Nature regulates complex structures in space and time via feedback loops, kinetically controlled transformations, and under energy dissipation to allow non-equilibrium processes. Although man-made static self-assemblies realize excellent control over hierarchical structures via molecular programming, managing their temporal destiny by self-regulation is a largely unsolved challenge. Herein, we introduce a generic concept to control the time domain by programming the lifetimes of switchable self-assemblies in closed systems. We conceive dormant deactivators that, in combination with fast promoters, enable a unique kinetic balance to establish an autonomously self-regulating, transient pH-state, whose duration can be programmed over orders of magnitude—from minutes to days. Coupling this non-equilibrium state to pH-switchable self-assemblies allows predicting their assembly/disassembly fate in time, similar to a precise self-destruction mechanism. We demonstrate a platform approach by programming self-assembly lifetimes of block copolymers, nanoparticles, and peptides, enabling dynamic materials with a self-regulation functionality.

Focal adhesions (FAs) are micron-sized protein assemblies that coordinate cell adhesion, migration, and mechanotransduction. How the many proteins within FAs are organized into force sensing and transmitting structures is poorly understood. We combined fluorescent molecular tension sensors with super-resolution light microscopy to visualize traction forces within FAs with <100 nm spatial resolution. We find that α_vβ₃ integrin selectively localizes to high force regions. Paxillin, which is not generally considered to play a direct role in force transmission, shows a higher degree of spatial correlation with force than vinculin, talin, or α-actinin, proteins with hypothesized roles as force transducers. These observations suggest that α_vβ₃ integrin and paxillin may play important roles in mechanotransduction.

We report a voltage controlled reversible creation and annihilation of a-axis oriented ∼10 nm wide ferroelastic nanodomains without a concurrent ferroelectric 180° switching of the surrounding c-domain matrix in archetypal ferroelectric Pb(Zr_0.2Ti_0.8)O₃ thin films by using the piezo-response force microscopy technique. In previous studies, the coupled nature of ferroelectric switching and ferroelastic rotation has made it difficult to differentiate the underlying physics of ferroelastic domain wall movement. Our observation of distinct thresholds for ferroelectric and ferroelastic switching allows us investigate the ferroelastic switching cleanly and demonstrate a new degree of nanoscale control over the ferroelastic domains.

The rise of bacterial antibiotic resistance has created a demand for alternatives to traditional antibiotics. Attractive possibilities include pro- and anti-quorum sensing therapies that function by modulating bacterial chemical communication circuits. We report the use of Flash NanoPrecipitation to deliver the Vibrio cholerae quorum-sensing signal CAI-1 ((S)-3-hydroxytridecan-4-one) in a water dispersible form as nanoparticles. The particles activate V. cholerae quorum-sensing responses 5 orders of magnitude higher than does the identically administered free CAI-1 and are diffusive across in vivo delivery barriers such as intestinal mucus. This work highlights the promise of combining quorum-sensing strategies with drug delivery approaches for the development of next-generation medicines.

Intramolecular current-induced vibronic excitations are reported in highly ordered monolayers of quaterphenylene dicarbonitriles at an electronically patterned boron nitride on copper platform (BN/Cu(111)). A first level of spatially modulated conductance at the nanometer-scale is induced by the substrate. Moreover, a second level of conductance variations at the molecular level is found. Low temperature scanning tunneling microscopy studies in conjunction with molecular dynamics calculations reveal collective amplification of the molecule’s interphenylene torsion angles in the monolayer. Librational modes influencing these torsion angles are identified as initial excitations during vibronic conductance. Density functional theory is used to map phenylene breathing modes and other vibrational excitations that are suggested to be at the origin of the submolecular features during vibronic conductance.

Photodynamic therapy is a promising treatment method, but its applications are limited by the shallow penetration of visible light. Here, we report a novel X-ray inducible photodynamic therapy (X-PDT) approach that allows PDT to be regulated by X-rays. Upon X-ray irradiation, the integrated nanosystem, comprised of a core of a nanoscintillator and a mesoporous silica coating loaded with photosensitizers, converts X-ray photons to visible photons to activate the photosensitizers and cause efficient tumor shrinkage.

Submolecular imaging by atomic force microscopy (AFM) has recently been established as a stunning technique to reveal the chemical structure of unknown molecules, to characterize intramolecular charge distributions and bond ordering, as well as to study chemical transformations and intermolecular interactions. So far, most of these feats were achieved on planar molecular systems because high-resolution imaging of three-dimensional (3D) surface structures with AFM remains challenging. Here we present a method for high-resolution imaging of nonplanar molecules and 3D surface systems using AFM with silicon cantilevers as force sensors. We demonstrate this method by resolving the step-edges of the (101) anatase surface at the atomic scale by simultaneously visualizing the structure of a pentacene molecule together with the atomic positions of the substrate and by resolving the contour and probe-surface force field on a C₆₀ molecule with intramolecular resolution. The method reported here holds substantial promise for the study of 3D surface systems such as nanotubes, clusters, nanoparticles, polymers, and biomolecules using AFM with high resolution.

Hexagonal boron nitride (hBN) is a wide-gap material that has attracted significant attention as an ideal dielectric substrate for 2D crystal heterostructures. We report here the first observation of in-plane charge transport in large-area monolayer hBN, grown by chemical vapor deposition. The quadratic scaling of current with voltage at high bias corresponds to a space-charge limited conduction mechanism, with a room-temperature mobility reaching up to 0.01 cm²/(V s) at electric fields up to 100 kV/cm in the absence of dielectric breakdown. The observation of in-plane charge transport highlights the semiconducting nature of monolayer hBN, and identifies hBN as a wide-gap 2D crystal capable of supporting charge transport at high field. Future exploration of charge transport in hBN is motivated by the fundamental study of UV optoelectronics and the massive Dirac fermion spectrum of hBN.

Two-dimensional (2D) heteronanosheets are currently the focus of intense study due to the unique properties that emerge from the interplay between two low-dimensional nanomaterials with different properties. However, the properties and new phenomena based on the two 2D heteronanosheets interacting in a 3D hierarchical architecture have yet to be explored. Here, we unveil the surface redox charge storage mechanism of surface-exposed WS₂ nanosheets assembled in a 3D hierarchical heterostructure using in situ synchrotron X-ray absorption and Raman spectroscopic methods. The surface dominating redox charge storage of WS₂ is manifested in a highly reversible and ultrafast capacitive fashion due to the interaction of heteronanosheets and the 3D connectivity of the hierarchical structure. In contrast, compositionally identical 2D WS₂ structures fail to provide a fast and high capacitance with different modes of lattice vibration. The distinctive surface capacitive behavior of 3D hierarchically structured heteronanosheets is associated with rapid proton accommodation into the in-plane W–S lattice (with the softening of the E_2g bands), the reversible redox transition of the surface-exposed intralayers residing in the electrochemically active 1T phase of WS₂ (with the reversible change in the interatomic distance and peak intensity of W–W bonds), and the change in the oxidation state during the proton insertion/deinsertion process. This proposed mechanism agrees with the dramatic improvement in the capacitive performance of the two heteronanosheets coupled in the hierarchical structure.

The thickness-dependent band structure of MoS₂ implies that discontinuities in energy bands exist at the interface of monolayer (1L) and multilayer (ML) thin films. The characteristics of such heterojunctions are analyzed here using current versus voltage measurements, scanning photocurrent microscopy, and finite element simulations of charge carrier transport. Rectifying I–V curves are consistently observed between contacts on opposite sides of 1L/ML junctions, and a strong bias-dependent photocurrent is observed at the junction. Finite element device simulations with varying carrier concentrations and electron affinities show that a type II band alignment at single layer/multilayer junctions reproduces both the rectifying electrical characteristics and the photocurrent response under bias. However, the zero-bias junction photocurrent and its energy dependence are not explained by conventional photovoltaic and photothermoelectric mechanisms, indicating the contributions of hot carriers.

