arXiv subjects

Bruno Ehrler

Publications and source records attributed to Bruno Ehrler.

At least 19 recordsLinked to original sources

arXiv2026

Near-field effects on cathodoluminescence outcoupling in perovskite thin films

Halide perovskite semiconductors are a promising material for high-efficiency solar cells. Their optical properties can vary within and between crystallographic grains. We present spatially-resolved cathodoluminescence (CL) spectroscopy at 2 keV and 5 keV on polycrystalline CsPbBr3 perovskite films to study these variations at the nanoscale. The CL maps show a strongly reduced intensity near the polycrystalline grain boundaries. We perform numerical simulations of the far-field emission of the electron beam-generated optical near fields using the surface profiles from AFM as input. We find that near grain boundaries the light outcoupling is strongly reduced due to enhanced internal reflection and light trapping at the curved surfaces. Lateral variations in CL intensity inside grains are due to Fabry-Perot-like resonances in the film, with the substrate acting as a back reflector. Our results show that near-field coupling and interference effects can dominate nanoscale luminescence maps of halide perovskite films. The results are broadly relevant for the analysis of cathodoluminescence and photoluminescence of corrugated thin films.

cond-mat.mtrl-sci↗

arXiv2025

Photoluminescence Mapping of Mobile and Fixed Defects in Halide Perovskite Films

Metal halide perovskites exhibit coupled electronic and ionic properties that determine their photovoltaic performance and operational stability. Understanding and quantifying ionic transport are therefore essential for advancing perovskite optoelectronics. Conventional electrical methods such as impedance spectroscopy require fully integrated devices, and their interpretation is often complicated by interfacial and contact effects, limiting the ability to isolate intrinsic ionic behavior. Here, a localized adaptation of intensity-modulated photoluminescence spectroscopy (IMPLS) is utilized to optically probe lateral ionic transport in perovskite films. The frequency-dependent photoluminescence response is measured under controlled carrier injection levels and correlated with the photoluminescence quantum yield (PLQY). The proposed diffusion model indicates that mobile ionic defects laterally migrate from high light intensity regions, giving rise to characteristic photoluminescence modulations. Ionic diffusion coefficients extracted from IMPLS agree well with literature values obtained from electrical measurements. Importantly, IMPLS mapping separates mobile and immobile defect contributions through a defect contrast coefficient (DCC), which quantifies the normalized difference between the area-averaged photoluminescence intensity and phase data. This work ultimately demonstrates that localized IMPLS provides a contact-free means to extract lateral ion diffusion coefficients while spatially distinguishing defect types across the sample.

cond-mat.mtrl-sci↗

arXiv2025

Facile Synthesis and On-Chip Color Tuning of CsPbBr$_{3}$@CsPbBr$_{3-x}$TFA$_{x}$ Nanoplatelets via Ion Engineering

Metal halide perovskites (MHPs) have emerged as attractive optoelectronic materials because of high fluorescence quantum yield, broad color tunability, and excellent color purity. However, the ionic nature of MHPs makes them susceptible to polar solvents, leading to defect-induced nonradiative recombination and photoluminescence (PL) quenching. Here, we present a combined in-synthesis ($\textit{in situ}$) and post-synthesis ion engineering to suppress nonradiative recombination and integrate multicolor MHP arrays on-chip through a perovskite-compatible photolithography process and $\textit{in situ}$ vapor-phase anion exchange. CsPbBr$_{3}$@CsPbBr$_{3-x}$TFA$_{x}$ nanoplatelets were grown on-chip via a single-step solution process incorporating trifluoroacetate (TFA$^{-}$) pseudohalides. X-ray photoelectron spectroscopy revealed that TFA$^{-}$ passivate uncoordinated Pb$^{2+}$ ions on nanoplatelet surface and suppresses the formation of metallic lead (Pb$^{0}$). This decreases the non-radiative recombination centers and yields a PL peak at 520 nm with a linewidth of 14.56$\% \pm$ 0.5 nm. The nanoplatelets were patterned via a top-down photolithography process and selectively masked with a PMMA/Al$_{2}$O$_{3}$ stack to enable vapor-phase anion exchange. The PL peak shifted in the unmasked regions from 520 nm to 413 nm, resulting in distinct green and blue emission arrays. Our method enables the scalable fabrication of highly luminescent, two-color MHP arrays with tailored optical properties, advancing their integration into next-generation optoelectronic devices.

