arXiv subjects

Paul Mulvaney

Publications and source records attributed to Paul Mulvaney.

16 recordsLinked to original sources

arXiv2024

A quasi-ohmic back contact achieved by inserting single-crystal graphene in flexible Kesterite solar cells

Flexible photovoltaics with a lightweight and adaptable nature that allows for deployment on curved surfaces and in building facades have always been a goal vigorously pursued by researchers in thin-film solar cell technology. The recent strides made in improving the sunlight-to-electricity conversion efficiency of kesterite Cu$_{2}$ZnSn(S, Se)$_{4}$ (CZTSSe) suggest it to be a perfect candidate. However, making use of rare Mo foil in CZTSSe solar cells causes severe problems in thermal expansion matching, uneven grain growth, and severe problems at the back contact of the devices. Herein, a strategy utilizing single-crystal graphene to modify the back interface of flexible CZTSSe solar cells is proposed. It will be shown that the insertion of graphene at the Mo foil/CZTSSe interface provides strong physical support for the subsequent deposition of the CZTSSe absorber layer, improving the adhesion between the absorber layer and the Mo foil substrate. Additionally, the graphene passivates the rough sites on the surface of the Mo foil, enhancing the chemical homogeneity of the substrate, and resulting in a more crystalline and homogeneous CZTSSe absorber layer on the Mo foil substrate. The detrimental reaction between Mo and CZTSSe has also been eliminated. Through an analysis of the electrical properties, it is found that the introduction of graphene at the back interface promotes the formation of a quasi-ohmic contact at the back contact, decreasing the back contact barrier of the solar cell, and leading to efficient collection of charges at the back interface. This investigation demonstrates that solution-based CZTSSe photovoltaic devices could form the basis of cheap and flexible solar cells.

cond-mat.mtrl-sci↗

arXiv2024

A "Redox-free" Synthesis of CZTS Nano Ink

A large open-circuit (V$_{oc}$) deficit restricts current kesterite device performance. The primary challenge is to achieve control over the phase composition and purity of the kesterite absorber. This is hampered by the fact that the metals copper and tin have multiple valence states and this leads inevitably to the formation of multiple phases. Specifically for solution-based fabrication procedures for kesterite, the pursuit of phase purity extends to the synthesis of CZTS precursor solution or nanoparticle dispersed inks (nano inks). In this work, a "redox-free" synthesis of CZTS nano ink is developed by mixing metal precursors with careful valence state control in non-toxic solvents. The issue of secondary phase formation during the synthesis process of kesterite is effectively resolved. Additionally, molecular solutions and nanoparticle inks with identical compositions exhibit significantly different abilities in phase control. Nanoparticles pre-synthesized in the solution state exhibit superior phase control by following a more ideal phase formation path. This provides a new pathway for the synthesis of kesterite with unprecedented control of the phase composition and purity.

cond-mat.mtrl-sci↗

arXiv2024

Understanding building blocks of photonic logic gates: Reversible, read-write-erase cycling using photoswitchable beads in micropatterned arrays

Using surface-templated electrophoretic deposition, we have created arrays of polymer beads (photonic units) incorporating photo-switchable DAE molecules, which can be reversibly and individually switched between high and low emission states by direct photo-excitation, without any energy or electron transfer processes within the molecular system. The micropatterned array of these photonic units is spectroscopically characterized in detail and optimized with respect to both signal contrast and cross-talk. The optimum optical parameters including laser intensity, wavelength and duration of irradiation are elucidated and ideal conditions for creating reversible on/off cycles in a micropatterned array are determined. 500 such cycles are demonstrated with no obvious on/off contrast attenuation. The ability to process binary information is demonstrated by selectively writing information to the given photonic unit, reading the resultant emissive signal pattern and finally erasing the information again, which in turn demonstrates the possibility of continuous recording. This basic study paves the way for building complex circuits using spatially well-arranged photonic units.

physics.optics↗

arXiv2023

When Like Destabilizes Like: Inverted Solvent Effects in Apolar Nanoparticle Dispersions

