Harnessing Viscoelasticity to Suppress Irreversibility Buildup in a Colloidal Stirling Engine.

Typically, the rate at which a heat engine can produce useful work is constrained by the buildup of irreversibility with increasing operating speed. Here, using a recently developed reservoir engineering technique, we designed and quantified the performance of a colloidal Stirling engine operating in a viscoelastic bath. While the bath acts like a viscous fluid in the quasistatic limit, and the engine's performance agrees with equilibrium predictions, on reducing the cycle time to the bath's structural relaxation time, the increasingly elastic response of the bath aids suppress the buildup of irreversibility. We show that the elastic energy stored during the isothermal compression step of the Stirling cycle facilitates quick equilibration in the isothermal expansion step. This results in equilibriumlike efficiencies even for cycle times shorter than the equilibration time of the colloidal particle.

Overcoming power-efficiency tradeoff in a micro heat engine by engineered system-bath interactions.

All real heat engines, be it conventional macro engines or colloidal and atomic micro engines, inevitably tradeoff efficiency in their pursuit to maximize power. This basic postulate of finite-time thermodynamics has been the bane of all engine design for over two centuries and all optimal protocols implemented hitherto could at best minimize only the loss in the efficiency. The absence of a protocol that allows engines to overcome this limitation has prompted theoretical studies to suggest universality of the postulate in both passive and active engines. Here, we experimentally overcome the power-efficiency tradeoff in a colloidal Stirling engine by selectively reducing relaxation times over only the isochoric processes using system bath interactions generated by electrophoretic noise. Our approach opens a window of cycle times where the tradeoff is reversed and enables the engine to surpass even their quasistatic efficiency. Our strategies finally cut loose engine design from fundamental restrictions and pave way for the development of more efficient and powerful engines and devices.

Ultrafast time-resolved carrier dynamics in tellurium nanowires using optical pump terahertz probe spectroscopy.

We report carrier relaxation dynamics in semiconducting tellurium nanowires (average diameter ∼ 10 nm) using ultrafast time-resolved terahertz spectroscopy. After photoexcitation using an 800 nm pump pulse, we observed an initial increase in the THz conductivity due to the absorption of THz radiation by photoexcited carriers. The time evolution of the differential conductivity (Δσ(τpp) = σpump on(τpp) - σpump off) shows a bi-exponential relaxation with the initial fast decay time scale of τ1 ∼ 25 ps followed by a longer relaxation time constant of τ2 ∼ 100 ps. Interestingly, the two time scales depend on the amount of the capping agent present on the surface of TeNWs, showing a faster relaxation of the photoexcited carriers as the percentage of capping decreases. This is physically interpreted as the surface state mediated relaxation mechanism of the photo-pumped carriers depending on the density of available surface states. A quantitative understanding is obtained using a coupled rate equation model taking into account the decay mechanisms determined from the surface mediated relaxation rate (DS) and direct recombination rate (DR) of the electron-hole pairs. Furthermore, the measured lattice temperature (TL) dependent dynamics, showing a faster relaxation at lower temperature, is understood using the same rate equation model, giving a power law dependence of the electron-hole recombination rate (DR) on TL as DR ∝ TL-1/2. This is explained by estimating DR using the van Roosbroeck-Shockley theory taking into account the density of states () of one-dimensional nanowires. Furthermore, to understand the measured frequency-dependent THz photoconductivity, we model Δσ(ω) using the Boltzmann transport equation taking into account the energy-dependent scattering rates showing the dominant role of short range (Γsr) and Coulomb scattering (ΓC) rates in the relaxation process, which further provides a measure of the charged and neutral impurity concentrations.

Intermediate-range order governs dynamics in dense colloidal liquids.