We report the synthesis of high-quality single-crystal two-dimensional, layered nanostructures of silicon telluride, Si₂Te₃, in multiple morphologies controlled by substrate temperature and Te seeding. Morphologies include nanoribbons formed by VLS growth from Te droplets, vertical hexagonal nanoplates through vapor–solid crystallographically oriented growth on amorphous oxide substrates, and flat hexagonal nanoplates formed through large-area VLS growth in liquid Te pools. We show the potential for doping through the choice of substrate and growth conditions. Vertical nanoplates grown on sapphire substrates, for example, can incorporate a uniform density of Al atoms from the substrate. We also show that the material may be modified after synthesis, including both mechanical exfoliation (reducing the thickness to as few as five layers) and intercalation of metal ions including Li⁺ and Mg²⁺, which suggests applications in energy storage materials. The material exhibits an intense red color corresponding to its strong and broad interband absorption extending from the red into the infrared. Si₂Te₃ enjoys chemical and processing compatibility with other silicon-based material including amorphous SiO₂ but is very chemically sensitive to its environment, which suggests applications in silicon-based devices ranging from fully integrated thermoelectrics to optoelectronics to chemical sensors.

Emerging photonic integrated circuit technologies require integrative functionality at ultrahigh speed and dimensional compatibility with ultrasmall electronics. Plasmonics offers a promise of addressing these challenges with novel nanophotonic approaches for on-chip information processing or sensing applications. Short communication range and strong light-matter interaction enabled by on-chip plasmonics allow us to extend beyond a conventional approach of integrating coherent and narrowband light source. Such hybrid electronic and photonic interconnection desires a on-chip photodetector that is highly responsive to broadband incoherent light, yet provides elegant design for nanoscale integration. Here we demonstrate an ultracompact broadband photodetection with greatly enhanced photoresponsivity using plasmonic nanoridge geometry. The nanoridge photodetector confines a wide spectrum of electromagnetic energy in a nanostructure through the excitation of multiple plasmons, which thus enables the detection of weak and broadband light. With nanoscale design, material, and dimensional compatibility for the integration, the nanoridge photodetector opens up a new possibility of highly sensitive on-chip photodetection for future integrated circuits and sensing applications.

The effect of elastic energy on nucleation and disappearance of a nanometer size intermediate melt (IM) region at a solid–solid (S₁S₂) phase interface at temperatures 120 K below the melting temperature is studied using a phase-field approach. Results are obtained for broad range of the ratios of S₁S₂ to solid–melt interface energies, k_E, and widths, k_δ. It is found that internal stresses only slightly promote barrierless IM nucleation but qualitatively alter the system behavior, allowing for the appearance of the IM when k_E < 2 (thermodynamically impossible without mechanics) and elimination of what we termed the IM-free gap. Remarkably, when mechanics is included within this framework, there is a drastic (16 times for HMX energetic crystals) reduction in the activation energy of IM critical nucleus. After this inclusion, a kinetic nucleation criterion is met, and thermally activated melting occurs under conditions consistent with experiments for HMX, elucidating what had been to date mysterious behavior. Similar effects are expected to occur for other material systems where S₁S₂ phase transformations via IM take place, including electronic, geological, pharmaceutical, ferroelectric, colloidal, and superhard materials.

We propose a plasmonic surface that produces an electrically controlled reflectance as a high-speed intensity modulator. The device is conceived as a metal-oxide-semiconductor capacitor on silicon with its metal structured as a thin patch bearing a contiguous nanoscale grating. The metal structure serves multiple functions as a driving electrode and as a grating coupler for perpendicularly incident p-polarized light to surface plasmons supported by the patch. Modulation is produced by charging and discharging the capacitor and exploiting the carrier refraction effect in silicon along with the high sensitivity of strongly confined surface plasmons to index perturbations. The area of the modulator is set by the area of the incident beam, leading to a very compact device for a strongly focused beam (∼2.5 μm in diameter). Theoretically, the modulator can operate over a broad electrical bandwidth (tens of gigahertz) with a modulation depth of 3 to 6%, a loss of 3 to 4 dB, and an optical bandwidth of about 50 nm. About 1000 modulators can be integrated over a 50 mm² area producing an aggregate electro-optic modulation rate in excess of 1 Tb/s. We demonstrate experimentally modulators operating at telecommunications wavelengths, fabricated as nanostructured Au/HfO₂/p-Si capacitors. The modulators break conceptually from waveguide-based devices and belong to the same class of devices as surface photodetectors and vertical cavity surface-emitting lasers.

A micromechanical resonator embedded with a nanomechanical resonator is developed whose dynamics can be captured by the coupled-Van der Pol–Duffing equations. Activating the nanomechanical resonator can dispersively shift the micromechanical resonance by more than 100 times its bandwidth and concurrently increase its energy dissipation rate to the point where it can even be deactivated. The coupled-Van der Pol–Duffing equations also suggest the possibility of self-oscillations. In the limit of strong excitation for the nanomechanical resonator, the dissipation in the micromechanical resonator can not only be reduced, resulting in a quality factor of >3× 10⁶, it can even be eliminated entirely resulting in the micromechanical resonator spontaneously vibrating.

The high speed on–off performance of GaN-based light-emitting diodes (LEDs) grown in c-plane direction is limited by long carrier lifetimes caused by spontaneous and piezoelectric polarization. This work demonstrates that this limitation can be overcome by m-planar core–shell InGaN/GaN nanowire LEDs grown on Si(111). Time-resolved electroluminescence studies exhibit 90–10% rise- and fall-times of about 220 ps under GHz electrical excitation. The data underline the potential of these devices for optical data communication in polymer fibers and free space.

We present theoretical and experimental studies of the effect of the density of states of a quantum dot (QD) on the rate of single-electron tunneling that can be directly measured by electrostatic force microscopy (e-EFM) experiments. In e-EFM, the motion of a biased atomic force microscope cantilever tip modulates the charge state of a QD in the Coulomb blockade regime. The charge dynamics of the dot, which is detected through its back-action on the capacitavely coupled cantilever, depends on the tunneling rate of the QD to a back-electrode. The density of states of the QD can therefore be measured through its effect on the energy dependence of tunneling rate. We present experimental data on individual 5 nm colloidal gold nanoparticles that exhibit a near continuous density of state at 77 K. In contrast, our analysis of already published data on self-assembled InAs QDs at 4 K clearly reveals discrete degenerate energy levels.

Nanoparticle-based therapy represents a novel and promising approach to treat glioblastoma, the most common and lethal malignant brain cancer. Although similar therapies have achieved significant cytotoxicity in cultured glioblastoma or glioblastoma stem cells (GSCs), the lack of an appropriate approach to monitor interactions between cells and nanoparticle-based therapies impedes their further clinical application in human patients. To address this critical issue, we first obtained NOTCH1 positive GSCs from patient-derived primary cultures. We then developed a new imaging approach to directly observe the dynamic nature of nanoparticles at the molecular level using in situ transmission electron microscopy (TEM). Utilizing these tools we were able to visualize real-time movements of nanoparticles interacting with GSCs for the first time. Overall, we show strong proof-of-concept results that real-time visualization of nanoparticles in single cells can be achieved at the nanoscale using TEM, thereby providing a powerful platform for the development of nanotherapeutics.

We study the evolution of the band gap structure in few-layer MoTe₂ crystals, by means of low-temperature microreflectance (MR) and temperature-dependent photoluminescence (PL) measurements. The analysis of the measurements indicate that in complete analogy with other semiconducting transition metal dichalchogenides (TMDs) the dominant PL emission peaks originate from direct transitions associated with recombination of excitons and trions. When we follow the evolution of the PL intensity as a function of layer thickness, however, we observe that MoTe₂ behaves differently from other semiconducting TMDs investigated earlier. Specifically, the exciton PL yield (integrated PL intensity) is identical for mono and bilayer, decreases slightly for trilayer, and it is significantly lower in the tetralayer. The analysis of this behavior and of all our experimental observations is fully consistent with mono and bilayer MoTe₂ being direct band gap semiconductors with tetralayer MoTe₂ being an indirect gap semiconductor and with trilayers having nearly identical direct and indirect gaps. This conclusion is different from the one reached for other recently investigated semiconducting transition metal dichalcogenides for which monolayers are found to be direct band gap semiconductors, and thicker layers have indirect band gaps that are significantly smaller (by hundreds of meV) than the direct gap. We discuss the relevance of our findings for experiments of fundamental interest and possible future device applications.

Yttrium-doped barium zirconate (BZY) thin films recently showed surprising electric transport properties. Experimental investigations conducted mainly by electrochemical impedance spectroscopy suggested that a consistent part of this BZY conductivity is of protonic nature. These results have stimulated further investigations by local unconventional techniques. Here, we use electrochemical strain microscopy (ESM) to detect electrochemical activity in BZY films with nanoscale resolution. ESM in a novel cross-sectional measuring setup allows the direct visualization of the interfacial activity. The local electrochemical investigation is compared with the structural studies performed by state of art scanning transmission electron microscopy (STEM). The ESM and STEM results show a clear correlation between the conductivity and the interface structural defects. We propose a physical model based on a misfit dislocation network that introduces a novel 2D transport phenomenon, whose fingerprint is the low activation energy measured.

