Deciphering the Role of Water in Promoting the Optoelectronic Performance of Surface-Engineered Lead Halide Perovskite Nanocrystals.

Lead halide perovskites are promising candidates for high-performance light-emitting diodes (LEDs); however, their applicability is limited by their structural instability toward moisture. Although a deliberate addition of water to the precursor solution has recently been shown to improve the crystallinity and optical properties of perovskites, the corresponding thin films still do not exhibit a near-unity quantum yield. Herein, we report that the direct addition of a minute amount of water to post-treated formamidinium lead bromide (FAPbBr3) nanocrystals (NCs) substantially enhances the stability while achieving a 95% photoluminescence quantum yield in a NC thin film. We unveil the mechanism of how moisture assists in the formation of an additional NH4Br component. Alongside, we demonstrate the crucial role of moisture in assisting localized etching of the perovskite crystal, facilitating the partial incorporation of NH4+, which is key for improved performance under ambient conditions. Finally, as a proof-of-concept, the application of post-treated and water-treated perovskites is tested in LEDs, with the latter exhibiting a superior performance, offering opportunities toward commercial application in moisture-stable optoelectronics.

Au3-Decorated graphene as a sensing platform for O2 adsorption and desorption kinetics.

The adsorption and desorption kinetics of molecules is of significant fundamental and applied interest. In this paper, we present a new method to quantify the energy barriers for the adsorption and desorption of gas molecules on few-atom clusters, by exploiting reaction induced changes of the doping level of a graphene substrate. The method is illustrated for oxygen adsorption on Au3 clusters. The gold clusters were deposited on a graphene field effect transistor and exposed to O2. From the change in graphene's electronic properties during adsorption, the energy barrier for the adsorption of O2 on Au3 is estimated to be 0.45 eV. Electric current pulses increase the temperature of the graphene strip in a controlled way and provide the required thermal energy for oxygen desorption. The oxygen binding energy on Au3/graphene is found to be 1.03 eV and the activation entropy is 1.4 meV K-1. The experimental values are compared and interpreted on the basis of density functional theory calculations of the adsorption barrier, the binding energy and the activation entropy. The large value of the activation entropy is explained by the hindering effect that the adsorbed O2 has on the fluxional motion of the Au3 cluster.

Tunable Noninteger Flux Quantum of Vortices in Superconducting Strips.

Flux quantization has been widely regarded as the hallmark of the macroscopic quantum state of superconductivity. However, practical design of superconductor devices exploiting finite size confinement effects may induce exotic phenomena, including nonquantized vortices. In our research, the magnetic flux of vortices has been studied in a series of superconducting strips as a function of the strip width and the penetration depth. In both circumstances, the observation using scanning Hall probe microscope (SHPM) displays a controlled evolution from singly quantized vortices to nonquantized ones. It is also found that the magnetic flux is immune to the flowing supercurrent. The simulations based on Ginzburg-Landau theory agree well with experimental results. The observed behavior of the vortex flux may open new perspectives for fundamental research and applications based on vortex matter, such as vortex-memory devices and magnetic field traps for ultracold atoms.

Interaction of graphene with Aunclusters: a first-principles study.

The interaction between Aun(n= 1-6) clusters and graphene is studied using first-principles simulations, based on density functional theory. The computed binding energy between Aunand graphene depends on the number of atoms in the cluster and lies between -0.6 eV and -1.7 eV, suggesting (weak) chemisorption of the clusters on graphene, rather than physisorption. Overall, the electronic properties, spin-orbit interaction and spin texture, as well as the transport properties of graphene strongly depend on the precise size of the Aunclusters. Doping of graphene is predicted for clusters with an odd number of Au atoms, due to overlap between Ausand carbonpzstates close to the Fermi level. On the other hand, there is no charge transfer between even size Au clusters and graphene, but a gap is formed at the Dirac cone, due to the breaking of the pseudo spin inversion symmetry of graphene's lattice. The adsorbed Aunclusters induce spin-orbit interactions as well as spin and pseudo spin interactions in graphene, as indicated by the splitting of the electronic band structure. A hedgehog spin texture is also predicted for adsorbed clusters with an even number of Au atoms. Ballistic transport simulations are performed to study the influence of the adsorbed clusters on graphene's electronic transport properties. The influence of the cluster on the electron transmission across the structure depends on the mixing of the valence orbitals in the transport energy window. In the specific case of the Au3/graphene system, the adsorbed clusters reduce the transmission and the conductance of graphene. The Au3clusters act as 'scattering centers' for charge carriers, in agreement with recent experimental studies.