The conventional wisdom is that liquids are completely disordered and lack nontrivial structure beyond nearest-neighbor distances. Recent observations have upended this view and demonstrated that the microstructure in liquids is surprisingly rich and plays a critical role in numerous physical, biological, and industrial processes. However, approaches to uncover this structure are either system-specific or yield results that are not physically intuitive. Here, through single-particle resolved three-dimensional confocal microscope imaging and the use of a recently introduced four-point correlation function, we show that bidisperse colloidal liquids have a highly nontrivial structure comprising alternating layers with icosahedral and dodecahedral order, which extends well beyond nearest-neighbor distances and grows with supercooling. By quantifying the dynamics of the system on the particle level, we establish that it is this intermediate-range order, and not the short-range order, which has a one-to-one correlation with dynamical heterogeneities, a property directly related to the relaxation dynamics of glassy liquids. Our experimental findings provide a direct and much sought-after link between the structure and dynamics of liquids and pave the way for probing the consequences of this intermediate-range order in other liquid state processes.

Shear jamming and fragility in fractal suspensions under confinement.

Under applied stress, the viscosity of many dense particulate suspensions increases drastically, a response known as discontinuous shear-thickening (DST). In some cases, the applied stress can even transform the suspension into a solid-like shear jammed state. Although shear jamming (SJ) has been probed for dense suspensions with particles having well-defined shapes, such a phenomenon for fractal objects has not been explored. Here, using rheology and in situ optical imaging, we study the flow behaviour of ultra-dilute fractal suspensions of multi-walled carbon nanotubes (MWCNT) under confinement. We show a direct transition from flowing to SJ state without a precursory DST in fractal suspensions at an onset volume fraction, ϕ ∼ 0.5%, significantly lower than that of conventional dense suspensions (ϕ ∼ 55%). The ultra-low concentration enables us to demonstrate the fragility and associated contact dynamics of the SJ state, which remain experimentally unexplored in suspensions. Furthermore, using a generalized Wyart-Cates model, we propose a generic phase diagram for fractal suspensions that captures the possibility of SJ without prior DST over a wide range of shear stress and volume fractions.

Synergistic action in colloidal heat engines coupled by non-conservative flows.

Colloidal heat engines are model systems to analyze mechanisms of transduction of heat to work at the mesoscale. While engines developed hitherto were realized using conservative potentials and operated in isolation, biological micromotors - their real counterparts - seldom perform under such simplifications. Here, we examine thermodynamics beyond such idealizations by constructing a pair of engines from two colloidal microspheres in optical traps at close separation. We demonstrate that at such proximity, non-conservative scattering forces that were hitherto neglected affect the particle motion. Hydrodynamics generated while dissipating these are hindered by the microsphere in the adjacent trap and energy that was otherwise rejected into the medium gets reused. Thus, despite being in contact with the same reservoir, the particles are driven out of equilibrium and can exchange energy, allowing cooperative behavior. Leveraging this in a manner analogous to microswimmers and active Brownian particles that utilize such flows to enhance propulsion, we construct two colloidal engines in close proximity. To estimate thermodynamic quantities, we develop a minimal model that is appropriate in the asymptotic limit and is similar to active Brownian particles. While complete theoretical frameworks to understand such scenarios remain to be developed, results based on our model demonstrate the intuitive idea that a pair of Stirling engines at close proximity outperform those that are well separated. Although these results explore the simplest case of two Stirling engines, the concepts unraveled could aid in designing larger collections akin to biological systems.

Observation of two-step melting on a sphere.

Melting in two-dimensional flat space is typically two-step and via the hexatic phase. How melting proceeds on a curved surface, however, is not known. Topology mandates that crystalline particle assemblies on these surfaces harbor a finite density of defects, which itself can be ordered, like the icosahedral ordering of 5-coordinated disclination defects on a sphere. Thus, melting even on a sphere, the simplest closed surface, involves the loss of both crystalline and defect order. Probing the interplay of these two forms of order, however, requires a system in which melting can be performed in situ, and this has not been achieved hitherto. Here, by tuning interparticle interactions in situ, we report an observation of an intermediate hexatic phase during the melting of colloidal crystals on a sphere. Remarkably, we observed a precipitous drop in icosahedral defect order in the hexatic phase where the shear modulus is expected to vanish. Furthermore, unlike in flat space, where disorder can fundamentally alter the nature of the melting process, on the sphere, we observed the signature characteristics of ideal melting. Our findings have profound implications for understanding, for instance, the self-assembly and maturation dynamics of viral capsids and also phase transitions on curved surfaces.

