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Metal-oxide semiconductors (MOS) are widely utilized for catalytic and photocatalytic applications in which the dynamics of charged carriers (e.g., electrons, holes) play important roles. Under operation conditions, photoinduced surface oxygen vacancies (PI-SOV) can greatly impact the dynamics of charge carriers. However, current knowledge regarding the effect of PI-SOV on the dynamics of hole migration in MOS films, such as titanium dioxide, is solely based upon volume-averaged measurements and/or vacuum conditions. This limits the basic understanding of hole-vacancy interactions, as they are not capable of revealing time-resolved variations during operation. Here, we measured the effect of PI-SOV on the dynamics of hole migration using time-resolved atomic force microscopy. Our findings demonstrate that the time constant associated with hole migration is strongly affected by PI-SOV, in a reversible manner. These results will nucleate an insightful understanding of the physics of hole dynamics and thus enable emerging technologies, facilitated by engineering hole-vacancy interactions.

Nanoscale oxide layer protected semiconductor photoelectrodes show enhanced stability and performance for solar fuels generation, although the mechanism for the performance enhancement remains unclear due to a lack of understanding of the microscopic interfacial field and its effects. Here, we directly probe the interfacial fields at p-GaP electrodes protected by n-TiO2 and its effect on charge carriers by transient reflectance spectroscopy. Increasing the TiO2 layer thickness from 0 to 35 nm increases the field in the GaP depletion region, enhancing the rate and efficiency of interfacial electron transfer from the GaP to TiO2 on the ps time scale as well as retarding interfacial recombination on the microsecond time scale. This study demonstrates a general method for providing a microscopic view of the photogenerated charge carrier's pathway and loss mechanisms from the bulk of the electrode to the long-lived separated charge at the interface that ultimately drives the photoelectrochemical reactions.

Polarity often refers to the charge carrier type of a semiconductor or the charging state of a functional group, generally dominating their functionality and performance. Herein we uncover a spontaneous and stochastic polarity-flipping phenomenon in monolayer WSe2, which randomly switches between the n-type and p-type states and is essentially triggered by fluctuating carrier flows from or to the adjacent WS2 monolayer. We have traced such fluctuating carrier flows by interfacial photocurrent measurements in a zero-bias two-terminal device. Such polarity flipping results in switching between the negative and positive correlations between the emission intensities of WS2 and WSe2 in the heterobilayer, which is further well-controlled by the electrostatic gate-tuning experiments in a capacitor-structure device. Our work not only demonstrates giant and intermittent carrier flows through long-range coupling in 2D heterostructures and a consequent spontaneous polarity flipping phenomenon but also provides a two-emitter system with a switchable correlation sign that could project future applications in optical logic devices.

Despite the great appeal of two-dimensional semiconductors for electronics and optoelectronics, to achieve the required charge carrier concentrations by means of chemical doping remains a challenge due to large defect ionization energies (IEs). Here, by decomposing the defect IEs into three parts based on ionization process, we propose a conceptual picture that the large defect IEs are caused by two effects of reduced dimensionality. While the quantum confinement effect makes the neutral single-electron point defect levels deep, the reduced screening effect leads to high energy cost for the electronic relaxation. The first-principles calculations for black phosphorus and MoS2 do demonstrate the general trend. Using BP monolayer either embedded into dielectric continuum or encapsulated between two hBN layers, we demonstrate the feasibility of increasing the screening to reduce the defect IEs. Our analysis is expected to help achieve effective carrier doping and open ways toward more extensive applications of 2D semiconductors.

Layered semiconducting transition metal dichalcogenides (TMDs) are promising materials for high-specific-power photovoltaics due to their excellent optoelectronic properties. However, in practice, contacts to TMDs have poor charge carrier selectivity, while imperfect surfaces cause recombination, leading to a low open-circuit voltage (VOC) and therefore limited power conversion efficiency (PCE) in TMD photovoltaics. Here, we simultaneously address these fundamental issues with a simple MoOx (x ≈ 3) surface charge-transfer doping and passivation method, applying it to multilayer tungsten disulfide (WS2) Schottky-junction solar cells with initially near-zero VOC. Doping and passivation turn these into lateral p-n junction photovoltaic cells with a record VOC of 681 mV under AM 1.5G illumination, the highest among all p-n junction TMD solar cells with a practical design. The enhanced VOC also leads to record PCE in ultrathin (2 photovoltaics. This easily scalable doping and passivation scheme is expected to enable further advances in TMD electronics and optoelectronics.

In a Fe/(Cd,Mg)Te/CdTe quantum well hybrid structure, short-range and long-range ferromagnetic proximity effects are found to coexist. The former is observed for conduction band electrons, while the latter is observed for holes bound to shallow acceptors in the CdTe quantum well. These effects arise from the interaction of charge carriers confined in the quantum well with different ferromagnets, where electrons interact with the Fe film and holes with an interfacial ferromagnet at the Fe/(Cd,Mg)Te interface. The two proximity effects originate from fundamentally different physical mechanisms. The short-range proximity effect for electrons is determined by the overlap of their wave functions with d-electrons of the Fe film. On the contrary, the long-range effect for holes bound to acceptors is not associated with overlapping wave functions and can be mediated by elliptically polarized phonons. The coexistence of the two ferromagnetic proximity effects reveals the presence of a nontrivial spin texture within the same heterostructure.