We report on the colloidal stability of nanoparticles with alkanethiol shells in apolar solvents. Small angle X-ray scattering and molecular dynamics simulations were used to characterize the interaction between nanoparticles in linear alkane solvents ranging from hexane to hexadecane, including \SI{4}{\nano\meter} gold cores with hexadecanethiol shells and \SI{6}{\nano\meter} cadmium selenide cores with octadecanethiol shells. We find that the agglomeration is enthalpically driven and that, contrary to what one would expect from classical colloid theory, the temperature at which the particles agglomerate increases with increasing solvent chain length. We demonstrate that the inverted trend correlates with the temperatures at which the ligands order in the different solvents, and show that the inversion is due to a combination of enthalpic and entropic effects that enhance the stability of the ordered ligand state as the solvent length increases. We also explain why cyclohexane is a better solvent than hexane, despite having very similar solvation parameters to hexadecane.

cond-mat.soft↗

arXiv2023

Predicting Contact Angle Hysteresis on Surfaces with Randomly and Periodically Distributed Cylindrical Pillars via Energy Dissipation

Hypothesis: Understanding contact angle hysteresis on rough surfaces is important as most industrially relevant and naturally occurring surfaces possess some form of random or structured roughness. We hypothesise that hysteresis originates from the energy dissipation during the $\textit{stick-slip}$ motion of the contact line and that this energy dissipation is key to developing a predictive equation for hysteresis. Experiments: We measured hysteresis on surfaces with randomly distributed and periodically arranged microscopic cylindrical pillars for a variety of different liquids in air. The inherent (flat surface) contact angles tested range from lyophilic ($θ_{\rm{e}}=33.8^{\circ}$) to lyophobic ($θ_{\rm{e}} = 112.0^{\circ}$). Findings: A new methodology for calculating the average advancing and receding contact angles on random surfaces is presented. Also, the correlations for roughness-induced energy dissipation were derived, and a predictive equation for the advancing and receding contact angles during homogeneous (Wenzel) wetting on random surfaces is presented. Significantly, equations that predict the onset of the alternate wetting conditions of hemiwicking, split-advancing, split-receding and heterogeneous (Cassie) wetting are also derived, thus defining the range of validity for the derived homogeneous wetting equation. A novel feature 'cluster' concept is introduced which explains the measurably higher hysteresis exhibited by structured surfaces compared to random surfaces observed experimentally.

physics.flu-dyn↗

arXiv2021

Memory in quantum dot blinking

The photoluminescence intermittency (blinking) of quantum dots is interesting because it is an easily-measured quantum process whose transition statistics cannot be explained by Fermi's Golden Rule. Commonly, the transition statistics are power-law distributed, implying that quantum dots possess at least trivial memories. By investigating the temporal correlations in the blinking data, we demonstrate with high statistical confidence that quantum dot blinking data has non-trivial memory, which we define to be statistical complexity greater than one. We show that this memory cannot be discovered using the transition distribution. We show by simulation that this memory does not arise from standard data manipulations. Finally, we conclude that at least three physical mechanisms can explain the measured non-trivial memory: 1) Storage of state information in the chemical structure of a quantum dot; 2) The existence of more than two intensity levels in a quantum dot; and 3) The overlap in the intensity distributions of the quantum dot states, which arises from fundamental photon statistics.

cond-mat.mes-hall↗

arXiv2021

Quantum-Probe Field Microscopy of Ultrafast Terahertz Excitations

Rapid evolutions of microscopic fields govern the majority of elementary excitations in condensed matter and drive microelectronic currents at increasing frequencies. Beyond nominal "radio frequencies", however, access to local electric waveforms remains a challenge. Several imaging schemes resolve sub-wavelength fields up to multi-Terahertz (THz) frequencies - including scanning-probe techniques, electro-optic sampling or recent ultrafast electron microscopy. Yet, various constraints on sample geometries, acquisition speed and maximum fields limit applications. Here, we introduce ubiquitous far-field microscopy of ultrafast local electric fields based on drop-cast quantum-dot probes. Our approach, termed Quantum-probe Field Microscopy (QFIM), combines fluorescence imaging of visible photons with phase-resolved sampling of electric fields deeply in the sub-wavelength regime. We capture stroboscopic movies of localized and propagating ultrafast Terahertz excitations with sub-picosecond temporal resolution. The scheme employs field-driven modulations of optical absorption in colloidal quantum-dots via the quantum-confined Stark-effect, accessible via far-field luminescence. The QFIM approach is compatible with strong-field sample excitation and sub-micrometer resolution - introducing a route towards ultrafast field imaging in active nanostructures during operation.