Most of the existing flexible lithium ion batteries (LIBs) adopt the conventional cofacial cell configuration where anode, separator, and cathode are sequentially stacked and so have difficulty in the integration with emerging thin LIB applications, such as smart cards and medical patches. In order to overcome this shortcoming, herein, we report a coplanar cell structure in which anodes and cathodes are interdigitatedly positioned on the same plane. The coplanar electrode design brings advantages of enhanced bending tolerance and capability of increasing the cell voltage by in series-connection of multiple single-cells in addition to its suitability for the thickness reduction. On the basis of these structural benefits, we develop a coplanar flexible LIB that delivers 7.4 V with an entire cell thickness below 0.5 mm while preserving stable electrochemical performance throughout 5000 (un)bending cycles (bending radius = 5 mm). Also, even the pouch case serves as barriers between anodes and cathodes to prevent Li dendrite growth and short-circuit formation while saving the thickness. Furthermore, for convenient practical use wireless charging via inductive electromagnetic energy transfer and solar cell integration is demonstrated.

We synthesized “mesoscale” nanoparticles, approximately 400 nm in diameter, which unexpectedly localized selectively in renal proximal tubules and up to 7 times more efficiently in the kidney than other organs. Although nanoparticles typically localize in the liver and spleen, modulating their size and opsonization potential allowed for stable targeting of the kidneys through a new proposed uptake mechanism. Applying this kidney targeting strategy, we anticipate use in the treatment of renal disease and the study of renal physiology.

We report a three-state nanofluidic field effect switch in an asymmetrically gated device with a forward (positive), off (zero), and a reverse (negative) current state for tunable control of ionic transport by systematically controlling the gate potential. The embedded gate electrode allows for modulation of the ionic current through the 16 nm deep channels as a function of electrolyte concentration and gate electrode location for a fixed streamwise potential.

An electric field built inside a crystal was proposed to enhance photoinduced carrier separation for improving photocatalytic property of semiconductor photocatalysts. However, a static built-in electric field can easily be saturated by the free carriers due to electrostatic screening, and the enhancement of photocatalysis, thus, is halted. To overcome this problem, here, we propose sonophotocatalysis based on a new hybrid photocatalyst, which combines ferroelectric nanocrystals (BaTiO₃) and semiconductor nanoparticles (Ag₂O) to form an Ag₂O–BaTiO₃ hybrid photocatalyst. Under periodic ultrasonic excitation, a spontaneous polarization potential of BaTiO₃ nanocrystals in responding to ultrasonic wave can act as alternating built-in electric field to separate photoinduced carriers incessantly, which can significantly enhance the photocatalytic activity and cyclic performance of the Ag₂O–BaTiO₃ hybrid structure. The piezoelectric effect combined with photoelectric conversion realizes an ultrasonic-wave-driven piezophototronic process in the hybrid photocatalyst, which is the fundamental of sonophotocatalysis.

Photonic quantum technologies have been extensively studied in quantum information science, owing to the high-speed transmission and outstanding low-noise properties of photons. However, applications based on photonic entanglement are restricted due to the diffraction limit. In this work, we demonstrate for the first time the maintaining of quantum polarization entanglement in a nanoscale hybrid plasmonic waveguide composed of a fiber taper and a silver nanowire. The transmitted state throughout the waveguide has a fidelity of 0.932 with the maximally polarization entangled state Φ⁺. Furthermore, the Clauser, Horne, Shimony, and Holt (CHSH) inequality test performed, resulting in value of 2.495 ± 0.147 > 2, demonstrates the violation of the hidden variable model. Because the plasmonic waveguide confines the effective mode area to subwavelength scale, it can bridge nanophotonics and quantum optics and may be used as near-field quantum probe in a quantum near-field micro/nanoscope, which can realize high spatial resolution, ultrasensitive, fiber-integrated, and plasmon-enhanced detection.

We report tip-enhanced Raman imaging experiments in which information on sample topography and local electric fields is simultaneously obtained using an all-optical detection scheme. We demonstrate how a Raman-active 4,4′-dimercaptostilbene (DMS)-coated gold tip of an atomic force microscope can be used to simultaneously map the topography and image the electric fields localized at nanometric (20 and 5 nm wide) slits lithographically etched in silver, all using optical signals. Bimodal imaging is feasible by virtue of the frequency-resolved optical response of the functionalized metal probe. Namely, the probe position-dependent signals can be subdivided into two components. The first is a 500–2250 cm^–1 Raman-shifted signal, characteristic of the tip-bound DMS molecules. The molecules report on topography through the intensity contrast observed as the tip scans across the nanoscale features. The variation in molecular Raman activity arises from the absence/formation of a plasmonic junction between the scanning probe and patterned silver surface, which translates into dimmed/enhanced Raman signatures of DMS. Using these molecular signals, we demonstrate that sub-15 nm spatial resolution is attainable using a 30 nm DMS-coated gold tip. The second response consists of two correlated sub-500 cm^–1 signals arising from mirror-like reflections of (i) the incident laser field and (ii) the Raman scattered response of an underlying glass support (at 100–500 cm^–1) off the gold tip. We show that both the reflected low-wavenumber signals trace the local electric fields in the vicinity of the nanometric slits.

The piezoelectronic transistor (PET) has been proposed as a transduction device not subject to the voltage limits of field-effect transistors. The PET transduces voltage to stress, activating a facile insulator–metal transition, thereby achieving multigigahertz switching speeds, as predicted by modeling, at lower power than the comparable generation field effect transistor (FET). Here, the fabrication and measurement of the first physical PET devices are reported, showing both on/off switching and cycling. The results demonstrate the realization of a stress-based transduction principle, representing the early steps on a developmental pathway to PET technology with potential to contribute to the IT industry.

With the discovery and first characterization of graphene, its potential for spintronic applications was recognized immediately. Since then, an active field of research has developed trying to overcome the practical hurdles. One of the most severe challenges is to find appropriate interfaces between graphene and ferromagnetic layers, which are granting efficient injection of spin-polarized electrons. Here, we show that graphene grown under appropriate conditions on Co(0001) demonstrates perfect structural properties and simultaneously exhibits highly spin-polarized charge carriers. The latter was conclusively proven by observation of a single-spin Dirac cone near the Fermi level. This was accomplished experimentally using spin- and angle-resolved photoelectron spectroscopy, and theoretically with density functional calculations. Our results demonstrate that the graphene/Co(0001) system represents an interesting candidate for applications in devices using the spin degree of freedom.

In this study, we communicate an investigation on efficient CH₃NH₃PbI₃-based solar cells with carbon electrode using mesoporous TiO₂ and NiO layers as electron and hole selective contacts. The device possesses an appreciated power conversion efficiency of 14.9% under AM 1.5G illumination. The detailed information can be disclosed with impedance spectroscopy via tuning the interfaces between CH₃NH₃PbI₃ and different charge selective contacts. The results clearly show charge accumulation at the interface of CH₃NH₃PbI₃. The NiO is believed to efficiently accelerate charge extraction to the external circuit. The extracted charge could improve photovoltaic performance by shifting hole Fermi level down, achieving a high device photovoltage. A fast interfacial recombination at the interface of CH₃NH₃PbI₃/electron selective contact layer (mesoporous TiO₂), occurring in millisecond domains, is the critical issue for charge carrier recombination loss.

Semiconductor quantum wells are ubiquitous in high-performance optoelectronic devices such as solar cells and lasers. Understanding and controlling of the (hot) carrier dynamics is essential to optimize their performance. Here, we study hot electron cooling in colloidal CdSe quantum-well nanoplatelets using ultrafast two-photon photoemission spectroscopy at low excitation intensities, resulting typically in 1–5 hot electrons per platelet. We observe initial electron cooling in the femtosecond time domain that slows down with decreasing electron energy and is finished within 2 ps. The cooling is considerably faster at cryogenic temperatures than at room temperature, and at least for the systems that we studied, independent of the thickness of the platelets (here 3–5 CdSe units) and the presence of a CdS shell. The cooling rates that we observe are orders of magnitude faster than reported for similar CdSe platelets under strong excitation. Our results are understood by a classic cooling mechanism with emission of longitudinal optical phonons without a significant influence of the surface.