cond-mat.mtrl-sci↗

arXiv2025

Microscale optoelectronic reservoir networks of halide perovskite for in-sensor computing

Physical reservoir computing is a promising framework for efficient neuromorphic in and near-sensor computing applications. Here, we demonstrate a multimodal optoelectronic reservoir network based on halide perovskite semiconductor devices, capable of processing both voltage and light inputs. The devices consist of micrometer-sized, asymmetric crossbars covered with a MAPbI3 perovskite film. In a network, we simulate the performance by transforming MNIST images and videos based on the NMNIST dataset using 4-bit inputs and training linear readout layers for classification. We demonstrate multimodal networks capable of processing both voltage and light inputs, reaching mean accuracies up to 95.3 p/m 0.1% and 87.8 p/m 0.1% for image and video classification, respectively. We observed only minor deterioration due to measurement noise. The networks significantly outperformed linear classifier references, by 3.1% for images and 14.6% for video. We show that longer retention times benefit classification accuracy for single-mode networks, and give guidelines for choosing optimal experimental parameters. Moreover, the microscale device architecture lends itself well to further downscaling in high-density sensor arrays, making the devices ideal for efficient in-sensor computing.

cond-mat.mtrl-sci↗

arXiv2025

Microscale optoelectronic synapses with switchable photocurrent from halide perovskite

Efficient visual data processing by neuromorphic networks requires volatile artificial synapses that detect and process light inputs, ideally in the same device. Here, we demonstrate microscale back-contacted optoelectronic halide perovskite artificial synapses that leverage ion migration induced by a bias voltage to modulate their photocurrent. The photocurrent changes are due to the accumulation of mobile ions, which induces a transient electric field in the perovskite. The photocurrent changes are volatile, decaying on the order of seconds. The photocurrent changes can be controlled by both the applied voltage and illumination. The symmetric device supports changing of the photocurrent polarity, switching between inhibitory and exhibitory functioning. The photocurrent can be updated by spike-timing-dependent plasticity (STDP)-learning rules inspired by biology. We show with simulations how this could be exploited as an attention mechanism in a neuromorphic detector. Our fabrication procedure is compatible with high-density integration with CMOS and memristive neuromorphic networks for energy-efficient visual data processing inspired by the brain.

cond-mat.mtrl-sci↗

arXiv2025

Quantification of mobile ions in perovskite solar cells with thermally activated ion current measurements

Mobile ions play a key role in the degradation of perovskite solar cells, making their quantification essential for enhancing device stability. Various electrical measurements have been applied to characterize mobile ions. However, discerning between different ionic migration processes can be difficult. Furthermore, multiple measurements at different temperatures are usually required to probe different ions and their activation energies. Here, we demonstrate a new characterization technique based on measuring the thermally activated ion current (TAIC) of perovskite solar cells. The method reveals density, diffusion coefficient, and activation energy of mobile ions within a single temperature sweep and offers an intuitive way to distinguish mobile ion species. We apply the TAIC technique to quantify mobile ions of MAPbI3 and triple-cation perovskite solar cells. We find a higher activation energy and a lower diffusion coefficient in the triple-cation devices. TAIC measurements are a simple yet powerful tool to better understand ion migration in perovskite solar cells.

