Rugged bialkali photocathodes encapsulated with graphene and thin metal film.

Protection of free-electron sources has been technically challenging due to lack of materials that transmit electrons while preventing corrosive gas molecules. Two-dimensional materials uniquely possess both of required properties. Here, we report three orders of magnitude increase in active pressure and factor of two enhancement in the lifetime of high quantum efficiency (QE) bialkali photocathodes (cesium potassium antimonide (CsK2Sb)) by encapsulating them in graphene and thin nickel (Ni) film. The photoelectrons were extracted through the graphene protection layer in a reflection mode, and we achieved QE of ~ 0.17% at ~ 3.4 eV, 1/e lifetime of 188 h with average current of 8.6 nA under continuous illumination, and no decrease of QE at the pressure of as high as ~ 1 × 10-3 Pa. In comparison, the QE decreased drastically at 10-6 Pa for bare, non-protected CsK2Sb photocathodes and their 1/e lifetime under continuous illumination was ~ 48 h. We attributed the improvements to the gas impermeability and photoelectron transparency of graphene.

Photoemission from Bialkali Photocathodes through an Atomically Thin Protection Layer.

Photocathodes are essential components for various applications requiring photon-to-free-electron conversion, for example, high-sensitivity photodetectors and electron injectors for free-electron lasers. Alkali antimonide thin films are widely used as photocathode materials owing to their high quantum efficiency (QE) in the visible spectral range; however, their lifetime can be limited even in ultrahigh vacuum due to their high reactivity to residual gases and sensitivity to ion back-bombardment in these applications. An ambitious technical challenge is to extend the lifetime of bialkali photocathodes by coating them with suitable materials that can isolate the photocathode films from residual gases while still maintaining their highly emissive properties. We propose the use of graphene, an atomically thin two-dimensional material with gas impermeability, as a promising candidate for this purpose. Here, we report that high-quality bialkali antimonide can be grown on a two-layer (2L) suspended graphene substrate with a peak QE of 15%. More importantly, by comparing the photoemission through varying layers of graphene, we demonstrate that photoelectrons can transmit through few-layer graphene with a maximum QE of over 0.7% at 4.5 eV for 2L graphene, corresponding to a transmission efficiency of 5%. These results demonstrate important progress toward fully encapsulated bialkali photocathodes having both high QEs and long lifetimes using atomically thin protection layers.

Gas Barrier Properties of Chemical Vapor-Deposited Graphene to Oxygen Imparted with Sub-electronvolt Kinetic Energy.

Graphene gas-barrier performance holds great interest from both scientific and technological perspectives. Using in situ synchrotron X-ray photoelectron spectroscopy, we demonstrate that chemical vapor-deposited monolayer graphene loses its gas-barrier performance almost completely when oxygen molecules are imparted with sub-electronvolt kinetic energy but retains its gas-barrier performance when the molecules are not energized. The permeation process is nondestructive. Molecular dynamics-based simulation suggests kinetic energy-mediated chemical reactions catalyzed by common graphene defects as a responsible mechanism.

Angular scattering of protons through ultrathin graphene foils: Application for time-of-flight instrumentation.

Space plasma instruments often rely on ultrathin carbon foils for incident ion detection, time-of-flight (TOF) mass spectrometry, and ionization of energetic neutral atoms. Angular scattering and energy loss of ions or neutral atoms in the foil can degrade instrument performance, including sensitivity and mass resolution; thus, there is an ongoing effort to manufacture thinner foils. Using new 3-layer graphene foils manufactured at the Los Alamos National Laboratory, we demonstrate that these are the thinnest foils reported to date and discuss future testing required for application in space instrumentation. We characterize the angular scattering distribution for 3-30 keV protons through the foils, which is used as a proxy for the foil thickness. We show that these foils are ∼2.5-4.5 times thinner than the state-of-the-art carbon foils and ∼1.6 times thinner than other graphene foils described in the literature. We find that the inverse relationship between angular scattering and energy no longer holds, reaffirming that this may indicate a new domain of beam-foil interactions for ultrathin (few-layer) graphene foils.

Graphene Supported MoS2 Structures with High Defect Density for an Efficient HER Electrocatalysts.