Natural photosynthesis relies on a sophisticated charge transfer pathway among multiple components with precise spatial, energetic, and temporal organizations in the aqueous environment. It continues to inspire and challenge the design and fabrication of artificial multicomponent colloidal nanostructures for solar-to-fuel conversion. Herein, we introduce a plasmonic photocatalyst synthesized with colloidal methods with five integrated components including cocatalysts installed in orthogonal locations. The precise deposition of individual inorganic components on an Au/TiO2 nanodumbell nanostructure is enabled by photoreduction and photo-oxidation, which selectively occurs at the TiO2 tip sites and Au lateral sites, respectively. Under visible-light irradiation, the photocatalyst exhibited activity of oxygen evolution from water without scavengers. We demonstrate that each component is essential for improving the photocatalytic performance. In addition, mechanistic studies suggest that the photocatalytic reaction requires combining the hot charge carriers derived from exciting both the d-sp interband transition and the localized surface plasmon resonance of Au.

When aliovalent dopants are sufficiently segregated to the core or near the surface of semiconductor nanocrystals, charge carriers donated by the dopants are also segregated to the core or near the surface, respectively. In Sn-doped indium oxide nanocrystals, we find that this contrast in free charge carrier concentration creates a core and shell with differing dielectric properties and results in two distinctly observable plasmonic extinction peaks. The trends in this dual-mode optical response with shell growth differ from core/shell nanoparticles composed of traditional plasmonic metals such as Au and Ag. We developed a model employing a core/shell effective medium approximation that can fit the dual-mode spectra and explain the trends in the extinction response. Lastly, we show that dopant segregation can improve sensitivity of plasmon spectra to changes in refractive index of the surrounding environment.

Quantum spin Hall (QSH) insulators are materials that feature an insulating bulk and host edge states protected by time-reversal symmetry. The helical locking of spin and momentum in these states suppresses backscattering of charge carriers, promising applications from low-power electronics to quantum computing. A major challenge for applications is the identification of large gap QSH materials, which would enable room temperature dissipationless transport in their edge states. Here we show that the layered mineral jacutingaite (Pt$_2$HgSe$_3$) is a candidate QSH material, realizing the long sought after the Kane-Mele insulator. Using scanning tunneling microscopy, we measure a band gap of 110 meV, above room temperature, and identify the hallmark edge states. By calculating the $\mathbb{Z}_2$ invariant, we confirm the topological nature of the gap. Being a layered mineral, it is stable in air and can be thinned down to a few atomic layers by mechanical exfoliation. Furthermore, we demonstrate that it can be integrated into heterostructures with other two-dimensional materials. This adds a topological insulator to the 2D quantum material library, greatly expanding the possibilities for tuning 2D electron systems using stacks of layered materials.

Auger recombination in semiconductors is a many-body phenomenon in which recombination of electrons and holes is accompanied by excitation of other charge carriers. Being nonradiative, it is detrimental to light emission. The excess energy of the excited carriers is normally rapidly converted to heat, making Auger processes difficult to probe directly. Here, we employ a technique in which the Auger-excited carriers are detected by their ability to tunnel out of the semiconductor through a thin barrier, generating a current. We employ vertical van der Waals (vdW) heterostructures with monolayer WSe2 as the semiconductor and the wide band gap hexagonal boron nitride (hBN) as the tunnel barrier to preferentially transmit high-energy Auger-excited carriers to a graphite electrode. The unambiguous signatures of Auger processes are a rise in the photocurrent when excitons are created by resonant excitation, and negative differential photoconductance resulting from the shifts of the exciton resonances with voltage. We detect holes Auger-excited by both neutral and charged excitons, and find that the Auger scattering is surprisingly strong under weak excitation. The selective extraction of Auger carriers at low, controlled carrier densities that is enabled by vdW heterostructures illustrates an important addition to the techniques available for probing relaxation processes in 2D materials.

Lead halide perovskites (LHPs) exhibit large spin-orbit coupling (SOC), leading to only twofold-degenerate valence and conduction bands and therefore allowing for efficient optical orientation. This makes them ideal materials to study charge carrier spins. With this study we elucidate the spin dynamics of photoexcited charge carriers and the underlying spin relaxation mechanisms in CsPbI3 nanocrystals by employing time-resolved differential transmission spectroscopy (DTS). We find that the photoinduced spin polarization significantly diminishes during thermalization and cooling toward the energetically favorable band edge. Temperature-dependent DTS reveals a decay in spin polarization that is more than 1 order of magnitude faster at room temperature (3 ps) than at cryogenic temperatures (32 ps). We propose that spin relaxation of free charge carriers in large-SOC materials like LHPs occurs as a result of carrier-phonon scattering, as described by the Elliott-Yafet mechanism.

Understanding the electronic structure and dynamics of semiconducting nanomaterials at the atomic level is crucial for the realization and optimization of devices in solar energy, catalysis, and optoelectronic applications. We report here on the use of ultrafast X-ray linear dichroism spectroscopy to monitor the carrier dynamics in epitaxial ZnO nanorods after band gap photoexcitation. By rigorously subtracting out thermal contributions and conducting ab initio calculations, we reveal an overall depletion of absorption cross sections in the transient X-ray spectra caused by photogenerated charge carriers screening the core-hole potential of the X-ray absorbing atom. At low laser excitation densities, we observe phase-space filling by excited electrons and holes separately. These results pave the way for carrier- and element-specific probing of charge transfer dynamics across heterostructured interfaces with ultrafast table-top and fourth-generation X-ray sources.