cond-mat.mtrl-sci↗

arXiv2024

Integrated Artificial Neurons from Metal Halide Perovskites

Hardware neural networks could perform certain computational tasks orders of magnitude more energy-efficiently than conventional computers. Artificial neurons are a key component of these networks and are currently implemented with electronic circuits based on capacitors and transistors. However, artificial neurons based on memristive devices are a promising alternative, owing to their potentially smaller size and inherent stochasticity. But despite their promise, demonstrations of memristive artificial neurons have so far been limited. Here we demonstrate a fully on-chip artificial neuron based on microscale electrodes and halide perovskite semiconductors as the active layer. By connecting a halide perovskite memristive device in series with a capacitor, the device demonstrates stochastic leaky integrate-and-fire behavior, with an energy consumption of 20 to 60 pJ per spike, lower than that of a biological neuron. We simulate populations of our neuron and show that the stochastic firing allows the detection of sub-threshold inputs. The neuron can easily be integrated with previously-demonstrated halide perovskite artificial synapses in energy-efficient neural networks.

cond-mat.mtrl-sci↗

arXiv2024

Circularly polarised electroluminescence from chiral excitons in vacuum-sublimed supramolecular semiconductor thin films

Materials with chiral electronic structures are of great interest. We report a triazatruxene, TAT, molecular semiconductor with chiral alkyl side chains that crystallises from solution to form chirally-stacked columns with a helical pitch of 6 TATs (2.3 nm). These crystals show strong circularly polarised, CP, green photoluminescence, with dissymmetry of 24%. Electronic structure calculations using the full crystal structure, show that this chiral stacking associates angular momentum to the valence and conduction states and thus gives rise to the observed CP luminescence. Free-standing crystals are not useful for active semiconductor devices, but we have discovered that co-sublimation of TAT as the guest in a structurally mismatched host enables the fabrication of thin films where the chiral crystallization is achieved in-situ by thermally-triggered nano-phase segregation of dopant and host whilst preserving the integrity of the film. This enables fabrication of bright (green) organic light-emitting diodes with unexpectedly high external quantum efficiencies of up to 16% and electroluminescence dissymmetries above 10%. These materials and this process method offer significant application potential in spintronics, optical displays and multidimensional optoelectronics.

cond-mat.mtrl-sci↗

arXiv2021

Pathways towards 30% efficient single-junction perovskite solar cells and the role of mobile ions

Perovskite semiconductors have demonstrated outstanding external luminescence quantum yields, enabling high power conversion efficiencies (PCE). However, the precise conditions to advance to an efficiency regime above monocrystalline silicon cells are not well understood. Here, we establish a simulation model that well describes efficient p-i-n type perovskite solar cells and a range of different experiments. We then study important device and material parameters and we find that an efficiency regime of 30% can be unlocked by optimizing the built-in potential across the perovskite layer by using either highly doped (10^19 cm-3), thick transport layers (TLs) or ultrathin undoped TLs, e.g. self-assembled monolayers. Importantly, we only consider parameters that have been already demonstrated in recent literature, that is a bulk lifetime of 10 us, interfacial recombination velocities of 10 cm/s, a perovskite bandgap of 1.5 eV and an EQE of 95%. A maximum efficiency of 31% is predicted for a bandgap of 1.4 eV. Finally, we demonstrate that the relatively high mobile ion density does not represent a significant barrier to reach this efficiency regime. Thus, the results of this paper promise continuous PCE improvements until perovskites may become the most efficient single-junction solar cell technology in the near future.

cond-mat.mtrl-sci↗

arXiv2021

Accelerated hot-carrier cooling in MAPbI3 perovskite by pressure-induced lattice compression

Hot-carrier cooling (HCC) in metal halide perovskites in the high-density regime is significantly slower compared to conventional semiconductors. This effect is commonly attributed to a hot-phonon bottleneck but the influence of the lattice properties on the HCC behaviour is poorly understood. Using pressure-dependent transient absorption spectroscopy (fs-TAS) we find that at an excitation density below Mott transition, pressure does not affect the HCC. On the contrary, above Mott transition, HCC in methylammonium lead iodide (MAPbI3) is around two times as fast at 0.3 GPa compared to ambient pressure. Our electron-phonon coupling calculations reveal about two times stronger electron-phonon coupling for the inorganic cage mode at 0.3 GPa. However, our experiments reveal that pressure promotes faster HCC only above Mott transition. Altogether, these findings suggest a change in the nature of excited carriers in the high-density regime, providing insights on the electronic behavior of devices operating at such high charge-carrier density.