Active nonreciprocal attraction between motile particles in an elastic medium.

We show from experiments and simulations on vibration-activated granular matter that self-propelled polar rods in an elastic medium on a substrate turn and move towards each other. We account for this effective attraction through a coarse-grained theory of a motile particle as a moving point-force density that creates elastic strains in the medium that reorient other particles. Our measurements confirm qualitatively the predicted features of the distortions created by the rods, including the |x|^{-1/2} tail of the trailing displacement field and nonreciprocal sensing and pursuit. A discrepancy between the magnitudes of displacements along and transverse to the direction of motion remains. Our theory should be of relevance to the interaction of motile cells in the extracellular matrix or in a supported layer of gel or tissue.

Structural origin of excitations in a colloidal glass-former.

Despite decades of intense research, whether the transformation of supercooled liquids into glass is a kinetic phenomenon or a thermodynamic phase transition remains unknown. Here, we analyzed optical microscopy experiments on 2D binary colloidal glass-forming liquids and investigated the structural links of a prominent kinetic theory of glass transition. We examined a possible structural origin for localized excitations, which are building blocks of the dynamical facilitation theory-a purely kinetic approach for the glass transition. To accomplish this, we utilize machine learning methods to identify a structural order parameter termed "softness" that has been found to be correlated with reorganization events in supercooled liquids. Both excitations and softness qualitatively capture the dynamical slowdown on approaching the glass transition and motivated us to explore spatial and temporal correlations between them. Our results show that excitations predominantly occur in regions with high softness and the appearance of these high softness regions precedes excitations, thus suggesting a causal connection between them. Thus, unifying dynamical and thermodynamical theories into a single structure-based framework may provide a route to understand the glass transition.

Motile Topological Defects Hinder Dynamical Arrest in Dense Liquids of Active Ellipsoids.

Recent numerical studies have identified the persistence time of active motion as a critical parameter governing glassy dynamics in dense active matter. Here we studied dynamics in liquids of granular active ellipsoids with tunable persistence and velocity. We show that increasing the persistence time at moderate supercooling is equivalent to increasing the strength of attraction in equilibrium liquids and results in reentrant dynamics not just in the translational degrees of freedom, as anticipated, but also in the orientational ones. However, at high densities, motile topological defects, unique to active liquids of elongated particles, hindered dynamical arrest. Most remarkably, for the highest activity, we observed intermittent dynamics due to the jamming-unjamming of these defects for the first time.

Tuning the performance of a micrometer-sized Stirling engine through reservoir engineering.

Colloidal heat engines are paradigmatic models to understand the conversion of heat into work in a noisy environment - a domain where biological and synthetic nano/micro machines function. While the operation of these engines across thermal baths is well-understood, how they function across baths with noise statistics that is non-Gaussian and also lacks memory, the simplest departure from the thermal case, remains unclear. Here we quantified the performance of a colloidal Stirling engine operating between an engineered memoryless non-Gaussian bath and a Gaussian one. In the quasistatic limit, the non-Gaussian engine functioned like a thermal one as predicted by theory. On increasing the operating speed, due to the nature of noise statistics, the onset of irreversibility for the non-Gaussian engine preceded its thermal counterpart and thus shifted the operating speed at which power is maximum. The performance of nano/micro machines can be tuned by altering only the nature of reservoir noise statistics.

Imaging the coherent propagation of collective modes in the excitonic insulator Ta2NiSe5 at room temperature.

Excitonic insulators host a condensate of electron-hole pairs at equilibrium, giving rise to collective many-body effects. Although several materials have emerged as excitonic insulator candidates, evidence of long-range coherence is lacking and the origin of the ordered phase in these systems remains controversial. Here, using ultrafast pump-probe microscopy, we investigate the possible excitonic insulator Ta2NiSe5 Below 328 K, we observe the anomalous micrometer-scale propagation of coherent modes at velocities of ~105 m/s, which we attribute to the hybridization between phonon modes and the phase mode of the condensate. We develop a theoretical framework to support this explanation and propose that electronic interactions provide a substantial contribution to the ordered phase in Ta2NiSe5 These results allow us to understand how the condensate's collective modes transport energy and interact with other degrees of freedom. Our study provides a unique paradigm for the investigation and manipulation of these properties in strongly correlated materials.