We have successfully developed a circularly polarized near-field scanning optical microscope (NSOM) that enables us to irradiate circularly polarized light with spatial resolution below the diffraction limit. As a demonstration, we perform real-space mapping of the quantum Hall chiral edge states near the edge of a Hall-bar structure by injecting spin polarized electrons optically at low temperature. The obtained real-space mappings show that spin-polarized electrons are injected optically to the two-dimensional electron layer. Our general method to locally inject spins using a circularly polarized NSOM should be broadly applicable to characterize a variety of nanomaterials and nanostructures.

We report generation of modular, artificial light-harvesting assemblies where an amphiphilic diblock copolymer, poly(ethylene oxide)-block-poly(butadiene), serves as the framework for noncovalent organization of BODIPY-based energy donor and bacteriochlorin-based energy acceptor chromophores. The assemblies are adaptive and form well-defined micelles in aqueous solution and high-quality monolayer and bilayer films on solid supports, with the latter showing greater than 90% energy transfer efficiency. This study lays the groundwork for further development of modular, polymer-based materials for light harvesting and other photonic applications.

Applying tensile strain in a single germanium crystal is a very promising way to tune its bandstructure and turn it into a direct band gap semiconductor. In this work, we stress vapor–liquid–solid grown germanium nanowires along their [111] axis thanks to the strain tranfer from a silicon nitride thin film by a microfabrication process. We measure the Γ-LH direct band gap transition by photocurrent spectrometry and quantify associated strain by X-ray Laue microdiffraction on beamline BM32 at the European Synchrotron Radiation Facility. Nanowires exhibit up to 1.48% strain and an absorption threshold down to 0.73 eV, which is in good agreement with theoretical computations for the Γ-LH transition, showing that the nanowire geometry is an efficient way of applying tensile uniaxial stress along the [111] axis of a germanium crystal.

Transdermal delivery of therapeutics is restricted by narrow limitations on size and hydrophobicity. Nanotopography has been shown to significantly enhance high molecular weight paracellular transport in vitro. Herein, we demonstrate for the first time that nanotopography applied to microneedles significantly enhances transdermal delivery of etanercept, a 150 kD therapeutic, in both rats and rabbits. We further show that this effect is mediated by remodeling of the tight junction proteins initiated via integrin binding to the nanotopography, followed by phosphorylation of myosin light chain (MLC) and activation of the actomyosin complex, which in turn increase paracellular permeability.

The success of topological insulators (TI) in creating devices with unique functionalities is directly connected to the ability of coupling their helical spin states to well-defined perturbations. However, up to now, TI-based heterostructures always resulted in very disordered interfaces, characterized by strong mesoscopic fluctuations of the chemical potential that make the spin-momentum locking ill-defined over length scales of few nanometers or even completely destroy topological states. These limitations call for the ability to control topological interfaces with atomic precision. Here, we demonstrate that molecular self-assembly processes driven by inherent interactions among the constituents offer the opportunity to create well-defined networks at TIs surfaces. Even more remarkably, we show that the symmetry of the overlayer can be finely controlled by appropriate chemical modifications. By analyzing the influence of the molecules on the TI electronic properties, we rationalize our results in terms of the charge redistribution taking place at the interface. Overall, our approach offers a precise and fast way to produce tailor-made nanoscale surface landscapes. In particular, our findings make organic materials ideal TIs counterparts, because they offer the possibility to chemically tune both electronic and magnetic properties within the same family of molecules, thereby bringing us a significant step closer toward an application of this fascinating class of materials.

A key quantity for molecule–metal interfaces is the energy level alignment of molecular electronic states with the metallic Fermi level. We develop and apply an efficient theoretical method, based on density functional theory (DFT) that can yield quantitatively accurate energy level alignment information for physisorbed metal–molecule interfaces. The method builds on the “DFT+Σ” approach, grounded in many-body perturbation theory, which introduces an approximate electron self-energy that corrects the level alignment obtained from conventional DFT for missing exchange and correlation effects associated with the gas-phase molecule and substrate polarization. Here, we extend the DFT+Σ approach in two important ways: first, we employ optimally tuned range-separated hybrid functionals to compute the gas-phase term, rather than rely on GW or total energy differences as in prior work; second, we use a nonclassical DFT-determined image-charge plane of the metallic surface to compute the substrate polarization term, rather than the classical DFT-derived image plane used previously. We validate this new approach by a detailed comparison with experimental and theoretical reference data for several prototypical molecule–metal interfaces, where excellent agreement with experiment is achieved: benzene on graphite (0001), and 1,4-benzenediamine, Cu-phthalocyanine, and 3,4,9,10-perylene-tetracarboxylic-dianhydride on Au(111). In particular, we show that the method correctly captures level alignment trends across chemical systems and that it retains its accuracy even for molecules for which conventional DFT suffers from severe self-interaction errors.

Myosin is a mechano-enzyme that hydrolyzes ATP in order to move unidirectionally along actin filaments. Here we show by single molecule imaging that myosin V motion can be activated by local heat. We constructed a dark-field microscopy that included optical tweezers to monitor 80 nm gold nanoparticles (GNP) bound to single myosin V molecules with nanometer and submillisecond accuracy. We observed 34 nm processive steps along actin filaments like those seen when using 200 nm polystyrene beads (PB) but dwell times (ATPase activity) that were 4.5 times faster. Further, by using DNA nanotechnology (DNA origami) and myosin V as a nanometric thermometer, the temperature gradient surrounding optically trapped GNP could be estimated with nanometer accuracy. We propose our single molecule measurement system should advance quantitative analysis of the thermal control of biological and artificial systems like nanoscale thermal ratchet motors.

We report on growth and characterization of wurtzite InP–In_1–xGa_xAs core–shell nanowire heterostructures. A range of nanowire structures with different Ga concentration in the shell was characterized with transmission electron microscopy and X-ray diffraction. We found that the main part of the nanowires has a pure wurtzite crystal structure, with occasional stacking faults occurring only at the top and bottom. This allowed us to determine the structural properties of wurtzite In_1–xGa_xAs. The InP–In_1–xGa_xAs core–shell nanowires show a triangular and hexagonal facet structure of {1100} and {101̅0} planes. X-ray diffraction measurements showed that the core and the shell are pseudomorphic along the c-axis, and the strained axial lattice constant is closer to the relaxed In_1–xGa_xAs shell. Microphotoluminescence measurements of the nanowires show emission in the infrared regime, which makes them suitable for applications in optical communication.

Fully ordered face-centered tetragonal (fct) FePt nanoparticles (NPs) are synthesized by thermal annealing of the MgO-coated dumbbell-like FePt-Fe₃O₄ NPs followed by acid washing to remove MgO. These fct-FePt NPs show strong ferromagnetism with room temperature coercivity reaching 33 kOe. They serve as a robust electrocatalyst for the oxygen reduction reaction (ORR) in 0.1 M HClO₄ and hydrogen evolution reaction (HER) in 0.5 M H₂SO₄ with much enhanced activity (the most active fct-structured alloy NP catalyst ever reported) and stability (no obvious Fe loss and NP degradation after 20 000 cycles between 0.6 and 1.0 V (vs RHE)). Our work demonstrates a reliable approach to FePt NPs with much improved fct-ordering and catalytic efficiency for ORR and HER.

A two-dimensional epitaxial growth template for organic semiconductors was developed using a new method for transferring clean graphene sheets onto a substrate with controlled surface wettability. The introduction of a sacrificial graphene layer between a patterned polymeric supporting layer and a monolayer graphene sheet enabled the crack-free and residue-free transfer of free-standing monolayer graphene onto arbitrary substrates. The clean graphene template clearly induced the quasi-epitaxial growth of crystalline organic semiconductors with lying-down molecular orientation while maintaining the “wetting transparency”, which allowed the transmission of the interaction between organic molecules and the underlying substrate. Consequently, the growth mode and corresponding morphology of the organic semiconductors on graphene templates exhibited distinctive dependence on the substrate hydrophobicity with clear transition from lateral to vertical growth mode on hydrophilic substrates, which originated from the high surface energy of the exposed crystallographic planes of the organic semiconductors on graphene. The optical properties of the pentacene layer, especially the diffusion of the exciton, also showed a strong dependency on the corresponding morphological evolution. Furthermore, the effect of pentacene–substrate interaction was systematically investigated by gradually increasing the number of graphene layers. These results suggested that the combination of a clean graphene surface and a suitable underlying substrate could serve as an atomically thin growth template to engineer the interaction between organic molecules and aromatic graphene network, thereby paving the way for effectively and conveniently tuning the semiconductor layer morphologies in devices prepared using graphene.