We combine state-of-the-art ultrafast photoluminescence and absorption spectroscopy and nonadiabatic molecular dynamics simulations to investigate charge-carrier cooling in CsPbBr3 nanocrystals over a very broad size regime, from 0.8 to 12 nm. Contrary to the prevailing notion that polaron formation slows down charge-carrier cooling in lead-halide perovskites, no suppression of carrier cooling is observed in CsPbBr3 nanocrystals except for a slow cooling (over ∼10 ps) of "warm" electrons in the vicinity (within ∼0.1 eV) of the conduction band edge. At higher excess energies, electrons and holes cool with similar rates, on the order of 1 eV ps-1 carrier-1, increasing weakly with size. Our ab initio simulations suggest that cooling proceeds via fast phonon-mediated intraband transitions driven by strong and size-dependent electron-phonon coupling. The presented experimental and computational methods yield the spectrum of involved phonons and may guide the development of devices utilizing hot charge carriers.

Auger recombination is a nonradiative process, where the recombination energy of an electron-hole pair is transferred to a third charge carrier. It is a common effect in colloidal quantum dots that quenches the radiative emission with an Auger recombination time below nanoseconds. In self-assembled QDs, the Auger recombination has been observed with a much longer recombination time on the order of microseconds. Here, we use two-color laser excitation on the exciton and trion transition in resonance fluorescence on a single self-assembled quantum dot to monitor in real-time single quantum events of the Auger process. Full counting statistics on the random telegraph signal give access to the cumulants and demonstrate the tunability of the Fano factor from a Poissonian to a sub-Poissonian distribution by Auger-mediated electron emission from the dot. Therefore, the Auger process can be used to tune optically the charge carrier occupation of the dot by the incident laser intensity, independently from the electron tunneling from the reservoir by the gate voltage. Our findings are not only highly relevant for the understanding of the Auger process but also demonstrate the perspective of the Auger effect for controlling precisely the charge state in a quantum system by optical means.

Monolayer heterojunctions such as MoS2/WS2 are attractive for solar energy conversion applications because the interfacial electric field spatially separates charge carriers in less than 100 fs. Photoelectrochemical cells represent an intriguing platform to collect the spatially separated carriers. However, the recombination, transport, and interfacial charge transfer processes that take place following the ultrafast charge separation step have not been investigated. Here we demonstrate novel charge recombination and transport pathways in monolayer MoS2/WS2 photoelectrochemical cells by spatially resolving the net collection of carriers (i.e., the photocurrent) at the single nanosheet level. We discovered an excitation-wavelength-dependent recombination pathway that depends on the heterojunction stacking configuration and the carrier generation profile in the heterostructure. Photocurrent mapping measurements revealed that charge transport occurs parallel to the layers over micrometer-scale distances even though the indium tin oxide electrode and liquid electrolyte provide efficient charge extraction pathways via intimate electron- and hole-selective contacts. Our results reveal how composition heterogeneity influences the performance of bulk heterojunction electrodes made from randomly oriented nanosheets and provide critical insight into the design of efficient heterojunction photoelectrodes for solar energy conversion applications.

High-performance photodetectors operating in the near-infrared (0.75-1.4 μm) and short-wave infrared (1.4-3.0 μm) portion of the electromagnetic spectrum are key components in many optical systems. Here, we report on a combined experimental and theoretical study of square millimeter array infrared photodetectors comprising 3 million n+-i-n+ InP nanowires grown by MOVPE from periodically ordered Au seed particles. The nominal i-segment, comprising 20 InAs0.40P0.60 quantum discs, was grown by use of an optimized Zn doping to compensate the nonintentional n-doping. The photodetectors exhibit bias- and power-dependent responsivities reaching record-high values of 250 A/W at 980 nm/20 nW and 990 A/W at 532 nm/60 nW, both at 3.5 V bias. Moreover, due to the embedded quantum discs, the photoresponse covers a broad spectral range from about 0.70 to 2.5 eV, in effect outperforming conventional single InGaAs detectors and dual Si/Ge detectors. The high responsivity, and related gain, results from a novel proposed photogating mechanism, induced by the complex charge carrier dynamics involving optical excitation and recombination in the quantum discs and interface traps, which reduces the electron transport barrier between the highly doped n+ contact and the i-segment. The experimental results obtained are in perfect agreement with the proposed theoretical model and represent a significant step forward toward understanding gain in nanoscale photodetectors and realization of commercially viable broadband photon detectors with ultrahigh gain.

The optical extinction coefficients of localized surface plasmon resonance (LSPR) in doped semiconductor nanocrystals (NCs) have intensities determined by the density and damping mechanisms of free charge carriers. We investigate the dependence of the extinction coefficient of tin-doped indium oxide (ITO) NCs on size and dopant concentration and find extinction coefficients as high as 56.6 μm-1 in the near-infrared for 20 nm diameter ITO NCs with 7.5 atomic% Sn. We find ITO NCs to be more efficient infrared light absorbers than metal nanoparticles or molecular dyes. We also find the intensive, volume-normalized extinction coefficient increases significantly with NC doping and NC diameter, but only up to the point of saturation in both cases. We qualitatively analyze trends in LSPR peak position and width to explain the effect of doping and size on extinction.