The development of novel efficient and robust electrocatalysts with sufficient active sites is one of the key parameters for hydrogen evolution reactions (HER) catalysis, which plays a key role in hydrogen production for clean energy harvesting. Recently, two-dimensional (2D) materials, especially those based upon transition metal dichalcogenides such as molybdenum disulfide (MoS2), have gained attention for the catalysis of hydrogen production because of their exceptional properties. Innovative strategies have been developed to engineer these material systems for improvements in their catalytic activity. Toward this aim, the facile growth of MoS2 clusters by sulfurization of molybdenum dioxide (MoO2) particles supported on reduced graphene oxide (rGO) foams using the chemical vapor deposition (CVD) method is reported. This approach created various morphologies of MoS2 with large edges and defect densities on the basal plane of rGO supported MoS2 structures, which are considered as active sites for HER catalysis. In addition, MoS2 nanostructures on the surface of the porous rGO network show robust physical interactions, such as van der Waals and π-π interactions between MoS2 and rGO. These features result in an improved process to yield a suitable HER catalyst. In order to gain a better understanding of the improvement of this MoS2-based HER catalyst, fully atomistic molecular dynamics (MD) simulations of different defect geometries were also performed.

Polariton hyperspectral imaging of two-dimensional semiconductor crystals.

Atomically thin crystals of transition metal dichalcogenides (TMDs) host excitons with strong binding energies and sizable light-matter interactions. Coupled to optical cavities, monolayer TMDs routinely reach the regime of strong light-matter coupling, where excitons and photons admix coherently to form polaritons up to room temperature. Here, we explore the two-dimensional nature of TMD polaritons with scanning-cavity hyperspectral imaging. We record a spatial map of polariton properties of extended WS2 monolayers coupled to a tunable micro cavity in the strong coupling regime, and correlate it with maps of exciton extinction and fluorescence taken from the same flake with the cavity. We find a high level of homogeneity, and show that polariton splitting variations are correlated with intrinsic exciton properties such as oscillator strength and linewidth. Moreover, we observe a deviation from thermal equilibrium in the resonant polariton population, which we ascribe to non-Markovian polariton-phonon coupling. Our measurements reveal a promisingly consistent polariton landscape, and highlight the importance of phonons for future polaritonic devices.

Cavity-control of interlayer excitons in van der Waals heterostructures.

Monolayer transition metal dichalcogenides integrated in optical microcavities host exciton-polaritons as a hallmark of the strong light-matter coupling regime. Analogous concepts for hybrid light-matter systems employing spatially indirect excitons with a permanent electric dipole moment in heterobilayer crystals promise realizations of exciton-polariton gases and condensates with inherent dipolar interactions. Here, we implement cavity-control of interlayer excitons in vertical MoSe2-WSe2 heterostructures. Our experiments demonstrate the Purcell effect for heterobilayer emission in cavity-modified photonic environments, and quantify the light-matter coupling strength of interlayer excitons. The results will facilitate further developments of dipolar exciton-polariton gases and condensates in hybrid cavity - van der Waals heterostructure systems.

From 2D to 1D Electronic Dimensionality in Halide Perovskites with Stepped and Flat Layers Using Propylammonium as a Spacer.

Two-dimensional (2D) hybrid halide perovskites are promising in optoelectronic applications, particularly solar cells and light-emitting devices (LEDs), and for their increased stability as compared to 3D perovskites. Here, we report a new series of structures using propylammonium (PA+), which results in a series of Ruddlesden-Popper (RP) structures with the formula (PA)2(MA)n-1PbnI3n+1 (n = 3, 4) and a new homologous series of "step-like" (SL) structures where the PbI6 octahedra connect in a corner- and face-sharing motif with the general formula (PA)2m+4(MA)m-2Pb2m+1I7m+4 (m = 2, 3, 4). The RP structures show a blue-shift in bandgap for decreasing n (1.90 eV for n = 4 and 2.03 eV for n = 3), while the SL structures have an even greater blue-shift (2.53 eV for m = 4, 2.74 eV for m = 3, and 2.93 eV for m = 2). DFT calculations show that, while the RP structures are electronically 2D quantum wells, the SL structures are electronically 1D quantum wires with chains of corner-sharing octahedra "insulated" by blocks of face-sharing octahedra. Dark measurements for RP crystals show high resistivity perpendicular to the layers (1011 Ω cm) but a lower resistivity parallel to them (107 Ω cm). The SL crystals have varying resistivity in all three directions, confirming both RP and SL crystals' utility as anisotropic electronic materials. The RP structures show strong photoresponse, whereas the SL materials exhibit resistivity trends that are dominated by ionic transport and no photoresponse. Solar cells were made with n = 3 giving an efficiency of 7.04% (average 6.28 ± 0.65%) with negligible hysteresis.