Pb_1–xSn_xTe is a unique topological crystalline insulator (TCI) that undergoes a topological phase transition from topological trivial insulator to TCI with the change of Sn content and temperature. Meanwhile, the surface states properties of Pb_1–xSn_xTe are strongly dependent on crystallographic plane orientation. In this work, we first reported controllable synthesis of rectangular prismatic Pb_xSn_1–xTe nanowires by vapor deposition method. Rectangular prismatic Pb_xSn_1–xTe nanowires exhibits distinct {100} surfaces. Furthermore, The Sn composition of Pb_1–xSn_xTe nanowires can be continuously controlled from 0 to 1. Low temperature magnetotransport shows that PbTe nanowire exhibits weak localization (WL) effect, whereas Pb_0.5Sn_0.5Te and Pb_0.2Sn_0.8Te nanowires display pronounced weak antilocalization (WAL) effect. This transition is explained by the topological phase transform of Pb_1–xSn_xTe from trivial to nontrivial insulator with Sn content (x) exceeding 0.38. Pb_xSn_1–xTe nanowires synthesized in this work lay a foundation for probing spin-correlated electron transport and show great potentials for future applications of tunable spintronic devices.

We describe a metal nanodisk–insulator–metal (MIM) structure that enhances lanthanide-based upconversion (UC) and downshifting (DS) simultaneously. The structure was fabricated using a nanotransfer printing method that facilitates large-area applications of nanostructures for optoelectronic devices. The proposed MIM structure is a promising way to harness the entire solar spectrum by converting both ultraviolet and near-infrared to visible light concurrently through resonant-mode excitation. The overall photoluminescence enhancements of the UC and DS were 174- and 29-fold, respectively.

Diverse transition metal hydroxide nanostructures were synthesized by laser-induced hydrolysis in a liquid precursor solution for alkaline oxygen evolution reaction (OER). Several active OER catalysts with fine control of composition, structure, and valence state were obtained including (Li_x)[Ni_0.66Mn_0.34(OH)₂](NO₃)(CO₃) · mH₂O, Li_x[Ni_0.67Co_0.33(OH)₂](NO₃)_0.25(ORO)_0.35 · mH₂O, etc. An operate overpotential less than 0.34 V at current density of 10 mA cm^–2 was achieved. Such a controllable laser–chemical route for assessing complex nanostructures in liquids opens many opportunities to design novel functional materials for advanced applications.

Luminescence blinking is an inherent feature of optical emission from individual fluorescent molecules and quantum dots. There have been intense efforts, although not with complete resolution, toward the understanding of the mechanistic origin of blinking and also its mitigation in quantum dots. As an advance in our microscopic view of blinking, we show that the luminescence blinking of a quantum dot becomes unusually heavy in the temporal vicinity of a reactive transformation. This stage of heavy blinking is a result of defects/dopants formed within the quantum dot on its path to conversion. The evolution of blinking behavior along the reaction path allows us to measure the lifetime of the critical dopant-related intermediate in the reaction. This work establishes luminescence blinking as a single-nanocrystal level probe of catalytic, photocatalytic, and electrochemical events occurring in the solid-state or on semiconductor surfaces.

Germanene, a 2D honeycomb structure similar to silicene, has been fabricated on Al(111). The 2D germanene layer covers uniformly the substrate with a large coherence over the Al(111) surface atomic plane. It is characterized by a (3 × 3) superstructure with respect to the substrate lattice, shown by low energy electron diffraction and scanning tunnelling microscopy. First-principles calculations indicate that the Ge atoms accommodate in a very regular atomic configuration with a buckled conformation.

Stable and high-performance nanoporous “black silicon” photoelectrodes with electrolessly deposited Pt nanoparticle (NP) catalysts are made with two metal-assisted etching steps. Doubly etched samples exhibit an ∼300 mV positive shift in photocurrent onset for photoelectrochemical proton reduction compared to oxide-free planar Si with identical catalysts. We find that the photocurrent onset voltage of black Si photocathodes prepared from single-crystal planar Si wafers by an Ag-assisted etching process increases in oxidative environments (e.g., aqueous electrolyte) owing to a positive flat-band potential shift caused by surface oxidation. However, within 24 h, the surface oxide layer becomes a kinetic barrier to interfacial charge transfer that inhibits proton reduction. To mitigate this issue, we developed a novel second Pt-assisted etch process that buries the Pt NPs deep into the nanoporous Si surface. This second etch shifts the onset voltage positively, from +0.25 V to +0.4 V versus reversible hydrogen electrode, and reduces the charge-transfer resistance with no performance decrease seen for at least two months. PEC performance was stable owing to Pt NP catalysts that were buried deeply in the photoelectrode by the second etch, below a thick surface layer comprised primarily of amorphous SiO₂ along with some degree of remaining crystalline Si as observed by scanning and transmission electron micrographs. Electrochemical impedance studies reveal that the second etch leads to a considerably smaller interfacial charge-transfer resistance than samples without the additional etch, suggesting that burying the Pt NPs improves the interfacial contact to the crystalline silicon surface.

The two-fold valley degeneracy in two-dimensional (2D) semiconducting transition metal dichalcogenides (TMDCs) (Mo,W)(S,Se)₂ is suitable for “valleytronics”, the storage and manipulation of information utilizing the valley degree of freedom. The conservation of luminescent photon helicity in these 2D crystal monolayers has been widely regarded as a benchmark indicator for charge carrier valley polarization. Here we perform helicity-resolved Raman scattering of the TMDC atomic layers. In drastic contrast to luminescence, the dominant first-order zone-center Raman bands, including the low energy breathing and shear modes as well as the higher energy optical phonons, are found to either maintain or completely switch the helicity of incident photons. In addition to providing a useful tool for characterization of TMDC atomic layers, these experimental observations shed new light on the connection between photon helicity and valley polarization.

The electric field control of functional properties is a crucial goal in oxide-based electronics. Nonvolatile switching between different resistivity or magnetic states in an oxide channel can be achieved through charge accumulation or depletion from an adjacent ferroelectric. However, the way in which charge distributes near the interface between the ferroelectric and the oxide remains poorly known, which limits our understanding of such switching effects. Here, we use a first-of-a-kind combination of scanning transmission electron microscopy with electron energy loss spectroscopy, near-total-reflection hard X-ray photoemission spectroscopy, and ab initio theory to address this issue. We achieve a direct, quantitative, atomic-scale characterization of the polarization-induced charge density changes at the interface between the ferroelectric BiFeO₃ and the doped Mott insulator Ca_1–xCe_xMnO₃, thus providing insight on how interface-engineering can enhance these switching effects.

The advantages of graphene photodetectors were utilized to design a new multifunctional graphene optoelectronic device. Organic semiconductors, gold nanoparticles (AuNPs), and graphene were combined to fabricate a photodetecting device with a nonvolatile memory function for storing photonic signals. A pentacene organic semiconductor acted as a light absorption layer in the device and provided a high hole photocurrent to the graphene channel. The AuNPs, positioned between the tunneling and blocking dielectric layers, acted as both a charge trap layer and a plasmonic light scatterer, which enable storing of the information about the incident light. The proposed pentacene-graphene-AuNP hybrid photodetector not only performed well as a photodetector in the visible light range, it also was able to store the photonic signal in the form of persistent current. The good photodetection performance resulted from the plasmonics-enabled enhancement of the optical absorption and from the photogating mechanisms in the pentacene. The device provided a photoresponse that depended on the wavelength of incident light; therefore, the signal information (both the wavelength and intensity) of the incident light was effectively committed to memory. The simple process of applying a negative pulse gate voltage could then erase the programmed information. The proposed photodetector with the capacity to store a photonic signal in memory represents a significant step toward the use of graphene in optoelectronic devices.