Targeted modifications of monolithic multiterminal superconducting weak-links.

In a multi-branch metallic interconnect we demonstrate the possibility to induce targeted modifications of the material properties by properly selecting the intensity and polarity of the applied current. We illustrate this effect in Y-shape multiterminal devices made of Nb on sapphire for which we show that the superconducting critical current can be lowered in a controlled manner at a preselected junction. We further observe the gradual appearance of Fraunhofer-like critical current oscillations with magnetic field which indicates the gradual modification of a superconducting weak link. This method permits progressive modifications of a hand-picked junction without affecting the neighboring terminals. The proposed approach has the benefit of being inexpensive and requiring conventional electronics. This technique represents a major step toward all-electric control of multiterminal Josephson junctions.

Tuning the Structural and Optoelectronic Properties of Cs2 AgBiBr6 Double-Perovskite Single Crystals through Alkali-Metal Substitution.

Lead-free double perovskites have great potential as stable and nontoxic optoelectronic materials. Recently, Cs2 AgBiBr6 has emerged as a promising material, with suboptimal photon-to-charge carrier conversion efficiency, yet well suited for high-energy photon-detection applications. Here, the optoelectronic and structural properties of pure Cs2 AgBiBr6 and alkali-metal-substituted (Cs1- x Yx )2 AgBiBr6 (Y: Rb+ , K+ , Na+ ; x = 0.02) single crystals are investigated. Strikingly, alkali-substitution entails a tunability to the material system in its response to X-rays and structural properties that is most strongly revealed in Rb-substituted compounds whose X-ray sensitivity outperforms other double-perovskite-based devices reported. While the fundamental nature and magnitude of the bandgap remains unchanged, the alkali-substituted materials exhibit a threefold boost in their fundamental carrier recombination lifetime at room temperature. Moreover, an enhanced electron-acoustic phonon scattering is found compared to Cs2 AgBiBr6 . The study thus paves the way for employing cation substitution to tune the properties of double perovskites toward a new material platform for optoelectronics.

Two-dimensional perovskites with alternating cations in the interlayer space for stable light-emitting diodes.

Lead halide perovskites have attracted tremendous attention in photovoltaics due to their impressive optoelectronic properties. However, the poor stability of perovskite-based devices remains a bottleneck for further commercial development. Two-dimensional perovskites have great potential in optoelectronic devices, as they are much more stable than their three-dimensional counterparts and rapidly catching up in performance. Herein, we demonstrate high-quality two-dimensional novel perovskite thin films with alternating cations in the interlayer space. This innovative perovskite provides highly stable semiconductor thin films for efficient near-infrared light-emitting diodes (LEDs). Highly efficient LEDs with tunable emission wavelengths from 680 to 770 nm along with excellent operational stability are demonstrated by varying the thickness of the interlayer spacer cation. Furthermore, the best-performing device exhibits an external quantum efficiency of 3.4% at a high current density (J) of 249 mA/cm2 and remains above 2.5% for a J up to 720 mA cm-2, leading to a high radiance of 77.5 W/Sr m2 when driven at 6 V. The same device also shows impressive operational stability, retaining almost 80% of its initial performance after operating at 20 mA/cm2 for 350 min. This work provides fundamental evidence that this novel alternating interlayer cation 2D perovskite can be a promising and stable photonic emitter.

Room temperature single electron transistor based on a size-selected aluminium cluster.

Single electron transistors (SETs) are powerful devices to study the properties of nanoscale objects. However, the capabilities of placing a nano-object between electrical contacts under pristine conditions are lacking. Here, we developed a versatile two point contacting approach that tackles this challenge, which is demonstrated by constructing in situ a prototypical SET device consisting of a single aluminium cluster of 66 ± 5 atoms, deposited directly in a gold nanogap using an innovative cluster beam deposition technique. The gate driven conductance measurements demonstrate Coulomb blockade oscillations at room temperature correlating with an extracted charging energy of 0.14 eV, which is five times larger than kBT at 300 K. Our work provides a model SET device platform to probe the quantum features of nano-objects with high precision.

Restoring self-limited growth of single-layer graphene on copper foil via backside coating.

