometry can cause significant changes in the properties of the perovskite layer as well as in the performance and stability of perovskite photovoltaic devices. We show that while the absorbance and morphology of the layers remains largely unaffected, the surface composition and energetics, crystallinity, emission efficiency, energetic disorder and storage stability are all very sensitive to the precise stoichiometry of the precursor solution. Our results elucidate the origin of the irreproducibility and inconsistencies of reported results among different groups as well as the wide spread in device performance even within individual studies. Finally, we propose a simple experimental method to identify the exact stoichiometry of the perovskite layer that researchers can employ to confirm their experiments are performed consistently without unintentional variations in precursor stoichiometry.

Perovskite-based solar cells are promising due to their rapidly improving efficiencies, but suffer from instability issues. Recently it has been claimed that one of the key contributors to the instability of perovskite solar cells is ion migration induced electrode degradation, which can be avoided by incorporating inorganic hole blocking layers (HBL) in the device architecture. In this work, we investigate the operational environmental stability of methylammonium lead iodide (MAPbI3) perovskite solar cells that contain either an inorganic or organic HBL, with only the former effectively blocking ions from migrating to the metal electrode. This is confirmed by X-ray photoemission spectroscopy measured on electrodes of degraded devices, where only electrodes of devices with an organic HBL show a significant iodine signal. Despite this, we show that when these devices are degraded under realistic operational conditions (i.e. constant illumination in a variety of atmospheric conditions), both types of devices exhibit nearly identical degradation behavior. These results demonstrate that contrary to prior suggestions, ion-induced electrode degradation is not the dominant factor in perovskite environmental instability under operational conditions.

The nature of dielectric echoes in amorphous solids at low temperatures is investigated. It is shown that at long delay times the echo amplitude is determined by a small subset of two level systems (TLS) having negligible relaxation and decoherence because of their weak coupling to phonons. The echo decay can then be described approximately by power law time dependencies with different powers at times longer and shorter than the typical TLS relaxation time. The theory is applied to recent measurements of two and three pulse dipolar echo in borosilicate glass BK7 and provides a perfect data fit in the broad time and temperature ranges under the assumption that there exist two TLS relaxation mechanisms due to TLS-phonons and TLS-TLS interaction. This interpretation is consistent with the previous experimental and theoretical investigations. Further experiments verifying the theory predictions are suggested., Comment: 10 pages, 8 figures

A study examined intervention activities for students identified as having high communication anxiety (CA). The study utilized 2 group interventions. Of 61 students in an introductory speech class invited to participate, the 8 who accepted were divided into 2 groups of 4. The groups met for 5 weeks. Group 1, facilitated by a female counseling psychologist, focused on group members' self-esteem issues and their relationship to communication apprehension, with the hypothesis that with a more positive sense of self, there would be less anxiety related to public speaking. Results for this group indicated that subjects had learned to deal with anxiety by thinking differently about themselves. A cognitive restructuring approach was used in group 2, facilitated by a male counselor-in-training, with a therapeutic approach to working with anxiety. The hypothesis was that students who learned to identify and change their self-talk, which was destructive and interfering, would be less anxious in public speaking situations. Findings for this group suggest that subjects became aware of their approaches to situations and had learned to identify and change self-talk messages. (Contains 20 references.) (CR)