Interfacial atoms, which result from interactions between the metal nanoparticles and support, have a large impact on the physical and chemical properties of nanoparticles. However, they are difficult to observe; the lack of knowledge has been a major obstacle toward unraveling their role in chemical transformations. Here we report conclusive evidence of interfacial Au atoms formed on the rutile (TiO₂) (110) surfaces by activation using high-temperature (∼500 °C) annealing in air. Three-dimensional imaging was performed using depth-sectioning enabled by aberration-corrected scanning transmission electron microscopy. Results show that the interface between Au nanocrystals and TiO₂ (110) surfaces consists of a single atomic layer with Au atoms embedded inside Ti–O. The number of interfacial Au atoms is estimated from ∼1–8 in an interfacial atomic column. Direct impact of interfacial Au atoms is observed on an enhanced Au-TiO₂ interaction and the reduction of surface TiO₂; both are critical to Au catalysis.

Graphene is a promising flexible, highly transparent, and elementally abundant electrode for organic electronics. Typical methods utilized to transfer large-area films of graphene synthesized by chemical vapor deposition on metal catalysts are not compatible with organic thin-films, limiting the integration of graphene into organic optoelectronic devices. This article describes a graphene transfer process onto chemically sensitive organic semiconductor thin-films. The process incorporates an elastomeric stamp with a fluorinated polymer release layer that can be removed, post-transfer, via a fluorinated solvent; neither fluorinated material adversely affects the organic semiconductor materials. We used Raman spectroscopy, atomic force microscopy, and scanning electron microscopy to show that chemical vapor deposition graphene can be successfully transferred without inducing defects in the graphene film. To demonstrate our transfer method’s compatibility with organic semiconductors, we fabricate three classes of organic thin-film devices: graphene field effect transistors without additional cleaning processes, transparent organic light-emitting diodes, and transparent small-molecule organic photovoltaic devices. These experiments demonstrate the potential of hybrid graphene/organic devices in which graphene is deposited directly onto underlying organic thin-film structures.

The low mass and high quality factors that nanomechanical resonators exhibit lead to exceptional sensitivity in the frequency domain. This is especially appealing for the design of ultrasensitive force and mass sensors. The sensitivity of a nanomechanical mass and force sensor depends on its mass and quality factor; a low resonator mass and a higher quality factor reduce both the minimum resolvable mass and force. Graphene, a single atomic layer thick membrane is an ideal candidate for nanoelectromechanical resonators due to its extremely low mass and high stiffness. Here, we show that by employing the intrinsic piezoresistivity of graphene to transduce its motion in nanoelectromechanical systems, we approach a force resolution of 16.3 ± 0.8 aN/Hz^1/2 and a minimum detectable mass of 1.41 ± 0.02 zeptograms (10^–21 g) at ambient temperature. Quality factors of the driven response of the order of 10³ at pressures ∼10^–6 Torr on several devices are also observed. Moreover, we demonstrate this at ambient temperature on chemical-vapor-deposition-grown graphene to allow for scale-up, thus demonstrating its potential for applications requiring exquisite force and mass resolution such as mass spectroscopy and magnetic resonance force microscopy.

The ability to change states using voltage in ferroelectric tunnel junctions (FTJs) offers a route for lowering the switching energy of memories. Enhanced tunneling electroresistance in FTJ can be achieved by asymmetric electrodes or introducing metal–insulator transition interlayers. However, a fundamental understanding of the role of each interface in a FTJ is lacking and compatibility with integrated circuits has not been explored adequately. Here, we report an incisive study of FTJ performance with varying asymmetry of the electrode/ferroelectric interfaces. Surprisingly high TER (∼400%) can be achieved at BaTiO₃ layer thicknesses down to two unit cells (∼0.8 nm). Further our results prove that band offsets at each interface in the FTJs control the TER ratio. It is found that the off state resistance (R_Off) increases much more rapidly with the number of interfaces compared to the on state resistance (R_On). These results are promising for future low energy memories.

The growth of colloidal nanoparticles is simultaneously driven by kinetic and thermodynamic effects that are difficult to distinguish. We have exploited in situ scanning transmission electron microscopy in liquid to study the growth of Au nanoplates by radiolysis and unravel the mechanisms influencing their formation and shape. The electron dose provides a straightforward control of the growth rate that allows quantifying the kinetic effects on the planar nanoparticles formation. Indeed, we demonstrate that the surface-reaction rate per unit area has the same dose-rate dependent behavior than the concentration of reducing agents in the liquid cell. Interestingly, we also determine a critical supply rate of gold monomers for nanoparticle faceting, corresponding to three layers per second, above which the formation of nanoplates is not possible because the growth is then dominated by kinetic effects. At lower electron dose, the growth is driven by thermodynamic and the formation and shape of nanoplates are directly related to the twin-planes formed during the growth.

Graphene plasmonic structures with long-range layering periodicity are presented. Resonance energy scaling with the number of graphene layers involved in plasmonic excitation allows these structures to support multiple plasmonic modes that couple and hybridize due to their physical proximity. Hybridized states exhibit bandwidth enhancements of 100–200% compared to unhybridized modes, and resonance energies deviate from what is usually observed in coupled plasmonic systems. Origins of this behavior are discussed, and experimental observations are computationally modeled. This work is a precursor and template for the study of plasmonic hybridization in other two-dimensional material systems with layering periodicity.

Hybrid nanostructures that couple plasmon and exciton resonances generate hybridized energy states, called plexcitons, which may result in unusual light-matter interactions. We report the formation of a transparency dip in the visible spectra of colloidal suspensions containing silver nanoplatelets and a cyanine dye, 1,1′-diethyl-2,2′-cyanine iodide (PIC). PIC was electrostatically adsorbed onto the surface of silver nanoplatelet core particles, forming an outer J-aggregate shell. This core–shell architecture provided a framework for coupling the plasmon resonance of the silver nanoplatelet core with the exciton resonance of the J-aggregate shell. The sizes and aspect ratios of the silver nanoplatelets were controlled to ensure the overlap of the plasmon and exciton resonances. As a measure of the plasmon-exciton coupling strength in the system, the experimentally observed transparency dips correspond to a Rabi splitting energy of 207 meV, among the highest reported for colloidal nanoparticles. The optical properties of the silver platelet-J-aggregate nanocomposites were supported numerically and analytically by the boundary-element method and temporal coupled-mode theory, respectively. Our theoretical predictions and experimental results confirm the presence of a transparency dip for the silver nanoplatelet core J-aggregate shell structures. Additionally, the numerical and analytical calculations indicate that the observed transparencies are dominated by the coupling of absorptive resonances, as opposed to the coupling of scattering resonances. Hence, we describe the suppressed extinction in this study as an induced transparency rather than a Fano resonance.

Despite the weak nature of interlayer forces in transition metal dichalcogenide (TMD) materials, their properties are highly dependent on the number of layers in the few-layer two-dimensional (2D) limit. Here, we present a combined scanning tunneling microscopy/spectroscopy and GW theoretical study of the electronic structure of high quality single- and few-layer MoSe₂ grown on bilayer graphene. We find that the electronic (quasiparticle) bandgap, a fundamental parameter for transport and optical phenomena, decreases by nearly one electronvolt when going from one layer to three due to interlayer coupling and screening effects. Our results paint a clear picture of the evolution of the electronic wave function hybridization in the valleys of both the valence and conduction bands as the number of layers is changed. This demonstrates the importance of layer number and electron–electron interactions on van der Waals heterostructures and helps to clarify how their electronic properties might be tuned in future 2D nanodevices.

Temperature-dependent surface-enhanced Raman scattering (SERS) is used to investigate the photoluminescence and background continuum always present in SERS but whose origin remains controversial. Both the Stokes and anti-Stokes background is found to be dominated by inelastic light scattering (ILS) from the electrons in the noble metal nanostructures supporting the plasmon modes. The anti-Stokes background is highly temperature dependent and is shown to be related to the thermal occupation of electronic states within the metal via a simple model. This suggests new routes to enhance SERS sensitivities, as well as providing ubiquitous and calibrated real-time temperature measurements of nanostructures.

Thermal transport behavior in nanostructures has become increasingly important for understanding and designing next generation electronic and energy devices. This has fueled vibrant research targeting both the causes and ability to induce extraordinary reductions of thermal conductivity in crystalline materials, which has predominantly been achieved by understanding that the phonon mean free path (MFP) is limited by the characteristic size of crystalline nanostructures, known as the boundary scattering or Casimir limit. Herein, by using a highly sensitive measurement system, we show that crystalline Si (c-Si) nanotubes (NTs) with shell thickness as thin as ∼5 nm exhibit a low thermal conductivity of ∼1.1 W m^–1 K^–1. Importantly, this value is lower than the apparent boundary scattering limit and is even about 30% lower than the measured value for amorphous Si (a-Si) NTs with similar geometries. This finding diverges from the prevailing general notion that amorphous materials represent the lower limit of thermal transport but can be explained by the strong elastic softening effect observed in the c-Si NTs, measured as a 6-fold reduction in Young’s modulus compared to bulk Si and nearly half that of the a-Si NTs. These results illustrate the potent prospect of employing the elastic softening effect to engineer lower than amorphous, or subamorphous, thermal conductivity in ultrathin crystalline nanostructures.