cond-mat.mtrl-sci↗

arXiv2020

Metal halide perovskite toxicity effects on plants are caused by iodide ions

Highly-efficient solar cells containing lead halide perovskites are expected to revolutionize sustainable energy production in the coming years. Combining these next-generation solar panels with agriculture, can optimize land-use, but brings new risks in case of leakage into the soil. Perovskites are generally assumed to be toxic because of the lead (Pb), but experimental evidence to support this prediction is scarce. We used Arabidopsis thaliana to test the toxicity of the lead-based perovskite MAPbI3 (MA = CH3NH3) and several of its precursors in plants. Our results show that MAPbI3 severely hampers plant growth at concentrations above 5 microM. Surprisingly, we find that the precursors MAI is equally toxic, while lead-based precursors without iodide are only toxic above 500 microM. These observations reveal that perovskite toxicity at low concentrations is caused by iodide ions specifically, and contrast the widespread idea that lead is the most harmful component. We calculate that iodide toxicity thresholds are likely to reach in the soil upon perovskite leakage, but much less so for lead toxicity thresholds. Hence, this work stresses the importance to further understand and predict harmful effects of iodide-containing perovskites in the environment.

cond-mat.mtrl-sci↗

arXiv2020

Sequentially Deposited versus Conventional Nonfullerene Organic Solar Cells: Interfacial Trap States, Vertical Stratification, and Exciton Dissociation

Bulk-heterojunction (BHJ) non-fullerene organic solar cells prepared from sequentially deposited donor and acceptor layers (sq-BHJ) have recently been promising to be highly efficient, environmentally friendly, and compatible with large area and roll-to-toll fabrication. However, the related photophysics at donor-acceptor interface and the vertical heterogeneity of donor-acceptor distribution, critical for exciton dissociation and device performance, are largely unexplored. Herein, steady-state and time-resolved optical and electrical techniques are employed to characterize the interfacial trap states. Correlation with the luminescent efficiency of interfacial states and its non-radiative recombination, interfacial trap states are characterized to be about 50% more populated in the sq-BHJ than as-cast BHJ (c-BHJ), which probably limits the device voltage output. Cross-sectional energy-dispersive X-ray spectroscopy and ultraviolet photoemission spectroscopy depth profiling directly vizualize the donor-acceptor vertical stratification with a precision of 1-2 nm. From the proposed "needle" model, the high exciton dissociation efficiency is rationalized. Our study highlights the promise of sequential deposition to fabricate efficient solar cells, and points towards improving the voltage output and overall device performance via eliminating interfacial trap states.

physics.app-ph↗

arXiv2020

Change in Tetracene Polymorphism Facilitates Triplet Transfer in Singlet Fission-Sensitized Silicon Solar Cells

Singlet fission in tetracene generates two triplet excitons per absorbed photon. If these triplet excitons can be effectively transferred into silicon (Si) then additional photocurrent can be generated from photons above the bandgap of Si. This could alleviate the thermalization loss and increase the efficiency of conventional Si solar cells. Here we show that a change in the polymorphism of tetracene deposited on Si due to air exposure, facilitates triplet transfer from tetracene into Si. Magnetic field-dependent photocurrent measurements confirm that triplet excitons contribute to the photocurrent. The decay of tetracene delayed photoluminescence was used to determine a triplet transfer time of 215 ns and a maximum yield of triplet transfer into Si of ~50 %. Our study suggests that control over the morphology of tetracene during deposition will be of great importance to boost the triplet transfer yield further.

physics.app-ph↗

arXiv2020

Lattice compression increases the activation barrier for phase segregation in mixed-halide perovskites

