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Matthew O. Blunt

Publications and source records attributed to Matthew O. Blunt.

6 recordsLinked to original sources

From London to Morse via Binnig, Quate, and Gerber

In their landmark paper introducing the atomic force microscope [Phys. Rev. Lett. \textbf{56}, 930 (1986)], Binnig, Quate, and Gerber presciently anticipated that the technique would ultimately be capable of probing interactions running the gamut from weak van der Waals interactions to strong covalent bonding. They also highlighted that the tip-sample forces central to AFM are present, and often highly influential, in scanning tunnelling microscopy; indeed, this realisation directly inspired the invention of the force microscope. In this perspective for the \textit{Forty Years of AFM} special issue, we review selected aspects of two decades of work from our group at the University of Nottingham that span the force range highlighted by BQG and are united by a common, central theme: the probe as active participant rather than passive observer. Our selection of results also covers length- and correlation-scales from the microscopic right down to the single chemical bond limit, tracking a spectrum of interactions from van der Waals/Hamaker forces, through hydrogen bonding, to covalent bonds and, finally, atom-by-atom assembly of metal clusters via vertical tip-sample transfer. Echoing BQG's own observations on the prevalence of probe-sample forces in STM, we also discuss recent evidence that tip-induced heterogeneity underpins first-passage dynamics in molecular diffusion and highlight the challenges in acquiring non-invasive measurements of diffusion barriers for adsorbed molecules that are readily perturbed by the probe. We close with a perspective on machine learning's growing role in automating tip-driven atomic and molecular manipulation.

cond-mat.mes-hall

Organic Semiconductor Alignment via Confinement in Vapor-Guided Droplets

Organic semiconductors are lightweight, solution-processable materials with strong potential for printed and flexible electronics, from deformable displays to wearable sensors. Despite significant advances in materials synthesis and manufacturing, controlling molecular and mesoscale alignment during deposition remains a central challenge, as film morphology critically governs charge transport and device performance. Here, we demonstrate that flows developing within the intrinsically confined volume of microliter vapor-guided droplets can be harnessed to produce highly aligned organic semiconductor films. As droplets move in response to an external vapor source, internal flows align organic semiconducting nanowires within the droplet prior to deposition, yielding films with pronounced directional order. Organic field-effect transistors fabricated with this approach exhibit approximately 40% enhancement in saturation current relative to spin-coated controls. Beyond improved device performance, the contactless and compact nature of our method enables the deposition and alignment of organic semiconductors on curved and flexible surfaces. More broadly, vapor-guided droplets offer a scalable framework for the confinement-induced alignment of functional soft materials, with potential for integration into existing additive manufacturing platforms for flexible electronics and beyond.

cond-mat.soft

Capillary-Assisted Printing of Droplets at a Solid-Like Liquid-Liquid Interface

Capillary forces guide the motion of biomolecular condensates, water-borne insects, and breakfast cereal. These surface-mediated interactions can be harnessed to build units into materials with exotic properties deriving from mesoscale structure. Droplets are promising building blocks for these materials, finding applications in tissue engineering, adaptive optics, and structural colour. However, the instability of water droplets at many liquid-liquid interfaces hampers the use of capillarity for the assembly of droplet-based materials. Here, we use nanoparticle surfactants to form solid-like oil-water interfaces at which aqueous droplets sit for extended periods. We find that microlitre-sized droplets at these interfaces attract each other over millimetric scales. We rationalize this interaction with a modified theory of capillarity. Applying printing methods allows us to finely control initial droplet positions, from which they self-assemble into cellular materials. Finally, by functionalising the interface with gold nanoparticles, we use plasmon-assisted optofluidics to manipulate these droplet-based materials with temperature gradients.

cond-mat.soft

Broken symmetry and the variation of critical properties in the phase behaviour of supramolecular rhombus tilings

The degree of randomness, or partial order, present in two-dimensional supramolecular arrays of isophthalate tetracarboxylic acids is shown to vary due to subtle chemical changes such as the choice of solvent or small differences in molecular dimensions. This variation may be quantified using an order parameter and reveals a novel phase behaviour including random tiling with varying critical properties as well as ordered phases dominated by either parallel or non-parallel alignment of neighbouring molecules, consistent with long-standing theoretical studies. The balance between order and randomness is driven by small differences in the intermolecular interaction energies, which we show, using numerical simulations, can be related to the measured order parameter. Significant variations occur even when the energy difference is much less than the thermal energy highlighting the delicate balance between entropic and energetic effects in complex self-assembly processes.

cond-mat.stat-mech

Entropically-stabilised growth of a two-dimensional random tiling

The assembly of molecular networks into structures such as random tilings and glasses has recently been demonstrated for a number of two-dimensional systems. These structures are dynamically-arrested on experimental timescales so the critical regime in their formation is that of initial growth. Here we identify a transition from energetic to entropic stabilisation in the nucleation and growth of a molecular rhombus tiling. Calculations based on a lattice gas model show that clustering of topological defects and the formation of faceted boundaries followed by a slow relaxation to equilibrium occurs under conditions of energetic stabilisation. We also identify an entropically-stabilised regime in which the system grows directly into an equilibrium configuration without the need for further relaxation. Our results provide a methodology for identifying equilibrium and non-equilibrium randomness in the growth of molecular tilings, and we demonstrate that equilibrium spatial statistics are compatible with exponentially slow dynamical behaviour.

cond-mat.stat-mech

Molecular random tilings as glasses

We have recently shown [Blunt et al., Science 322, 1077 (2008)] that p-terphenyl-3,5,3',5'-tetracarboxylic acid adsorbed on graphite self-assembles into a two-dimensional rhombus random tiling. This tiling is close to ideal, displaying long range correlations punctuated by sparse localised tiling defects. In this paper we explore the analogy between dynamic arrest in this type of random tilings and that of structural glasses. We show that the structural relaxation of these systems is via the propagation--reaction of tiling defects, giving rise to dynamic heterogeneity. We study the scaling properties of the dynamics, and discuss connections with kinetically constrained models of glasses.

cond-mat.stat-mech