Transition metal dichalcogenides (TMDs) have emerged as a new class of two-dimensional materials that are promising for electronics and photonics. To date, optoelectronic measurements in these materials have shown the conventional behavior expected from photoconductors such as a linear or sublinear dependence of the photocurrent on light intensity. Here, we report the observation of a new regime of operation where the photocurrent depends superlinearly on light intensity. We use spatially resolved photocurrent measurements on devices consisting of CVD-grown monolayers of TMD alloys spanning MoS₂ to MoSe₂ to show the photoconductive nature of the photoresponse, with the photocurrent dominated by recombination and field-induced carrier separation in the channel. Time-dependent photoconductivity measurements show the presence of persistent photoconductivity for the S-rich alloys, while photocurrent measurements at fixed wavelength for devices of different alloy compositions show a systematic decrease of the responsivity with increasing Se content associated with increased linearity of the current–voltage characteristics. A model based on the presence of different types of recombination centers is presented to explain the origin of the superlinear dependence on light intensity, which emerges when the nonequilibrium occupancy of initially empty fast recombination centers becomes comparable to that of slow recombination centers.

Understanding the formation mechanism of colloidal nanocrystals is of paramount importance in order to design new nanostructures and synthesize them in a predictive fashion. However, reliable data on the pathways leading from molecular precursors to nanocrystals are not available yet. We used synchrotron-based time-resolved in situ small and wide-angle X-ray scattering to experimentally monitor the formation of CdSe quantum dots synthesized in solution through the heating up of precursors in octadecene at 240 °C. Our experiment yields a complete movie of the structure of the solution from the self-assembly of the precursors to the formation of the quantum dots. We show that the initial cadmium precursor lamellar structure melts into small micelles at 100 °C and that the first CdSe nuclei appear at 218.7 °C. The size distributions and concentration in nanocrystals are measured in a quantitative fashion as a function of time. We show that a short nucleation burst lasting 30 s is followed by a slow decrease of nanoparticle concentration. The rate-limiting process of the quantum dot formation is found to be the thermal activation of selenium.

We develop a robust and versatile platform to define nanostructures at oxide interfaces via patterned top gates. Using LaAlO₃/SrTiO₃ as a model system, we demonstrate controllable electrostatic confinement of electrons to nanoscale regions in the conducting interface. The excellent gate response, ultralow leakage currents, and long-term stability of these gates allow us to perform a variety of studies in different device geometries from room temperature down to 50 mK. Using a split-gate device we demonstrate the formation of a narrow conducting channel whose width can be controllably reduced via the application of appropriate gate voltages. We also show that a single narrow gate can be used to induce locally a superconducting to insulating transition. Furthermore, in the superconducting regime we see indications of a gate-voltage controlled Josephson effect.

Plasmonic nanoparticles offer a broad range of functionalities, owing to their ability to amplify light in the near-field or convert it into heat. However, their ultrafast nonlinear optical response remains too low to envisage all-optical high-rate photonic processing applications. Here, we tackle this challenge by coupling the localized plasmon mode in gold nanoparticles with a localized photonic mode in a 1D resonant cavity. Despite the nonradiative losses, we demonstrate that a strong, reversible, and ultrafast optical modulation can be achieved. By using a light pumping fluence of less than 1 mJ cm^–2, a change of signal transmittance of more than 100% is generated within a few picosecond time scale. The nanoparticle transient optical response is enhanced by a factor of 30 to 40 while its spectral profile is strongly sharpened. The large nonlinear response of such plasmonic cavities could open new opportunities for ultrafast light processing at the nanoscale.

Electroluminescence in light-emitting devices relies on the encounter and radiative recombination of electrons and holes in the emissive layer. In organometal halide perovskite light-emitting diodes, poor film formation creates electrical shunting paths, where injected charge carriers bypass the perovskite emitter, leading to a loss in electroluminescence yield. Here, we report a solution-processing method to block electrical shunts and thereby enhance electroluminescence quantum efficiency in perovskite devices. In this method, a blend of perovskite and a polyimide precursor dielectric (PIP) is solution-deposited to form perovskite nanocrystals in a thin-film matrix of PIP. The PIP forms a pinhole-free charge-blocking layer, while still allowing the embedded perovskite crystals to form electrical contact with the electron- and hole-injection layers. This modified structure reduces nonradiative current losses and improves quantum efficiency by 2 orders of magnitude, giving an external quantum efficiency of 1.2%. This simple technique provides an alternative route to circumvent film formation problems in perovskite optoelectronics and offers the possibility of flexible and high-performance light-emitting displays.

Two-dimensional (2D) atomic-layered heterostructures stacked by van der Waals interactions recently introduced new research fields, which revealed novel phenomena and provided promising applications for electronic, optical, and optoelectronic devices. In this study, we report the van der Waals epitaxial growth of high-quality atomically thin Bi₂Se₃ on single crystalline hexagonal boron nitride (h-BN) by chemical vapor deposition. Although the in-plane lattice mismatch between Bi₂Se₃ and h-BN is approximately 65%, our transmission electron microscopy analysis revealed that Bi₂Se₃ single crystals epitaxially grew on h-BN with two commensurate states; that is, the (1̅21̅0) plane of Bi₂Se₃ was preferably parallel to the (1̅100) or (1̅21̅0) plane of h-BN. In the case of the Bi₂Se₃ (2̅110) ∥ h-BN (11̅00) state, the Moiré pattern wavelength in the Bi₂Se₃/h-BN superlattice can reach 5.47 nm. These naturally formed thin crystals facilitated the direct assembly of h-BN/Bi₂Se₃/h-BN sandwiched heterostructures without introducing any impurity at the interfaces for electronic property characterization. Our quantum capacitance (QC) measurements showed a compelling phenomenon of thickness-dependent topological phase transition, which was attributed to the coupling effects of two surface states from Dirac Fermions at/or above six quintuple layers (QLs) to gapped Dirac Fermions below six QLs. Moreover, in ultrathin Bi₂Se₃ (e.g., 3 QLs), we observed the midgap states induced by intrinsic defects at cryogenic temperatures. Our results demonstrated that QC measurements based on h-BN/Bi₂Se₃/h-BN sandwiched structures provided rich information regarding the density of states of Bi₂Se₃, such as quantum well states and Landau quantization. Our approach in fabricating h-BN/Bi₂Se₃/h-BN sandwiched device structures through the combination of bottom–up growth and top–down dry transferring techniques can be extended to other two-dimensional layered heterostructures.

Polytype nanodots are arguably the simplest nanodots than can be made, but their technological control was, up to now, challenging. We have developed a technique to produce nanowires containing exactly one polytype nanodot in GaAs with thickness control. These nanodots have been investigated by photoluminescence, which has been cross-correlated with transmission electron microscopy. We find that short (4–20 nm) zincblende GaAs segments/dots in wurtzite GaAs confine electrons and that the inverse system confines holes. By varying the thickness of the nanodots we find strong quantum confinement effects which allows us to extract the effective mass of the carriers. The holes at the top of the valence band have an effective mass of approximately 0.45 m₀ in wurtzite GaAs. The thinnest wurtzite nanodot corresponds to a twin plane in zincblende GaAs and gives efficient photoluminescence. It binds an exciton with a binding energy of roughly 50 meV, including central cell corrections.

Two-dimensional (2D) topological crystalline insulators (TCIs) were recently predicted in thin films of the SnTe class of IV–VI semiconductors, which can host metallic edge states protected by mirror symmetry. As thickness decreases, quantum confinement effect will increase and surpass the inverted gap below a critical thickness, turning TCIs into normal insulators. Surprisingly, based on first-principles calculations, here we demonstrate that (001) monolayers of rocksalt IV–VI semiconductors XY (X = Ge, Sn, Pb and Y = S, Se, Te) are 2D TCIs with the fundamental band gap as large as 260 meV in monolayer PbTe. This unexpected nontrivial topological phase stems from the strong crystal field effect in the monolayer, which lifts the degeneracy between p_x,y and p_z orbitals and leads to band inversion between cation p_z and anion p_x,y orbitals. This crystal field effect induced topological phase offers a new strategy to find and design other atomically thin 2D topological materials.