The bandgap tunability of mixed-halide perovskites makes them promising candidates for light emitting diodes and tandem solar cells. However, illuminating mixed-halide perovskites results in the formation of segregated phases enriched in a single-halide. This segregation occurs through ion migration, which is also observed in single-halide compositions, and whose control is thus essential to enhance the lifetime and stability. Using pressure-dependent transient absorption spectroscopy, we find that the formation rates of both iodide- and bromide-rich phases in MAPb(BrxI1-x)3 reduce by two orders of magnitude on increasing the pressure to 0.3 GPa. We explain this reduction from a compression-induced increase of the activation energy for halide migration, which is supported by first-principle calculations. A similar mechanism occurs when the unit cell volume is reduced by incorporating a smaller cation. These findings reveal that stability with respect to halide segregation can be achieved either physically through compressive stress or chemically through compositional engineering.

physics.app-ph↗

arXiv2020

Thermodynamic stabilization of mixed-halide perovskites against phase segregation

Mixing iodide and bromide in halide perovskite semiconductors is an effective strategy to tune their bandgap, therefore mixed-halide perovskites hold great promise for color-tunable LEDs and tandem solar cells. However, the bandgap of mixed-halide perovskites is unstable under (sun-)light, since the halides segregate into domains of different bandgaps. Using pressure-dependent ultrafast transient absorption spectroscopy, we show that high external pressure increases the range of thermodynamically stable halide mixing ratios. Chemical pressure, by inserting a smaller cation, has the same effect, which means that any iodide-to-bromide ratio can be thermodynamically stabilized by tuning the crystal volume and compressibility. We interpret this stabilization by an alteration of the Helmholtz free energy via the largely overlooked PdeltaV term.

physics.chem-ph↗

arXiv2020

The impact of exciton delocalization on exciton-vibration interactions in organic semiconductors

Organic semiconductors exhibit properties of individual molecules and extended crystals simultaneously. The strongly bound excitons they host are typically described in the molecular limit, but excitons can delocalize over many molecules, raising the question of how important the extended crystalline nature is. Using accurate Green's function based methods for the electronic structure and non-perturbative finite difference methods for exciton-vibration coupling, we describe exciton interactions with molecular and crystal degrees of freedom concurrently. We find that the degree of exciton delocalization controls these interactions, with thermally activated crystal phonons predominantly coupling to delocalized states, and molecular quantum fluctuations predominantly coupling to localized states. Based on this picture, we quantitatively predict and interpret the temperature and pressure dependence of excitonic peaks in the acene series of organic semiconductors, which we confirm experimentally, and we develop a simple experimental protocol for probing exciton delocalization. Overall, we provide a unified picture of exciton delocalization and vibrational effects in organic semiconductors, reconciling the complementary views of finite molecular clusters and periodic molecular solids.

cond-mat.mtrl-sci↗

arXiv2019

Pitfalls and prospects of optical spectroscopy to characterize perovskite-transport layer interfaces

Perovskite photovoltaics has witnessed an unprecedented increase in power conversion efficiency over the last decade. The choice of transport layers, through which photo-generated electrons and holes are transported to the electrodes, is a crucial factor for further improving both the device performance and stability. In this perspective, we critically examine the application of optical spectroscopy to characterize the quality of the transport layer-perovskite interface. We highlight the power of complementary studies that use both continuous wave (cw) and time-resolved photoluminescence (PL) to understand non-radiative losses, and additional transient spectroscopies for characterizing the potential for loss-less carrier extraction at the solar cell interfaces. Based on this discussion, we make recommendations on how to extrapolate results from optical measurements to assess the quality of a transport layer, and its impact on solar cell efficiency.

physics.app-ph↗

arXiv2019

Quantifying mobile ions in perovskite-based devices with temperature-dependent capacitance measurements: frequency versus time domain

Perovskites have proven to be a promising candidate for highly-efficient solar cells, light-emitting diodes, and X-ray detectors, overcoming limitations of inorganic semiconductors. However, they are notoriously unstable. The main reason for this instability is the migration of mobile ions through the device during operation, as they are mixed ionic-electronic conductors. Here we show how measuring the capacitance in both the frequency and the time domain can be used to study ionic dynamics within perovskite-based devices, quantifying activation energy, diffusion coefficient, sign of charge, concentration, and the length of the ionic double layer in the vicinity of the interfaces. Measuring the transient of the capacitance furthermore allows for distinguishing between ionic and electronic effects.

physics.app-ph↗