arXiv subjects

Paul Meredith

Publications and source records attributed to Paul Meredith.

At least 19 recordsLinked to original sources

arXiv2026

What Photocurrent Versus Effective Voltage Tells Us About Charge Generation in Organic Solar Cells

The photocurrent of an organic solar cell is routinely plotted against an effective voltage and used to extract an exciton dissociation probability, and through it a free-charge generation efficiency. The photocurrent measures neither. Using a drift-diffusion model in which free-charge generation is field independent and losses occur only by bimolecular recombination, we show that the apparent dissociation probability returned by this procedure lies well below unity even for complete dissociation. Across wide variations of carrier mobility and recombination strength it is a single-valued function of the fill factor and coincides with the short-circuit charge collection efficiency, reporting neither the generation yield nor anything about collection beyond what the fill factor already shows. Even for ideal transport the normalised photocurrent saturates below unity at an intensity-independent first-order limit set by recombination of photogenerated carriers with injected equilibrium charge. Applied to four organic solar cells whose generation efficiencies are known independently, the apparent dissociation probabilities track the short-circuit collection efficiency rather than the generation yield. We therefore suggest this construction not be used, particularly in the high-efficiency non-fullerene acceptor systems that are now state of the art.

physics.app-ph↗

arXiv2026

Roadmap on UV-C photodetectors: materials, applications and industry perspectives

UV-C photodetectors are poised to play an increasingly important role in future photonic technologies, driven by the rapid emergence of UV-C light sources and new wide bandgap semiconductors. These advances are enabling new levels of spectral selectivity, radiation hardness, sensitivity, and device integration, while opening opportunities across a broad range of applications. This roadmap provides a comprehensive overview of the current landscape of UV-C photodetection, spanning established and emerging material platforms (Ga2O3, AlGaN, BN, diamond, MgZnO, 2-dimensional materials, metal halide perovskites, micro-electromechanical systems), and their applications in metrology, astronomy, communications, environmental monitoring, fire detection, missile warning, gas sensing, and medical diagnostics. By identifying opportunities, bottlenecks, and future directions, this roadmap aims to support both newcomers and established researchers, with the aim of accelerating the translation of UV-C photodetectors into impactful technologies.

physics.app-ph↗

arXiv2023

Roadmap on Photovoltaic Absorber Materials for Sustainable Energy Conversion

Photovoltaics (PVs) are a critical technology for curbing growing levels of anthropogenic greenhouse gas emissions, and meeting increases in future demand for low-carbon electricity. In order to fulfil ambitions for net-zero carbon dioxide equivalent (CO 2 eq) emissions worldwide, the global cumulative capacity of solar PVs must increase by an order of magnitude from 0.9 TWp in 2021 to 8.5 TWp by 2050 according to the International Renewable Energy Agency, which is considered to be a highly conservative estimate. In 2020, the Henry Royce Institute brought together the UK PV community to discuss the critical technological and infrastructure challenges that need to be overcome to address the vast challenges in accelerating PV deployment. Herein, we examine the key developments in the global community, especially the progress made in the field since this earlier roadmap, bringing together experts primarily from the UK across the breadth of the photovoltaics community. The focus is both on the challenges in improving the efficiency, stability and levelized cost of electricity of current technologies for utility-scale PVs, as well as the fundamental questions in novel technologies that can have a significant impact on emerging markets, such as indoor PVs, space PVs, and agrivoltaics. We discuss challenges in advanced metrology and computational tools, as well as the growing synergies between PVs and solar fuels, and offer a perspective on the environmental sustainability of the PV industry. Through this roadmap, we emphasize promising pathways forward in both the short- and long-term, and for communities working on technologies across a range of maturity levels to learn from each other.

physics.app-ph↗

arXiv2023

The effect of direct electron beam patterning on the water uptake and ionic conductivity of Nafion thin films