The greatly enhanced fields near metal nanoparticles have demonstrated remarkable optical properties and are promising for applications from solar energy to biosensing. However, direct experimental study of these light-matter interactions at the nanoscale has remained difficult due to the limitations of optical microscopy. Here, we use single-molecule fluorescence imaging to probe how a plasmonic nanoantenna modifies the fluorescence emission from a dipole emitter. We show that the apparent fluorophore emission position is strongly shifted upon coupling to an antenna and that the emission of dyes located up to 90 nm away is affected by this coupling. To predict this long-ranged effect, we present a framework based on a distance-dependent partial coupling of the dye emission to the antenna. Our direct interpretation of these light-matter interactions will enable more predictably optimized, designed, and controlled plasmonic devices and will permit reliable plasmon-enhanced single-molecule nanoscopy.

Novel lithium metal polymer solid state batteries with nano C-LiFePO₄ and nano Li_1.2V₃O₈ counter-electrodes (average particle size 200 nm) were studied for the first time by in situ SEM and impedance during cycling. The kinetics of Li-motion during cycling is analyzed self-consistently together with the electrochemical properties. We show that the cycling life of the nano Li_1.2V₃O₈ is limited by the dissolution of the vanadium in the electrolyte, which explains the choice of nano C-LiFePO₄ (1300 cycles at 100% DOD): with this olivine, no dissolution is observed. In combination with lithium metal, at high loading and with a stable SEI an ultrahigh energy density battery was thus newly developed in our laboratory.

We report a remotely mediated and fast responsive plasmonic–magnetic nanorod array with extremely large variability in optical appearance (up to 100 nm shifts in scattering maxima) and concurrently for multiple wavelengths in a broad range from UV–vis to near-infrared (at 450, 550, and 670 nm) with an external magnetic field with variable direction. The observed phenomenon demonstrates a rapid, wide-range response controlled via a noninvasive remote stimulus. The remotely controlled system suggested here is a magnetic field-directed assembly of an ordered monolayer array of unipolar oriented magnetic–plasmonic nickel–gold nanorods flexibly hinged to a sticky substrate. The unique geometry of the mobile nanorod array allows for the instant alteration of the surface plasmon polariton modes in the gold segment of the controllably tilting nanorods. This design demonstrates the utility of hybrid bimetallic nanoparticles and gives a novel approach to the design of fast-acting, remotely controlled color-changing nanomaterials for sensing and interfacial transport.

We conduct spectroscopic and theoretical studies of photoluminescence (PL) from Ge quantum dots (QDs) fabricated via colloidal synthesis. The dynamics of late-time PL exhibit a pronounced dependence on temperature and applied magnetic field, which can be explained by radiative decay involving two closely spaced, slowly emitting exciton states. In 3.5 nm QDs, these states are separated by ∼1 meV and are characterized by ∼82 μs and ∼18 μs lifetimes. By using a four-band formalism, we calculate the fine structure of the indirect band-edge exciton arising from the electron–hole exchange interaction and the Coulomb interaction of the Γ-point hole with the anisotropic charge density of the L-point electron. The calculations suggest that the observed PL dynamics can be explained by phonon-assisted recombination of excitons thermally distributed between the lower-energy “dark” state with the momentum projection J = ± 2 and a higher energy “bright” state with J = ± 1. A fairly small difference between lifetimes of these states is due to their mixing induced by the exchange term unique to crystals with a highly symmetric cubic lattice such as Ge.

Fast and efficient transport of molecular cargoes along tracks or on supramolecular platforms is an important prerequisite for the development of future nanorobotic systems and assembly lines. Here, we study the diffusive transport of DNA cargo strands bound to a supramolecular DNA origami structure via an extended tether arm. For short distances (on the order of a few nanometers), transport from a start to a target site is found to be less efficient than for direct transfer without tether. For distances on the scale of the origami platform itself, however, cargo transfer mediated by a rigid tether arm occurs very fast and robust, whereas a more flexible, hinged tether is found to be considerably less efficient. Our results suggest diffusive motion on a molecular tether as a highly efficient mechanism for fast transfer of cargoes over long distances.

Single-layer direct band gap semiconductors such as transition metal dichalcogenides are quite attractive for a wide range of electronics, photonics, and optoelectronics applications. Their monolayer thickness provides significant advantages in many applications such as field-effect transistors for high-performance electronics, sensor/detector applications, and flexible electronics. However, for optoelectronics and photonics applications, inherent monolayer thickness poses a significant challenge for the interaction of light with the material, which therefore results in poor light emission and absorption behavior. Here, we demonstrate enhanced light emission from large-area monolayer MoS₂ using plasmonic silver nanodisc arrays, where enhanced photoluminescence up to 12-times has been measured. Observed phenomena stem from the fact that plasmonic resonance couples to both excitation and emission fields and thus boosts the light–matter interaction at the nanoscale. Reported results allow us to engineer light–matter interactions in two-dimensional materials and could enable highly efficient photodetectors, sensors, and photovoltaic devices, where photon absorption and emission efficiency highly dictate the device performance.

Recent studies of the coupling between the plasmonic excitations of metallic nanostructures with the excitonic excitations of molecular species have revealed a rich variety of emergent phenomena known as plexcitonics. Here, we use a combined experimental and theoretical approach to demonstrate new and intriguing aspects in the ultrafast nonlinear responses of strongly coupled hybrid Fano systems consisting of gold nanorods decorated with near-infrared dye molecules. We show that the severely suppressed linear absorption around the Fano dip significantly enhances the unidirectional energy transfer from the plasmons to the excitons and further allows one-photon nonlinearity to be drastically and reversibly tuned. These striking observations are interpreted within a microscopic model stressing on two competing processes: saturated plasmonic absorption and weakened destructive Fano interference from the bleached excitonic absorption. The unusually strong one-photon nonlinearity revealed here provides a promising strategy in fabricating nanoplasmonic devices with both pronounced nonlinearities and good figures of merit.

A growth mode was revealed by an in situ TEM study of nucleation and growth of Au on Pt icosahedral nanoparticles. Quantitative analysis of growth kinetics was carried out based on real-time TEM data, which shows the process involves: (1) deposition of Au on corner sites of Pt icosahedral nanoparticles, (2) diffusion of Au from corners to terraces and edges, and (3) subsequent layer-by-layer growth of Au on Au surfaces to form Pt@Au core–shell nanoparticles. The in situ TEM results indicate diffusion of Au from corner islands to terraces and edges is a kinetically controlled growth, as evidenced by a measurement of diffusion coefficients for these growth processes. We demonstrated that in situ electron microscopy is a valuable tool for quantitative study of nucleation and growth kinetics and can provide new insight into the design and precise control of heterogeneous nanostructures.

The chemical composition of core–shell nanoparticle clusters have been determined through principal component analysis (PCA) and independent component analysis (ICA) of an energy-dispersive X-ray (EDX) spectrum image (SI) acquired in a scanning transmission electron microscope (STEM). The method blindly decomposes the SI into three components, which are found to accurately represent the isolated and unmixed X-ray signals originating from the supporting carbon film, the shell, and the bimetallic core. The composition of the latter is verified by and is in excellent agreement with the separate quantification of bare bimetallic seed nanoparticles.

H₂ generation under sunlight offers great potential for a sustainable fuel production system. To achieve high efficiency solar-to-hydrogen conversion, multijunction photoelectrodes have been commonly employed to absorb a large portion of the solar spectrum and to provide energetic charge carriers for water splitting. However, the design and performance of such tandem devices has been fundamentally limited by the current matching between various absorbing layers. Here, by exploiting the lateral carrier extraction scheme of one-dimensional nanowire structures, we have demonstrated that a dual absorber photocathode, consisting of p-InGaN/tunnel junction/n-GaN nanowire arrays and a Si solar cell wafer, can operate efficiently without the strict current matching requirement. The monolithically integrated photocathode exhibits an applied bias photon-to-current efficiency of 8.7% at a potential of 0.33 V versus normal hydrogen electrode and nearly unity Faradaic efficiency for H₂ generation. Such an adaptive multijunction architecture can surpass the design and performance restrictions of conventional tandem photoelectrodes.