Shear-Induced Ordering of Nanopores and Instabilities in Concentrated Surfactant Mesh Phases.

Mixed surfactant systems with strongly bound counterions show many interesting phases such as the random mesh phase consisting of a disordered array of defects (water-filled nanopores in the bilayers). The present study addresses the non-equilibrium phase transition of the random mesh phase under shear to an ordered mesh phase with a high degree of coherence between nanopores in three dimensions. In situ small-angle synchrotron X-ray study under different shear stress conditions shows sharp Bragg peaks in the X-ray diffraction, successfully indexed to the rhombohedral lattice with R3̅m space group symmetry. The ordered mesh phase shows isomorphic twinning and buckling at higher shear stress. Our experimental studies bring out rich non-equilibrium phase transitions in concentrated cationic surfactant systems with strongly bound counterions hitherto not well explored and provide motivation for a quantitative understanding.

Anomalous thermopower oscillations in graphene-nanowire vertical heterostructures.

Thermoelectric measurements have the potential to uncover the density of states (DOSs) of low-dimensional materials. Here, we present the anomalous thermoelectric behavior of monolayer graphene-nanowire (NW) heterostructures, showing large oscillations as a function of the doping concentration. Our devices consist of InAs NW and graphene vertical heterostructures, which are electrically isolated by thin (∼10 nm) hexagonal boron nitride (hBN) layers. In contrast to conventional thermoelectric measurements, where a heater is placed on one side of a sample, we use the InAs NW (diameter ∼50 nm) as a local heater placed in the middle of the graphene channel. We measure the thermoelectric voltage induced in graphene due to Joule heating in the NW as a function of temperature (1.5-50 K) and carrier concentration. The thermoelectric voltage in bilayer graphene (BLG)-NW heterostructures shows sign change around the Dirac point, as predicted by Mott's formula. In contrast, the thermoelectric voltage measured across monolayer graphene (MLG)-NW heterostructures shows anomalous large-amplitude oscillations around the Dirac point, not seen in the Mott response derived from the electrical conductivity measured on the same device. The anomalous oscillations are a signature of the modified DOSs in MLG by the electrostatic potential of the NW, which is much weaker in the NW-BLG devices. Thermal calculations of the heterostructure stack show that the temperature gradient is dominant in the graphene region underneath the NW, and thus sensitive to the modified DOSs resulting in anomalous oscillations in the thermoelectric voltage. Furthermore, with the application of a magnetic field, we detect modifications in the DOSs due to the formation of Landau levels in both MLG and BLG.

Dirac surface plasmons in photoexcited bismuth telluride nanowires: optical pump-terahertz probe spectroscopy.

Collective excitation of Dirac plasmons in graphene and topological insulators has opened new possibilities of tunable plasmonic materials ranging from THz to mid-infrared regions. Using time resolved Optical Pump-Terahertz Probe (OPTP) spectroscopy, we demonstrate the presence of plasmonic oscillations in bismuth telluride nanowires (Bi2Te3 NWs) after photoexcitation using an 800 nm pump pulse. In the frequency domain, the differential conductivity (Δσ = σpump on-σpump off) spectrum shows a Lorentzian response where the resonance frequency (ωp), attributed to surface plasmon oscillations, shifts with photogenerated carrier density (n) as . This dependence establishes the absorption of THz radiation by the Dirac surface plasmon oscillations of the charge carriers in the Topological Surface States (TSS) of Bi2Te3 NWs. Moreover, we obtain a modulation depth, tunable by pump fluence, of ∼40% over the spectral range of 0.5 to 2.5 THz. In addition, the time evolution of Δσ(t) represents a long relaxation channel lasting for more than 50 ps. We model the decay dynamics of Δσ(t) using coupled second order rate equations, highlighting the contributions from surface recombination as well as from trap mediated relaxation channels of the photoinjected carriers.

Ultrafast melting and recovery of collective order in the excitonic insulator Ta2NiSe5.