physics.optics↗

arXiv2019

On the colloidal stability of apolar nanoparticles: The role of ligand length

Inorganic nanoparticle cores are often coated with organic ligands to render them dispersible in apolar solvents. However, the effect of the ligand shell on the colloidal stability of the overall hybrid particle is not fully understood. In particular, it is not known how the length of an apolar alkyl ligand chain affects the stability of a nanoparticle dispersion against agglomeration. Here, Small-Angle X-ray Scattering and molecular dynamics simulations have been used to study the interactions between gold nanoparticles and between cadmium selenide nanoparticles passivated by alkanethiol ligands with 12 to 18 carbons in the solvent decane. We find that increasing the ligand length increases colloidal stability in the core-dominated regime but decreases it in the ligand-dominated regime. This unexpected inversion is connected to the transition from ligand- to core-dominated agglomeration when the core diameter increases at constant ligand length. Our results provide a microscopic picture of the forces that determine the colloidal stability of apolar nanoparticles and explain why classical colloid theory fails.

cond-mat.soft↗

arXiv2018

On the colloidal stability of apolar nanoparticles: The role of particle size and ligand shell structure

Being able to predict and tune the colloidal stability of nanoparticles is essential for a wide range of applications, yet our ability to do so is currently poor due to a lack of understanding of how they interact with one another. Here, we show that the agglomeration of apolar particles is dominated by either the core or the ligand shell, depending on the particle size and materials. We do this by using Small-Angle X-ray Scattering and molecular dynamics simulations to characterize the interaction between hexadecanethiol passivated gold nanoparticles in decane solvent. For smaller particles, the agglomeration temperature and interparticle spacing are determined by ordering of the ligand shell into bundles of aligned ligands that attract one another and interlock. In contrast, the agglomeration of larger particles is driven by van der Waals attraction between the gold cores, which eventually becomes strong enough to compress the ligand shell. Our results provide a microscopic description of the forces that determine the colloidal stability of apolar nanoparticles and explain why classical colloid theory fails.

cond-mat.soft↗

arXiv2017

Quantum magnetic resonance microscopy

Magnetic resonance spectroscopy is universally regarded as one of the most important tools in chemical and bio-medical research. However, sensitivity limitations typically restrict imaging resolution to length scales greater than 10 μm. Here we bring quantum control to the detection of chemical systems to demonstrate high resolution electron spin imaging using the quantum properties of an array of nitrogen-vacancy (NV) centres in diamond. Our quantum magnetic resonance microscope selectively images electronic spin species by precisely tuning a magnetic field to bring the quantum probes into resonance with the external target spins. This provides diffraction limited spatial resolution of the target spin species over a field of view of ~50x50 μm^2. We demonstrate imaging and spectroscopy on aqueous Cu2+ ions over microscopic volumes (0.025 μm^3), with detection sensitivity at resonance of 104 spins/voxel, ~100 zeptomol (10^-19 mol). The ability to image, perform spectroscopy and dynamically monitor spin-dependent redox reactions and transition metal biochemistry at these scales opens up a new realm of nanoscopic electron spin resonance and zepto-chemistry in the physical and life sciences.

physics.bio-ph↗

arXiv2016

A virtual instrument to standardise the calibration of atomic force microscope cantilevers

Atomic force microscope (AFM) users often calibrate the spring constants of cantilevers using functionality built into individual instruments. This is performed without reference to a global standard, which hinders robust comparison of force measurements reported by different laboratories. In this article, we describe a virtual instrument (an internet-based initiative) whereby users from all laboratories can instantly and quantitatively compare their calibration measurements to those of others - standardising AFM force measurements - and simultaneously enabling non-invasive calibration of AFM cantilevers of any geometry. This global calibration initiative requires no additional instrumentation or data processing on the part of the user. It utilises a single website where users upload currently available data. A proof-of-principle demonstration of this initiative is presented using measured data from five independent laboratories across three countries, which also allows for an assessment of current calibration.

physics.ins-det↗

arXiv2016

In-situ 3D Imaging of Catalysis Induced Strain in Gold Nanoparticles

Multi-electron transfer processes, such as hydrogen and oxygen evolution reactions, are crucially important in energy and biological science but require favorable catalysts to achieve fast kinetics. Nanostructuring catalysts can dramatically improve their properties, which can be difficult to understand due to strain and size dependent thermodynamics, the influence of defects, and substrate dependent activities. Here, we report 3D imaging of single gold nanoparticles during catalysis of ascorbic acid decomposition using Bragg coherent diffractive imaging (BCDI) as a route to eliminate ensemble effects while elucidating the strain-activity connection. Local strains were measured in single nanoparticles and modeled using reactive molecular dynamics (RMD) simulations and finite element analysis (FEA) simulations. RMD reveals a new chemical pathway for local strain generation in the gold lattice: chemisorption of hydroxyl ions. FEA reveals that the RMD results are transferable to the larger nanocrystal sizes studied in the experiment. Our study reveals the strain-activity connection and opens a powerful new avenue for joint theoretical and experimental studies of multi-electron transfer processes catalyzed by nanocrystals.