We report the effect of electron-beam patterning on the water uptake and ionic conductivity of Nafion films using a combination of x-ray photoelectron spectroscopy, quartz crystal microbalance studies, neutron reflectometry, and AC impedance spectroscopy. The aim was to more fully characterize the nature of the nanoscale patterned Nafion structures recently used as a key element in novel ion-to-electron transducers by Gluschke et al. To enable these studies, we develop the electron beam patterning process for large areas, achieving patterning speeds approaching 1 cm$^{2}$/hr, and patterned areas as large as 7 cm$^{2}$ for the neutron reflectometry studies. We ultimately show that electron-beam patterning affects both the water uptake and the ionic conductivity, depending on film thickness. We see Type-II adsorption isotherm behaviour for all films. For thick films (~230 nm), we see a strong reduction in water uptake with electron-beam patterning. In contrast, for thin films (~30 nm), electron-beam patterning enhances water uptake. Notably, we find that for either thickness the reduction in ionic conductivity arising from electron-beam patterning is kept to less than an order of magnitude. We propose mechanisms for the observed behaviour based on the known complex morphology of Nafion films to motivate future studies of electron-beam processed Nafion.

cond-mat.soft↗

arXiv2023

The Thermodynamic Limit of Indoor Photovoltaics Based on Energetically-Disordered Molecular Semiconductors

Due to their tailorable optical properties, organic semiconductors show considerable promise for use in indoor photovoltaics (IPVs), which present a sustainable route for powering ubiquitous "Internet-of-Things" devices in the coming decades. However, owing to their excitonic and energetically disordered nature, organic semiconductors generally display considerable sub-gap absorption and relatively large nonradiative losses in solar cells. To optimize organic semiconductor-based photovoltaics, it is therefore vital to understand how energetic disorder and non-radiative recombination limit the performance of these devices under indoor light sources. In this work, we explore how energetic disorder, sub-optical gap absorption, and non-radiative open-circuit voltage losses detrimentally affect the upper performance limits of organic semiconductor-based IPVs. Based on these considerations, we provide realistic upper estimates for the power conversion efficiency. The energetic disorder, inherently present in molecular semiconductors, is generally found to shift the optimal optical gap from 1.83 eV to ~1.9 eV for devices operating under LED spectra. Finally, we also describe a methodology (accompanied by a computational tool with a graphical user interface) for predicting IPV performance under arbitrary illumination conditions. Using this methodology, we estimate the indoor PCEs of several photovoltaic materials, including the state-of-the-art systems PM6:Y6 and PM6:BTP-eC9.

physics.app-ph↗

arXiv2022

A quasi steady-state measurement of exciton diffusion lengths in organic semiconductors

Understanding the role that exciton diffusion plays in organic solar cells is a crucial to understanding the recent rise in power conversion effciencies brought about by non-fullerene acceptors (NFA). Established methods for measuring exciton diffusion lengths in organic solar cells require specialized equipment designed for measuring high-resolution time-resolved photoluminescence (TRPL). Here we introduce a technique, coined pulsed-PLQY, to measure the diffusion length of organic solar cells without any temporal measurements. Using a Monte-Carlo model we simulate the dynamics within a thin film semiconductor and analyse the results using both pulsed-PLQY and TRPL methods. We find that pulsed-PLQY has a larger operational region and depends less on the excitation fuence than the TRPL approach. We validate these simulated results by preforming both measurements on organic thin films and reproduce the predicted trends. Pulsed-PLQY is then used to evaluate the diffusion length in a variety of technologically relevant organic semiconductors. It is found that the diffusion lengths in NFA's are much larger than in the benchmark fullerene and that this increase is driven by an increase in diffusivity.