The knowledge of the phonon coherence length is of great importance for two-dimensional-based materials since phonons can limit the lifetime of charge carriers and heat dissipation. Here we use tip-enhanced Raman spectroscopy (TERS) to measure the spatial correlation length Lc of the A1g1 and A1g2 phonons of monolayer and few-layer gallium sulfide (GaS). The differences in Lc values are responsible for different enhancements of the A1g modes, with A1g1 always enhancing more than the A1g2, independently of the number of GaS layers. For five layers, the results show an Lc of 64 and 47 nm for A1g1 and A1g2, respectively, and the coherence lengths decrease when decreasing the number of layers, indicating that scattering with the surface roughness plays an important role.

We report a comprehensive study of the impact of the structural properties in radial GaAs-Al0.3Ga0.7As nanowire-quantum well heterostructures on the optical recombination dynamics and electrical transport properties, emphasizing particularly the role of the commonly observed variations of the quantum well thickness at different facets. Typical thickness fluctuations of the radial quantum well observed by transmission electron microscopy lead to pronounced localization. Our optical data exhibit clear spectral shifts and a multipeak structure of the emission for such asymmetric ring structures resulting from spatially separated, yet interconnected quantum well systems. Charge carrier dynamics induced by a surface acoustic wave are resolved and prove efficient carrier exchange on native, subnanosecond time scales within the heterostructure. Experimental findings are corroborated by theoretical modeling, which unambiguously show that electrons and holes localize on facets where the quantum well is the thickes...

Terahertz (THz) photoconductive devices are used for generation, detection, and modulation of THz waves, and they rely on the ability to switch electrical conductivity on a subpicosecond time scale using optical pulses. However, fast and efficient conductivity switching with high contrast has been a challenge, because the majority of photoexcited charge carriers in the switch do not contribute to the photocurrent due to fast recombination. Here, we improve efficiency of electrical conductivity switching using a network of electrically connected nanoscale GaAs resonators, which form a perfectly absorbing photoconductive metasurface. We achieve perfect absorption without incorporating metallic elements, by breaking the symmetry of cubic Mie resonators. As a result, the metasurface can be switched between conductive and resistive states with extremely high contrast using an unprecedentedly low level of optical excitation. We integrate this metasurface with a THz antenna to produce an efficient photoconductive THz detector. The perfectly absorbing photoconductive metasurface opens paths for developing a wide range of efficient optoelectronic devices, where required optical and electronic properties are achieved through nanostructuring the resonator network.

Ultrathin photovoltaics made of MoS2 or WSe2 have the potential to convert solar energy to electricity with high efficiency because all photogenerated carriers are produced at a charge-collecting interface. However, solid-state monolayer photovoltaic devices typically require that charge carriers travel parallel to, instead of perpendicular to, the three atom-thick material toward charge-collecting contacts. Parallel charge transport across long distances decreases energy conversion efficiency. Here we demonstrate proof-of-concept monolayer and bilayer TMD|I–,I3–|Pt photoelectrochemical solar cells that use a conformal liquid electrolyte junction for efficient perpendicular charge transport over significantly larger active areas than solid state systems. Efficient perpendicular charge transport is evidenced by high peak internal quantum efficiencies (IQE) of 44.2, 9.1, and 10.5% for 0.4 mm2 MoS2, WSe2, and MoS2/WSe2 domains in a predominantly monolayer MoS2/WSe2 film. The monochromatic energy conversion e...

Control over the charge states of color centers in solids is necessary in order to fully utilize them in quantum technologies. However, the microscopic charge dynamics of deep defects in wide-bandgap semiconductors are complex, and much remains unknown. Here, we utilize single shot charge state readout of an individual nitrogen-vacancy (NV) center to probe charge dynamics of the surrounding defects in diamond. We show that the NV center charge state can be converted through the capture of holes produced by optical illumination of defects many microns away. With this method, we study the optical charge conversion of silicon-vacancy (SiV) centers and provide evidence that the dark state of the SiV center under optical illumination is SiV2-. These measurements illustrate that charge carrier generation, transport, and capture are important considerations in the design and implementation of quantum devices with color centers, and provide a novel way to probe and control charge dynamics in diamond., Comment: Main text: 18 pages, 4 figures, 32 references. Supporting Information: 20 pages, 9 figures, 2 tables, 12 references

Quantum states in graphene are four-fold degenerate: two fold in spins, and two fold in valleys.Both degrees of freedom can be utilized for qubit preparations. In our bilayer graphene quantumdots, we demonstrate that the valley g-factorgv, defined analogously as the spin g-factorgsforvalley splitting in perpendicular magnetic field, is tunable by over a factor of 4 from 20 to 90. Wefind that largergvresults from larger electronic dot sizes, determined from the charging energy.This control is achieved by adjusting voltages on merely two gates, which also allows for tuning ofthe dot-lead tunnel coupling. On our versatile device, bipolar operation, charging our quantum dotwith charge carriers of the same or the opposite polarity as the leads, can be performed. Dots ofboth polarity are tunable to the first charge carrier by action of the plunger gate, such that thetransition from an electron to a hole dot can be observed. By adding more gates, this system caneasily be extended to host double dots., Comment: 10 pages, 7 figures

Central to spintronics is the interconversion between electronic charge and spin currents, and this can arise from the chirality-induced spin selectivity (CISS) effect. CISS is often studied as magnetoresistance (MR) in two-terminal (2T) electronic nanodevices containing a chiral (molecular) component and a ferromagnet. However, fundamental understanding of when and how this MR can occur is lacking. Here, we uncover an elementary mechanism that generates such an MR for nonlinear response. It requires energy-dependent transport and energy relaxation within the device. The sign of the MR depends on chirality, charge carrier type, and bias direction. Additionally, we reveal how CISS can be detected in the linear response regime in magnet-free 2T nanodevices, either by forming a chirality-based spin-valve using two or more chiral components or by Hanle spin precession in devices with a single chiral component. Our results provide operation principles and design guidelines for chirality-based spintronic nanodevices and technologies.