The growth of single-layer graphene (SLG) by chemical vapor deposition (CVD) on copper surfaces is very popular because of the self-limiting effect that, in principle, prevents the growth of few-layer graphene (FLG). However, the reproducibility of the CVD growth of homogeneous SLG remains a major challenge, especially if one wants to avoid heavy surface treatments, monocrystalline substrates and expensive equipment to control the atmosphere inside the growth system. We demonstrate here that backside tungsten coating of copper foils allows for the exclusive growth of SLG with full coverage by atmospheric pressure CVD implemented in a vacuum-free furnace. We show that the absence of FLG patches is related to the suppression of carbon diffusion through copper. In the perspective of large-scale production of graphene, this approach constitutes a significant improvement to the traditional CVD growth process since (1) a tight control of the hydrocarbon flow is no longer required to avoid FLG formation and, consequently, (2) the growth duration necessary to reach full coverage can be drastically shortened.

Nano-SQUIDs with controllable weak links created via current-induced atom migration.

As the most sensitive magnetic field sensor, the superconducting quantum interference device (SQUID) became an essential component in many applications due to its unmatched performance. Through recently achieved miniaturization, using state-of-the-art fabrication methods, this fascinating device extended its functionality and became an important tool in nanomaterial characterization. Here, we present an accessible and yet powerful technique of targeted atom displacement in order to reduce the size of the weak links of a DC nano-SQUID beyond the limits of conventional lithography. The controllability of our protocol allows us to characterize in situ the full superconducting response after each electromigration step. From this in-depth analysis, we reveal an asymmetric evolution of the weak links at cryogenic temperatures. A comparison with time resolved scanning electron microscopy images of the atom migration process at room temperature confirms the peculiar asymmetric evolution of the parallel constrictions. Moreover, we observe that when electromigration has sufficiently reduced the junction's cross section, superconducting phase coherence is attained in the dissipative state, where magnetic flux readout from voltage becomes possible.

Controlled electromigration protocol revised.

Electromigration has evolved from an important cause of failure in electronic devices to an appealing method, capable of modifying the material properties and geometry of nanodevices. Although this technique has been successfully used by researchers to investigate low dimensional systems and nanoscale objects, its low controllability remains a serious limitation. This is in part due to the inherent stochastic nature of the process, but also due to the inappropriate identification of the relevant control parameters. In this study, we identify a suitable process variable and propose a novel control algorithm that enhances the controllability and, at the same time, minimizes the intervention of an operator. As a consequence, the algorithm facilitates the application of electromigration to systems that require exceptional control of, for example, the width of a narrow junction. It is demonstrated that the electromigration rate can be stabilized on pre-set values, which eventually defines the final geometry of the electromigrated structures.

In situ tailoring of superconducting junctions via electro-annealing.

We demonstrate the in situ engineering of superconducting nanocircuitry by targeted modulation of material properties through high applied current densities. We show that the sequential repetition of such customized electro-annealing in a niobium (Nb) nanoconstriction can broadly tune the superconducting critical temperature Tc and the normal-state resistance Rn in the targeted area. Once a sizable Rn is reached, clear magneto-resistance oscillations are detected along with a Fraunhofer-like field dependence of the critical current, indicating the formation of a weak link but with further adjustable characteristics. Advanced Ginzburg-Landau simulations fully corroborate this picture, employing the detailed parametrization from the electrical characterization and high resolution electron microscope images of the region within the constriction where the material has undergone amorphization by electro-annealing.

Electrically Driven Unidirectional Optical Nanoantennas.

Directional antennas revolutionized modern day telecommunication by enabling precise beaming of radio and microwave signals with minimal loss of energy. Similarly, directional optical nanoantennas are expected to pave the way toward on-chip wireless communication and information processing. Currently, on-chip integration of such antennas is hampered by their multielement design or the requirement of complicated excitation schemes. Here, we experimentally demonstrate electrical driving of in-plane tunneling nanoantennas to achieve broadband unidirectional emission of light. Far-field interference, as a result of the spectral overlap between the dipolar emission of the tunnel junction and the fundamental quadrupole-like resonance of the nanoantenna, gives rise to a directional radiation pattern. By tuning this overlap using the applied voltage, we record directivities as high as 5 dB. In addition to electrical tunability, we also demonstrate passive tunability of the directivity using the antenna geometry. These fully configurable electrically driven nanoantennas provide a simple way to direct optical energy on-chip using an extremely small device footprint.

Decorating graphene with size-selected few-atom clusters: a novel approach to investigate graphene-adparticle interactions.

We investigated the interaction between size-selected Au2 and Au3 clusters and graphene. Hereto preformed clusters are deposited on graphene field-effect transistors, a novel approach which offers a high control over the number of atoms per cluster, the deposition energy and the deposited density. The induced p-doping and charge carrier scattering indicate that a major part of the deposited clusters remains on the graphene flake as either individual or sub-nm coalesced entities. This is independently confirmed by scanning electron microscopy on the same devices after current annealing. Our novel approach provides perspectives for the electronic sensing of metallic clusters down to their atom-by-atom size-specific properties, and exploiting the tunability of clusters for tailoring desired properties in graphene.