physics.app-ph↗

arXiv2021

Quantifying the Excitonic Static Disorder in Organic Semiconductors

Organic semiconductors are disordered molecular solids and as a result, their internal charge dynamics and ultimately, the performance of the optoelectronic devices they constitute, are governed by energetic disorder. To ascertain how energetic disorder impacts charge generation, exciton transport, charge transport, and the performance of organic semiconductor devices, an accurate approach is first required to measure this critical parameter. In this work, we show that the static disorder has no relation with the so-called Urbach energy in organic semiconductors. Instead, it can be obtained from photovoltaic external quantum efficiency spectra at wavelengths near the absorption onset. We then present a detailed methodology, alongside a computational framework, for quantifying the static energetic disorder associated with singlet excitons. Moreover, the role of optical interference in this analysis is considered to achieve a high-accuracy quantification. Finally, the excitonic static disorder was quantified in several technologically-relevant donor-acceptor blends, including high-efficiency PM6:Y6.

physics.app-ph↗

arXiv2021

A Universal Urbach Rule for Disordered Organic Semiconductors

In crystalline semiconductors, absorption onset sharpness is characterized by temperature dependent Urbach energies. These energies quantify the static, structural disorder causing localized exponential-tail states, and dynamic disorder from electron-phonon scattering. Applicability of this exponential-tail model to disordered solids has been long debated. Nonetheless, exponential fittings are routinely applied to sub-gap absorption analysis of organic semiconductors. Herein, we elucidate the sub-gap spectral line-shapes of organic semiconductors and their blends by temperature-dependent quantum efficiency measurements. We find that sub-gap absorption due to singlet excitons is universally dominated by thermal broadening at low photon energies and the associated Urbach energy equals the thermal energy, regardless of static disorder. This is consistent with absorptions obtained from a convolution of Gaussian density of excitonic states weighted by Boltzmann-like thermally activated optical transitions. A simple model is presented that explains absorption line-shapes of disordered systems, and we also provide a strategy to determine the excitonic disorder energy. Our findings elaborate the meaning of the Urbach energy in molecular solids and relate the photo-physics to static disorder, crucial for optimizing organic solar cells for which we present a new radiative open-circuit voltage limit.

physics.optics↗

arXiv2021

Direct quantification of quasi-Fermi level splitting in organic semiconductor devices

Non-radiative losses to the open-circuit voltage are a primary factor in limiting the power conversion efficiency of organic photovoltaic devices. The dominant non-radiative loss is intrinsic to the active layer and can be determined from the quasi-Fermi level splitting (QFLS) and the radiative thermodynamic limit of the photovoltage. Quantification of the QFLS in thin film devices with low mobility is challenging due to the excitonic nature of photoexcitation and additional sources of nonradiative loss associated with the device structure. This work outlines an experimental approach based on electro-modulated photoluminescence, which can be used to directly measure the intrinsic non-radiative loss to the open-circuit voltage; thereby, quantifying the QFLS. Drift-diffusion simulations are carried out to show that this method accurately predicts the QFLS in the bulk of the device regardless of device-related non-radiative losses. State-of-the-art PM6:Y6-based organic solar cells are used as a model to test the experimental approach, and the QFLS is quantified and shown to be independent of device architecture. This work provides a method to quantify the QFLS of organic solar cells under operational conditions, fully characterizing the different contributions to the non-radiative losses of the open-circuit voltage. The reported method will be useful in not only characterizing and understanding losses in organic solar cells, but also other device platforms such as light-emitting diodes and photodetectors.

physics.app-ph↗

arXiv2019

Determining Ultra-low Absorption Coefficients of Organic Semiconductors from the Sub-bandgap Photovoltaic External Quantum Efficiency