Core-shell semiconductor quantum dots (QDs) are one of the biggest nanotechnology successes so far. In particular, type-I QDs with straddling band offset possess the ability to enhance the charge carriers capturing which is useful for memory application. Here, the type-I core-shell QD-based bipolar resistive switching (RS) memory with anomalous multiple SET and RESET processes was demonstrated. The synergy and competition between space charge limited current conduction (arising from charge trapping in potential well of type-I QDs) and electrochemical metallization (ECM, originating from redox reaction of Ag electrode) process were employed for modulating the RS behavior. Through utilizing stochastic RS mechanisms in QD-based devices, four situations of RS behaviors can be classified into three states in Markov chain for implementing the application of a true random number generator. Furthermore, a 6 × 6 cross-bar array was demonstrated to realize the generation of random letters with case distinction.

Although solution processing methods provide an attractive route toward development of low-cost functional materials, these accessible fabrication approaches can engender high concentrations of microscopic structural defects that are detrimental to performance. In lead halide perovskites, structural disorder derived from solution processing has been implicated as an important determiner of photophysical properties. However, a direct correlation between the functional properties of these materials and the local crystal structure in which non-equilibrium states evolve has remained elusive, in part because structural heterogeneities occur on length scales that defy conventional characterization techniques. To address this knowledge gap, we have combined ultrafast pump-probe microscopy and electron backscattering diffraction to directly correlate charge carrier transport with the local diffraction pattern contrast, an indicator of crystal quality. Spatial correlation of these measurements strongly suggests that even on individual single crystal CsPbBr

Heterogeneous integration of semiconductors combines the functionality of different materials, enabling technologies such as III-V lasers and solar cells on silicon and GaN LEDs on sapphire. However, threading dislocations generated during the epitaxy of these dissimilar materials remain a key obstacle to the success of this approach due to reduced device efficiencies and reliability. Strategies to alleviate this and understand charge carrier recombination at threading dislocations now need an accurate description of the structure of threading dislocations in semiconductor heterostructures. We show that the composition around threading dislocations in technologically important InGaAs/GaAs/Ge/Si heterostructures are indeed different from that of the matrix. Site-specific atom probe tomography enabled by electron channeling contrast imaging reveals this at individual dislocations. We present evidence for the simultaneous fast diffusion of germanium and indium up and down a dislocation, respectively, leading to unique compositional profiles. We also detect the formation of clusters of metastable composition at the interface between Ge and GaAs, driven by intermixing in these two nearly immiscible materials. Together, our results have important implications for the properties of dislocations and interfaces in semiconductors and provide new tools for their study.

Strong light absorbing properties, and the ability to drive electrochemical reactions on their surface has sparked, allow plasmonic metal nanoparticles to serve as photocatalysts. After plasmon excitation, hot charge carriers are generated in the metal nanoelectrode, driving electrochemical reactions. To achieve plasmonic photocatalysis, the hot charge carriers must be harnessed before they decay by giving off heat to the surroundings. Here, we demonstrate the role of photogenerated hot holes in oxidative electrodissolution of individual gold nanorods in chloride electrolyte. We monitor the plasmon resonance spectroscopically using snapshot hyperspectral imaging with millisecond time resolution, while electrochemically tuning charge carrier density. We show that light induced hot charge carriers enhance the rate of gold oxidation and subsequent electrodissolution tenfold. Importantly, we find that hot holes generated from interband transitions compared to holes in the sp-band around the Fermi level contribute to electro-oxidation. We further show that the reaction onset potential cannot be lowered below the chloride onset potential, demonstrating that electrochemical mediation is required. These results provide new insights into hot hole driven photocatalysis while emphasizing the need for statistical descriptions of electrochemical non-equilibrium processes on innately heterogeneous nanoparticle supports. Figure: Schematic representation of experimental setup and mechanism. a: when positive potentials are applied while illuminating the nanoparticle, the scattering intensity and hence volume of the nanoparticle decreases (see inset). b: photo-generated hot holes inject into the HOMO of adsorbed chloride. Figure 1

With exceptional charge carrier mobilities and a direct bandgap at most thicknesses, indium selenide (InSe) is an emerging layered semiconductor that has generated significant interest for electronic and optoelectronic applications. However, exfoliated InSe nanosheets are susceptible to rapid degradation in ambient conditions, thus limiting their technological potential. In addition to morphological changes upon ambient exposure, the mobilities and current modulation on/off ratios of InSe transistors, as well as the responsivities of InSe photodetectors, decrease by over 3 orders of magnitude within 12 h of ambient exposure. In an effort to mitigate these deleterious effects, here we present an encapsulation scheme based on seeded atomic layer deposition that provides pinhole-free growth of alumina without compromising the intrinsic electronic properties of the underlying InSe. In particular, this encapsulation provides reproducible InSe field-effect transistor characteristics and InSe photodetector responsivities in excess of 107 A/W following ambient exposure for time periods on the order of months. Because atomic layer deposition is a highly scalable and manufacturable process, this work will accelerate ongoing efforts to integrate InSe nanosheets into electronic and optoelectronic technologies.