Statistics of localized phase slips in tunable width planar point contacts.

The main dissipation mechanism in superconducting nanowires arises from phase slips. Thus far, most of the studies focus on long nanowires where coexisting events appear randomly along the nanowire. In the present work we investigate highly confined phase slips at the contact point of two superconducting leads. Profiting from the high current crowding at this spot, we are able to shrink in-situ the nanoconstriction. This procedure allows us to investigate, in the very same sample, thermally activated phase slips and the probability density function of the switching current Isw needed to trigger an avalanche of events. Furthermore, for an applied current larger than Isw, we unveil the existence of two distinct thermal regimes. One corresponding to efficient heat removal where the constriction and bath temperatures remain close to each other, and another one in which the constriction temperature can be substantially larger than the bath temperature leading to the formation of a hot spot. Considering that the switching current distribution depends on the exact thermal properties of the sample, the identification of different thermal regimes is of utmost importance for properly interpreting the dissipation mechanisms in narrow point contacts.

Nanoscale assembly of superconducting vortices with scanning tunnelling microscope tip.

Vortices play a crucial role in determining the properties of superconductors as well as their applications. Therefore, characterization and manipulation of vortices, especially at the single-vortex level, is of great importance. Among many techniques to study single vortices, scanning tunnelling microscopy (STM) stands out as a powerful tool, due to its ability to detect the local electronic states and high spatial resolution. However, local control of superconductivity as well as the manipulation of individual vortices with the STM tip is still lacking. Here we report a new function of the STM, namely to control the local pinning in a superconductor through the heating effect. Such effect allows us to quench the superconducting state at nanoscale, and leads to the growth of vortex clusters whose size can be controlled by the bias voltage. We also demonstrate the use of an STM tip to assemble single-quantum vortices into desired nanoscale configurations.

Determination of the spin-lifetime anisotropy in graphene using oblique spin precession.

We determine the spin-lifetime anisotropy of spin-polarized carriers in graphene. In contrast to prior approaches, our method does not require large out-of-plane magnetic fields and thus it is reliable for both low- and high-carrier densities. We first determine the in-plane spin lifetime by conventional spin precession measurements with magnetic fields perpendicular to the graphene plane. Then, to evaluate the out-of-plane spin lifetime, we implement spin precession measurements under oblique magnetic fields that generate an out-of-plane spin population. We find that the spin-lifetime anisotropy of graphene on silicon oxide is independent of carrier density and temperature down to 150 K, and much weaker than previously reported. Indeed, within the experimental uncertainty, the spin relaxation is isotropic. Altogether with the gate dependence of the spin lifetime, this indicates that the spin relaxation is driven by magnetic impurities or random spin-orbit or gauge fields.

Thermal and quantum depletion of superconductivity in narrow junctions created by controlled electromigration.

Superconducting nanowires currently attract great interest due to their application in single-photon detectors and quantum-computing circuits. In this context, it is of fundamental importance to understand the detrimental fluctuations of the superconducting order parameter as the wire width shrinks. In this paper, we use controlled electromigration to narrow down aluminium nanoconstrictions. We demonstrate that a transition from thermally assisted phase slips to quantum phase slips takes place when the cross section becomes less than ∼150 nm(2). In the regime dominated by quantum phase slips the nanowire loses its capacity to carry current without dissipation, even at the lowest possible temperature. We also show that the constrictions exhibit a negative magnetoresistance at low-magnetic fields, which can be attributed to the suppression of superconductivity in the contact leads. These findings reveal perspectives of the proposed fabrication method for exploring various fascinating superconducting phenomena in atomic-size contacts.

Dynamic visualization of nanoscale vortex orbits.

Due to the atomic-scale resolution, scanning tunneling microscopy is an ideal technique to observe the smallest objects. Nevertheless, it suffers from very long capturing times in order to investigate dynamic processes at the nanoscale. We address this issue, for vortex matter in NbSe2, by driving the vortices using an ac magnetic field and probing the induced periodic tunnel current modulations. Our results reveal different dynamical modes of the driven vortex lattices. In addition, by recording and synchronizing the time evolution of the tunneling current at each pixel, we visualize the overall dynamics of the vortex lattice with submillisecond time resolution and subnanometer spatial resolution.