Energy states below the bandgap of a semiconductor, such as trap states or charge transfer states in organic donor acceptor blends, can contribute to light absorption. Due to their low number density or ultrasmall absorption cross-section, the absorption coefficient of these states is challenging to measure using conventional transmission reflection spectrophotometry. As an alternative, the external quantum efficiency (EQE) of photovoltaic devices is often used as a representative of the absorption coefficient, where the spectral line shape of the EQE is considered to follow the absorption coefficient of the active layer material. In this work, it is shown that the subbandgap EQE is subject to thickness dependent low finesse cavity interference effects within the device, making this assumption questionable. A better estimate for the absorption coefficient is obtained when EQE spectra corresponding to different active layer thicknesses are fitted simultaneously for one attenuation coefficient using an iterative transfer matrix method. The principle is demonstrated for two model acceptor-donor systems (PCE12ITIC and PBTTTPC71BM) and accurate subgap absorption coefficients are determined. This approach has particular relevance for both understanding sub-gap states and their utilization in organic optoelectronic devices.

physics.app-ph↗

arXiv2019

A Theoretical Perspective on Transient Photovoltage and Charge Extraction Techniques

Transient photovoltage (TPV) is a technique frequently used to determine charge carrier lifetimes in thin-film solar cells such as organic, dye sensitized and perovskite solar cells. As this lifetime is often incident light intensity dependent, its relevance to understanding the intrinsic properties of a photoactive material system as a material or device figure of merit has been questioned. To extract complete information on recombination dynamics, the TPV measurements are often performed in conjunction with charge extraction (CE) measurements, employed to determine the photo-generated charge carrier density and thereby the recombination rate constant and its order. In this communication, the underlying theory of TPV and CE is reviewed and expanded. Our theoretical findings are further solidified by numerical simulations and experiments on organic solar cells. We identify regimes of the open-circuit voltage within which accurate lifetimes and carrier densities can be determined with TPV and CE experiments. A wide range of steady-state light intensities is required in performing these experiments in order to identify their 'working dynamic range' from which the recombination kinetics in thin-film solar cells can be determined.

physics.app-ph↗

arXiv2014

Molecular weight dependent bimolecular recombination in organic solar cells

Charge carrier recombination is studied in operational organic solar cells made from the polymer:fullerene system PCDTBT:PC71BM (poly[N-9"-heptadecanyl-2,7-carbazole-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)] : [6,6]-phenyl-C$_{70}$-butyric acid methyl ester). A newly developed technique High Intensity Resistance dependent PhotoVoltage (HI-RPV) is presented for reliably quantifying the bimolecular recombination coefficient independently of variations in experimental conditions, thereby resolving key limitations of previous experimental approaches. Experiments are performed on solar cells of varying thicknesses and varying polymeric molecular weights. It is shown that solar cells made from low molecular weight PCDTBT exhibit Langevin recombination, whereas suppressed (non-Langevin) recombination is found in solar cells made with high molecular weight PCDTBT.

cond-mat.mtrl-sci↗

arXiv2014

The impact of hot charge carrier mobility on photocurrent losses in polymer-based solar cells

A typical signature of charge extraction in disordered organic systems is dispersive transport, which implies a distribution of charge carrier mobilities that negatively impact on device performance. Dispersive transport has been commonly understood to originate from a time-dependent mobility of hot charge carriers that reduces as excess energy is lost during relaxation in the density of states. In contrast, we show via photon energy, electric field and film thickness independence of carrier mobilities that the dispersive photocurrent in organic solar cells originates not from the loss of excess energy during hot carrier thermalization, but rather from the loss of carrier density to trap states during transport. Our results emphasize that further efforts should be directed to minimizing the density of trap states, rather than controlling energetic relaxation of hot carriers within the density of states.

cond-mat.mtrl-sci↗

arXiv2010

Competition between Superconductivity and Weak Localization in Metal-Mixed Ion-Implanted Polymers

We study the effects of varying the pre-implant film thickness and implant temperature on the electrical and superconducting properties of metal-mixed ion-implanted polymers. We show that it is possible to drive a superconductor-insulator transition in these materials via control of the fabrication parameters. We observe peaks in the magnetoresistance and demonstrate that these are caused by the interplay between superconductivity and weak localization in these films, which occurs due to their granular structure. We compare these magnetoresistance peaks with those seen in unimplanted films and other organic superconductors, and show that they are distinctly different.