Electrostatic confinement of charge carriers in bilayer graphene provides a unique platform for carbon-based spin, charge or exchange qubits. By exploiting the possibility to induce a band gap with electrostatic gating, we form a versatile and widely tunable multi-quantum dot system. We demonstrate the formation of single, double and triple quantum dots that are free of any sign of disorder. In bilayer graphene we have the possibility to form tunnel barriers using different mechanisms. We can exploit the ambipolar nature of bilayer graphene where pn-junctions form natural tunnel barriers. Alternatively, we can use gates to form tunnel barriers, where we can vary the tunnel coupling by more than two orders of magnitude tuning between a deeply Coulomb blockaded system and a Fabry-P\'erot-like cavity. Demonstrating such tunability is an important step towards graphene-based quantum computation., Comment: 8 pages, 5 figures

Free-standing semiconductor nanowires constitute an ideal material system for the direct manipulation of electrical and optical properties by strain engineering. In this study, we present a direct quantitative correlation between electrical conductivity and nanoscale lattice strain of individual InAs nanowires passivated with a thin epitaxial In0.6Ga0.4As shell. With an in situ electron microscopy electromechanical testing technique, we show that the piezoresistive response of the nanowires is greatly enhanced compared to bulk InAs, and that uniaxial elastic strain leads to increased conductivity, which can be explained by a strain-induced reduction in the band gap. In addition, we observe inhomogeneity in strain distribution, which could have a reverse effect on the conductivity by increasing the scattering of charge carriers. These results provide a direct correlation of nanoscale mechanical strain and electrical transport properties in free-standing nanostructures.

Conversion of solar energy into liquid fuel often relies on multielectron redox processes that include highly reactive intermediates, with back reaction routes that hinder the overall efficiency of the process. Here, we reveal that these undesirable reaction pathways can be minimized, rendering the photocatalytic reactions more efficient, when charge carriers are harvested from a multiexcitonic state of a semiconductor photocatalyst. A plasmonic antenna, comprising Au nanoprisms, was employed to accomplish feasible levels of multiple carrier excitations in semiconductor nanocrystal-based photocatalytic systems (CdSe@CdS core-shell quantum dots and CdSe@CdS seeded nanorods). The antenna's near-field amplifies the otherwise inherently weak biexciton generation in the semiconductor. The two-electron photoreduction of Pt and Pd metal precursors served as model reactions. In the presence of the plasmonic antenna, these photocatalyzed two-electron reactions exhibited enhanced yields and kinetics. This work uniquely relies on a nonlinear enhancement that has potential for large amplification of photocatalytic activity in the presence of a plasmonic near-field.

Electron transport layers (ETLs) with suitable energy level alignment for facilitating charge carrier transport as well as electron extraction are essential for planar heterojunction perovskite solar cells (PSCs) to achieve high open-circuit voltage (VOC) and short-circuit current. Herein we systematically investigate band offset between ETL and perovskite absorber by tuning F doping level in SnO2 nanocrystal. We demonstrate that gradual substitution of F– into the SnO2 ETL can effectively reduce the band offset and result in a substantial increase in device VOC. Consequently, a power conversion efficiency of 20.2% with VOC of 1.13 V can be achieved under AM 1.5 G illumination for planar heterojunction PSCs using F-doped SnO2 bilayer ETL. Our finding provides a simple pathway to tailor ETL/perovskite band offset to increase built-in electric field of planar heterojunction PSCs for maximizing VOC and charge collection simultaneously.

Two-dimensional transition metal dichalcogenides (TMDs) have drawn strong attention due to their unique properties and diverse applications. However, TMD performance depends strongly on material quality and defect morphology. Experiments show that samples grown by chemical vapor deposition (CVD) outperform those obtained by physical vapor deposition (PVD). Experiments also show that CVD samples exhibit vacancy defects, while antisite defects are frequently observed in PVD samples. Our time-domain ab initio study demonstrates that both antisites and vacancies accelerate trapping and nonradiative recombination of charge carriers, but antisites are much more detrimental than vacancies. Antisites create deep traps for both electrons and holes, reducing energy gaps for recombination, while vacancies trap primarily holes. Antisites also perturb band-edge states, creating significant overlap with the trap states. In comparison, vacancy defects overlap much less with the band-edge states. Finally, antisites can c...

Alloying different semiconductors is a powerful approach to tuning the optical and electronic properties of semiconductor materials. In halide perovskites (ABX3), alloys with different anions have been widely studied, and great band gap tunability in the visible range has been achieved. However, perovskite alloys with different cations at the "B" site are less understood due to the synthetic challenges. Herein, we first have developed the synthesis of single-crystalline CsPb xSn1- xI3 nanowires (NWs). The electronic band gaps of CsPb xSn1- xI3 NWs can be tuned from 1.3 to 1.78 eV by varying the Pb/Sn ratio, which leads to the tunable photoluminescence (PL) in the near-infrared range. More importantly, we found that the electrical conductivity increases as more Sn2+ is alloyed with Pb2+, possibly due to the increase of charge carrier concentration when more Sn2+ is introduced. The wide tunability of the optical and electronic properties makes CsPb xSn1- xI3 alloy NWs promising candidates for future optoelectronic device applications.