cond-mat.mtrl-sci↗

arXiv2016

Hot Carrier extraction with plasmonic broadband absorbers

Hot charge carrier extraction from metallic nanostructures is a very promising approach for applications in photo-catalysis, photovoltaics and photodetection. One limitation is that many metallic nanostructures support a single plasmon resonance thus restricting the light-to-charge-carrier activity to a spectral band. Here we demonstrate that a monolayer of plasmonic nanoparticles can be assembled on a multi-stack layered configuration to achieve broad-band, near-unit light absorption, which is spatially localised on the nanoparticle layer. We show that this enhanced light absorbance leads to $\sim$ 40-fold increases in the photon-to-electron conversion efficiency by the plasmonic nanostructures. We developed a model that successfully captures the essential physics of the plasmonic hot-electron charge generation and separation in these structures. This model also allowed us to establish that efficient hot carrier extraction is limited to spectral regions where the photons possessing energies higher than the Schottky junctions and the localised light absorption of the metal nanoparticles overlap.

physics.chem-ph↗

arXiv2015

Scanning nano-spin ensemble microscope for nanoscale magnetic and thermal imaging

Quantum sensors based on solid-state spins provide tremendous opportunities in a wide range of fields from basic physics and chemistry to biomedical imaging. However, integrating them into a scanning probe microscope to enable practical, nanoscale quantum imaging is a highly challenging task. Recently, the use of single spins in diamond in conjunction with atomic force microscopy techniques has allowed significant progress towards this goal, but generalisation of this approach has so far been impeded by long acquisition times or by the absence of simultaneous topographic information. Here we report on a scanning quantum probe microscope which solves both issues, by employing a nano-spin ensemble hosted in a nanodiamond. This approach provides up to an order of magnitude gain in acquisition time, whilst preserving sub-100 nm spatial resolution both for the quantum sensor and topographic images. We demonstrate two applications of this microscope. We first image nanoscale clusters of maghemite particles through both spin resonance spectroscopy and spin relaxometry, under ambient conditions. Our images reveal fast magnetic field fluctuations in addition to a static component, indicating the presence of both superparamagnetic and ferromagnetic particles. We next demonstrate a new imaging modality where the nano-spin ensemble is used as a thermometer. We use this technique to map the photo-induced heating generated by laser irradiation of a single gold nanoparticle in a fluid environment. This work paves the way towards new applications of quantum probe microscopy such as thermal/magnetic imaging of operating microelectronic devices and magnetic detection of ion channels in cell membranes.

cond-mat.mes-hall↗

arXiv2013

Detection of atomic spin labels in a lipid bi-layer using a single-spin nanodiamond probe

Magnetic field fluctuations arising from fundamental spins are ubiquitous in nanoscale biology, and are a rich source of information about the processes that generate them. However, the ability to detect the few spins involved without averaging over large ensembles has remained elusive. Here we demonstrate the detection of gadolinium spin labels in an artificial cell membrane under ambient conditions using a single-spin nanodiamond sensor. Changes in the spin relaxation time of the sensor located in the lipid bilayer were optically detected and found to be sensitive to near-individual proximal gadolinium atomic labels. The detection of such small numbers of spins in a model biological setting, with projected detection times of one second, opens a new pathway for in-situ nanoscale detection of dynamical processes in biology.

physics.bio-ph↗

arXiv2006

Spectral diffusion of single semiconductor nanocrystals: the influence of the dielectric environment

We have explored the influence of different matrices on the emission line shape of individual homogeneously coated CdSe/CdS/ZnS nanocrystals. The results obtained corroborate previous observations of a correlation between blinking events and spectral diffusion but in addition we have found that the extent of spectral diffusion is almost independent of the dielectric environment of the NC. Additionally, we report the observation of a correlation between the line width and emission energy which is not expected to occur in the spherical - symmetric NCs employed in this work. The implications of these results are discussed.

cond-mat.mtrl-sci↗