cond-mat.supr-con↗

arXiv2009

Preparation of Metal Mixed Plastic Superconductors: Electrical Properties of Tin-Antimony Thin Films on Plastic Substrates

Metal mixed polymers are a cheap and effective way to produce flexible metals and superconductors. As part of an on-going effort to learn how to tune the properties of these systems with ion implantation, we present a study of the electrical properties of these systems prior to metal-mixing. We show that the electrical properties of tin-antimony thin films are remarkably robust to variations in the substrate morphology. We demonstrate that the optical absorbance of the films at a fixed wavelength provides a reliable and reproducible characterization of the relative film thickness. We find that as the film thickness is reduced, the superconducting transition in the unimplanted thin films is broadened, but the onset of the transition remains at ~3.7 K, the transition temperature of bulk Sn. This is in marked contrast to the behavior of metal mixed films, which suggests that the metal mixing process has a significant effect of the physics of the superconducting state beyond that achieved by reducing the film thickness alone.

cond-mat.mtrl-sci↗

arXiv2005

Quantitative scattering of melanin solutions

The optical scattering coefficient of a dilute, well solubilised eumelanin solution has been accurately measured as a function of incident wavelength, and found to contribute less than 6% of the total optical attenuation between 210 and 325nm. At longer wavelengths (325nm to 800nm) the scattering was less than the minimum sensitivity of our instrument. This indicates that UV and visible optical density spectra can be interpreted as true absorption with a high degree of confidence. The scattering coefficient vs wavelength was found to be consistent with Rayleigh Theory for a particle radius of 38+-1nm.

physics.bio-ph↗

arXiv2005

Chemical and Structural Disorder in Eumelanins - A Possible Explanation for Broad Band Absorbance

We report the results of an experimental and theoretical study of the electronic and structural properties of a key eumelanin precursor - 5,6,-dihydroxyindole-2-carboxylic acid (DHICA) and its dimeric forms. We have used optical spectroscopy to follow the oxidative polymerization of DHICA to eumelanin, and observe red shifting and broadening of the absorption spectrum as the reaction proceeds. First principles density functional theory calculations indicate that DHICA oligomers (possible reaction products of oxidative polymerization) have red shifted HOMO-LUMO gaps with respect to the monomer. Furthermore, different bonding configurations (leading to oligomers with different structures) produce a range of gaps. These experimental and theoretical results lend support to the chemical disorder model where the broad band monotonic absorption characteristic of all melanins is a consequence of the superposition of a large number of inhomogeneously broadened Gaussian transitions associated with each of the components of a melanin ensemble. These results suggest that the traditional model of eumelanin as an amorphous organic semiconductor is not required to explain its optical properties, and should be thoroughly re-examined. These results have significant implications for our understanding of the physics, chemistry and biological function of these important biological macromolecules. Indeed, one may speculate that the robust functionality of melanins in vitro is a direct consequence of its heterogeneity, i.e. chemical disorder is a "low cost" natural resource in these systems.

q-bio.BM↗

arXiv2005

Towards Structure-Property-Function Relationships for Eumelanin

We discuss recent progress towards the establishment of important structure-property-function relationships in eumelanins - key functional bio-macromolecular systems responsible for photo-protection and immune response in humans, and implicated in the development of melanoma skin cancer. We focus on the link between eumelanin's secondary structure and optical properties such as broad band UV-visible absorption and strong non-radiative relaxation; both key features of the photo-protective function. We emphasise the insights gained through a holistic approach combining optical spectroscopy with first principles quantum chemical calculations, and advance the hypothesis that the robust functionality characteristic of eumelanin is related to extreme chemical and structural disorder at the secondary level. This inherent disorder is a low cost natural resource, and it is interesting to speculate as to whether it may play a role in other functional bio-macromolecular systems.

q-bio.BM↗