The solar to electric power conversion efficiency (PCE) of perovskite solar cells (PSCs) has recently reached 22.7%, exceeding that of competing thin film photovoltaics and the market leader polycrystalline silicon. Further augmentation of the PCE toward the Shockley–Queisser limit of 33.5% warrants suppression of radiationless carrier recombination by judicious engineering of the interface between the light harvesting perovskite and the charge carrier extraction layers. Here, we introduce a mesoscopic oxide double layer as electron selective contact consisting of a scaffold of TiO2 nanoparticles covered by a thin film of SnO2, either in amorphous (a-SnO2), crystalline (c-SnO2), or nanocrystalline (quantum dot) form (SnO2-NC). We find that the band gap of a-SnO2 is larger than that of the crystalline (tetragonal) polymorph leading to a corresponding lift in its conduction band edge energy which aligns it perfectly with the conduction band edge of both the triple cation perovskite and the TiO2 scaffold. Th...

High-quality organic-inorganic hybrid perovskite films are crucial for excellent performance of photoelectric devices. Herein, we demonstrate a pressure-assisted space-confined solvent-engineering strategy to grow highly oriented, pinhole-free thin films of CH3NH3PbI3 with large-scale crystalline grains, high smoothness and crystalline fusion on grain boundaries. These single-crystalline grains vertically span the entire film thickness. Such film feature dramatically reduces recombination loss and then improve the transport property of charge carriers in the films. Consequently, the photodetectors devices, based on the high-quality CH3NH3PbI3 films, exhibit high photocurrent (105 μA under 671 nm laser with a power density of 20.6 mW/cm2 at 10 V), good stability and, especially, ultrahigh on/off ratio (Ilight/Idark >2.2×104 under an incident light of 20.6 mW/cm2). These excellent performances indicate that the high-quality films will be potential candidates in other CH3NH3PbI3-based photoelectric devices.

Surface photovoltage spectroscopy (SPS) is used to measure the photopotential across a Ru–SrTiO3:Rh/BiVO4 particle tandem overall water splitting photocatalyst. The tandem is synthesized from Ru-modified SrTiO3:Rh nanocrystals and BiVO4 microcrystals by electrostatic assembly followed by thermal annealing. It splits water into H2 and O2 with an apparent quantum efficiency of 1.29% at 435 nm and a solar to hydrogen conversion efficiency of 0.028%. According to SPS, a photovoltage develops above 2.20 eV, the effective band gap of the tandem, and reaches its maximal value of −2.45 V at 435 nm (2.44 mW cm–2), which corresponds to 96% of the theoretical limit of the photocatalyst film on the fluorine-doped tin-oxide-coated glass (FTO) substrate. Charge separation is 82% reversible with 18% of charge carriers being trapped in defect states. The unusually strong light intensity dependence of the photovoltage (1.16 V per decade) is attributed to depletion layer changes inside of the BiVO4 microcrystals. These fin...

Quasiparticles with Dirac type dispersion can be observed in nearly gapless bulk semiconductors alloys where the bandgap is controlled through the material composition. We demonstrate that the Dirac dispersion can be realized in short period InAs1-xSbx/InAs1-ySby metamorphic superlattices with the bandgap tuned to zero by adjusting the superlattice period and layer strain. The new material has anisotropic carrier dispersion: the carrier energy associated with the in-plane motion is proportional to the wave vector and characterized by the Fermi velocity vF, the dispersion corresponding to the motion in the growth direction is quadratic. Experimental estimate of the Fermi velocity gives vF=6.7∙ 105 m/s. Remarkably, the Fermi velocity in this system can be controlled by varying the overlap between electron and hole states in the superlattice. Extreme design flexibility makes the short-period metamorphic InAs1-xSbx/InAs1-ySby superlattice a new prospective platform for studying the effects of charge carrier c...

Strong correlations between electrons and holes can drive the existence of an electron–hole liquid (EHL) state, typically at high carrier densities and low temperatures. The recent emergence of quasi-two-dimensional (2D) monolayer transition metal dichalcogenides (TMDCs) provides ideal systems to explore the EHL state since ineffective screening of the out-of-plane field lines in these quasi-2D systems allows for stronger charge carrier correlations in contrast to conventional 3D bulk semiconductors and enables the existence of the EHL at high temperatures. Here we construct the phase diagram for the photoinduced first-order phase transition from a plasma of electron–hole pairs to a correlated EHL state in suspended monolayer MoS2. We show that the quasi-2D nature of monolayer TMDCs and the ineffective screening of the out-of-plane field lines allow for this phase transition to occur at and above room temperature, thereby opening avenues for studying many-body phenomena without the constraint of cryogenics.

Two-dimensional transition metal dichalcogenides (TMDs) have appeared on the horizon of materials science and solid-state physics due to their unique properties and diverse applications. TMD performance depends strongly on material quality and defect morphology. Calculations predict that sulfur adatom and vacancy are among the most energetically favorable defects in MoS2 with vacancies frequently observed during chemical vapor deposition. By performing ab initio quantum dynamics calculations we demonstrate that both adatom and vacancy accelerate nonradiative charge carrier recombination but this happens through different mechanisms. Surprisingly, holes never significantly populate the shallow trap state created by the sulfur adatom because the trap is strongly localized and decoupled from free charges. Charge recombination bypasses the hole trap. Instead, it occurs directly between free electron and hole. The recombination is faster than in pristine MoS2 because the adatom strongly perturbs the MoS2 layer...