The layered chalcogenide Ta2NiSe5 has been proposed to host an excitonic condensate in its ground state, a phase that could offer a unique platform to study and manipulate many-body states at room temperature. However, identifying the dominant microscopic contribution to the observed spontaneous symmetry breaking remains challenging, perpetuating the debate over the ground state properties. Here, using broadband ultrafast spectroscopy we investigate the out-of-equilibrium dynamics of Ta2NiSe5 and demonstrate that the transient reflectivity in the near-infrared range is connected to the system's low-energy physics. We track the status of the ordered phase using this optical signature, establishing that high-fluence photoexcitations can suppress this order. From the sub-50 fs quenching timescale and the behaviour of the photoinduced coherent phonon modes, we conclude that electronic correlations provide a decisive contribution to the excitonic order formation. Our results pave the way towards the ultrafast control of an exciton condensate at room temperature.

Emergent stereoselective interactions and self-recognition in polar chiral active ellipsoids.

In many active matter systems, particle trajectories have a well-defined handedness or chirality. Whether such chiral activity can introduce stereoselective interactions between particles is not known. Here, we developed a strategy to tune the nature of chiral activity of three-dimensionally printed granular ellipsoids without altering their shape or size. In vertically agitated monolayers of these particles, we observed two types of dimers form depending on the chirality of the pairing monomers. Heterochiral dimers moved collectively as a single achiral active unit, while homochiral ones formed a translationally immobile spinner. In active racemic mixtures, the former was more abundant than the latter, indicating that interactions were stereoselective. Through dimer lifetime measurements, we further provide evidence for chiral self-recognition in mixtures of particles with different chiral activities. We lastly show that, at fixed particle number density, changing the net chirality of a dense active liquid fundamentally alters the nature of collective relaxation.

Doping controlled Fano resonance in bilayer 1T'-ReS2: Raman experiments and first-principles theoretical analysis.

In the bilayer ReS2 channel of a field-effect transistor (FET), we demonstrate using Raman spectroscopy that electron doping (n) results in softening of frequency and broadening of linewidth for the in-plane vibrational modes, leaving the out-of-plane vibrational modes unaffected. The largest change is observed for the in-plane Raman mode at ∼151 cm-1, which also shows doping induced Fano resonance with the Fano parameter 1/q = -0.17 at a doping concentration of ∼3.7 × 1013 cm-2. A quantitative understanding of our results is provided by first-principles density functional theory (DFT), showing that the electron-phonon coupling (EPC) of in-plane modes is stronger than that of out-of-plane modes, and its variation with doping is independent of the layer stacking. The origin of large EPC is traced to 1T to 1T' structural phase transition of ReS2 involving in-plane displacement of atoms whose instability is driven by the nested Fermi surface of the 1T structure. Results are compared with those of the isostructural trilayer ReSe2.

Symmetry induced phonon renormalization in few layers of 2H-MoTe2 transistors: Raman and first-principles studies.

Understanding of electron-phonon coupling (EPC) in two-dimensional (2D) materials manifesting as phonon renormalization is essential to their possible applications in nanoelectronics. Here we report in situ Raman measurements of electrochemically top-gated 2, 3 and 7 layered 2H-MoTe2 channel based field-effect transistors. While the [Formula: see text] and B2g phonon modes exhibit frequency softening and linewidth broadening with hole doping concentration (p) up to ∼2.3 × 1013/cm2, A1g shows relatively small frequency hardening and linewidth sharpening. The dependence of frequency renormalization of the [Formula: see text] mode on the number of layers in these 2D crystals confirms that hole doping occurs primarily in the top two layers, in agreement with recent predictions. We present first-principles density functional theory analysis of bilayer MoTe2 that qualitatively captures our observations, and explain that a relatively stronger coupling of holes with [Formula: see text] or B2g modes as compared with the A1g mode originates from the in-plane orbital character and symmetry of the states at valence band maximum. The contrast between the manifestation of EPC in monolayer MoS2 and those observed here in a few-layered MoTe2 demonstrates the role of the symmetry of phonons and electronic states in determining the EPC in these isostructural systems.