The electronic and lattice heating accompanying plasmonic structures under illumination is suggested to be utilized in a broad range of thermoplasmonic applications. Specifically, in molecular electronics precise determination of the temperature of illuminated junctions is crucial, because the temperature-dependent energy distribution of charge carriers in the leads affects the possibility to steer various light-controlled conductance processes. Existing optical methods to characterize the local temperature in all these applications lack the spatial resolution to probe the few nanometers in size hot spots and therefore typically report average values over a diffraction limited length scale. Here we demonstrate that inelastic electron tunneling spectroscopy of molecular junctions based on thiol-alkyl chains can be used to precisely measure the temperature of metal nanoscale gaps under illumination. The nature of this measurement guarantees that the reported temperature indeed characterizes the confined volume in which heat is produced by the relaxation of hot carriers. Using a simple model, we suggest that the accuracy of the method enables also one to semiquantify the energy distribution of the hot carriers.

Small semiconductor structures often exhibit "telegraph noise". If the number of charge carriers is small, then spontaneous changes in the number of carriers can lead to abrupt switching between two or more discrete levels, leading to burst noise or popcorn noise in transistors. We have observed similar behavior in the fluorescence of organic semiconductor nanoparticles, where typical carrier populations are often less than ∼10 carriers per nanoparticle. Spontaneous changes in the number of charges results in abrupt switching between 2 or more fluorescence intensity levels, because the charges act as highly efficient fluorescence quenchers. The equilibrium number of charges is determined by competition between a photodriven ionization process and spontaneous recombination. Doping with redox-active molecules also affects the balance. Nanoparticles of the conjugated polymer PFBT doped with the fullerene derivative PCBM, rapidly establish a fluctuating steady-state population of tens of hole polaron charge carriers, sufficient to nearly completely suppress nanoparticle fluorescence. However, fluctuations in the number of charges lead to occasional bursts of fluorescence. This spontaneous photoswitching phenomenon can be exploited for superresolution imaging. The repeated, spontaneous generation of short, intense bursts of fluorescence photons results in a localization precision of ∼0.6 nm, about 4 times better than typical resolution obtained by localization of dye molecules.

When coherent charge carriers cross micron-scale cavities, their dynamics can be governed by a few resonant states, also called “quantum scars”, determined by the cavity geometry. Quantum scars can be described using theoretical tools but have also been directly imaged in the case of high-quality semiconductor cavities as well as in disordered graphene devices, thanks to scanning gate microscopy (SGM). Here, we discuss spatially resolved SGM images of low-temperature charge transport through a mesoscopic ring fabricated from high-quality monolayer graphene lying on top of hexagonal boron nitride. SGM images are decorated with a pattern of radial scars in the ring area, which is found to evolve smoothly and reappear when varying the charge-carrier energy. The energies separating recurrent patterns are found to be directly related to geometric dimensions of the ring. Moreover, a recurrence is also observed in simulations of the local density of states of a model graphene quantum ring. The observed recurrences are discussed in the light of recent predictions of relativistic quantum scars in mesoscopic graphene cavities.

We present transport measurements through an electrostatically defined bilayer graphene double quantum dot in the single electron regime. With the help of a back gate, two split gates and two finger gates we are able to control the number of charge carriers on two gate-defined quantum dot independently between zero and five. The high tunability of the device meets requirements to make such a device a suitable building block for spin-qubits. In the single electron regime, we determine interdot tunnel rates on the order of 2~GHz. Both, the interdot tunnel coupling, as well as the capacitive interdot coupling increase with dot occupation, leading to the transition to a single quantum dot. Finite bias magneto-spectroscopy measurements allow to resolve the excited state spectra of the first electrons in the double quantum dot; being in agreement with spin and valley conserving interdot tunneling processes., 4 Figures, 5 pages

Nano Letters, 20 (4), ISSN:1530-6984, ISSN:1530-6992

We report smart color-sensing devices of two-dimensional lead halide perovskites that exhibit a graded band gap across the film. We observe that the device short-circuit photocurrent is strongly dependent on excitation wavelength λ, and this arises through photoabsorption at different depths in the sample due to the graded bandgaps present. This λ signature in the response of the device is observed in case of steady-state excitation when incident from the high bandgap side of the film, where a complete reversal in the polarity of the photocurrent

Two-dimensional transition metal dichalcogenides (TMDs) draw strong interest in materials science, with applications in optoelectronics and many other fields. Good performance requires high carrier concentrations and long lifetimes. However, high concentrations accelerate energy exchange between charged particles by Auger-type processes, especially in TMDs where many-body interactions are strong, thus facilitating carrier trapping. We report time-resolved optical pump-THz probe measurements of carrier lifetimes as a function of carrier density. Surprisingly, the lifetime reduction with increased density is very weak. It decreases only by 20% when we increase the pump fluence 100 times. This unexpected feature of the Auger process is rationalized by our time-domain

The observation of quantum light emission from atomically thin transition metal dichalcogenides has opened a new field of applications for these material systems. The corresponding excited charge-carrier localization has been linked to defects and strain, while open questions remain regarding the microscopic origin. We demonstrate that the bending rigidity of these materials leads to wrinkling of the two-dimensional layer. The resulting strain field facilitates strong carrier localization due to its pronounced influence on the band gap. Additionally, we consider charge carrier confinement due to local changes of the dielectric environment and show that both effects contribute to modified electronic states and optical properties. The interplay of surface wrinkling, strain-induced confinement, and local changes of the dielectric environment is demonstrated for the example of nanobubbles that form when monolayers are deposited on substrates or other two-dimensional materials.