Tuning the Fröhlich exciton-phonon scattering in monolayer MoS2.

Charge carriers in semiconducting transition metal dichalcogenides possess a valley degree of freedom that allows for optoelectronic applications based on the momentum of excitons. At elevated temperatures, scattering by phonons limits valley polarization, making a detailed knowledge about strength and nature of the interaction of excitons with phonons essential. In this work, we directly access exciton-phonon coupling in charge tunable single layer MoS2 devices by polarization resolved Raman spectroscopy. We observe a strong defect mediated coupling between the long-range oscillating electric field induced by the longitudinal optical phonon in the dipolar medium and the exciton. This so-called Fröhlich exciton phonon interaction is suppressed by doping. The suppression correlates with a distinct increase of the degree of valley polarization up to 20% even at elevated temperatures of 220 K. Our result demonstrates a promising strategy to increase the degree of valley polarization towards room temperature valleytronic applications.

Opto-valleytronic imaging of atomically thin semiconductors.

Transition metal dichalcogenide semiconductors represent elementary components of layered heterostructures for emergent technologies beyond conventional optoelectronics. In their monolayer form they host electrons with quantized circular motion and associated valley polarization and valley coherence as key elements of opto-valleytronic functionality. Here, we introduce two-dimensional polarimetry as means of direct imaging of the valley pseudospin degree of freedom in monolayer transition metal dichalcogenides. Using MoS2 as a representative material with valley-selective optical transitions, we establish quantitative image analysis for polarimetric maps of extended crystals, and identify valley polarization and valley coherence as sensitive probes of crystalline disorder. Moreover, we find site-dependent thermal and non-thermal regimes of valley-polarized excitons in perpendicular magnetic fields. Finally, we demonstrate the potential of wide-field polarimetry for rapid inspection of opto-valleytronic devices based on atomically thin semiconductors and heterostructures.

Ultrafast Optical Microscopy of Single Monolayer Molybdenum Disulfide Flakes.

We have performed ultrafast optical microscopy on single flakes of atomically thin CVD-grown molybdenum disulfide, using non-degenerate femtosecond pump-probe spectroscopy to excite and probe carriers above and below the indirect and direct band gaps. These measurements reveal the influence of layer thickness on carrier dynamics when probing near the band gap. Furthermore, fluence-dependent measurements indicate that carrier relaxation is primarily influenced by surface-related defect and trap states after above-bandgap photoexcitation. The ability to probe femtosecond carrier dynamics in individual flakes can thus give much insight into light-matter interactions in these two-dimensional nanosystems.

Direct imaging of charge transport in progressively reduced graphene oxide using electrostatic force microscopy.

Graphene oxide (GO) has emerged as a multifunctional material that can be synthesized in bulk quantities and can be solution processed to form large-area atomic layered photoactive, flexible thin films for optoelectronic devices. This is largely due to the potential ability to tune electrical and optical properties of GO using functional groups. For the successful application of GO, it is key to understand the evolution of its optoelectronic properties as the GO undergoes a phase transition from its insulating and optically active state to the electrically conducting state with progressive reduction. In this paper, we use a combination of electrostatic force microscopy (EFM) and optical spectroscopy to monitor the emergence of the optoelectronic properties of GO with progressive reduction. EFM measurements enable, for the first time, direct visualization of charge propagation along the conducting pathways that emerge on progressively reduced graphene oxide (rGO) and demonstrate that with the increasing degree of reduction, injected charges can rapidly migrate over a distance of several micrometers, irrespective of their polarities. Direct imaging reveals the presence of an insurmountable potential barrier between reduced GO (rGO) and GO, which plays the decisive role in the charge transport. We complement charge imaging with theoretical modeling using quantum chemistry calculations that further demonstrate that the role of barrier in regulating the charge transport. Furthermore, by correlating the EFM measurements with photoluminescence imaging and electrical conductivity studies, we identify a bifunctional state in GO, where the optical properties are preserved along with good electrical conductivity, providing design principles for the development of GO-based, low-cost, thin-film optoelectronic applications.

Spatially resolved photoexcited charge-carrier dynamics in phase-engineered monolayer MoS2.

A fundamental understanding of the intrinsic optoelectronic properties of atomically thin transition-metal dichalcogenides (TMDs) is crucial for its integration into high performance semiconductor devices. Here, we investigate the transport properties of chemical vapor deposition (CVD) grown monolayer molybdenum disulfide (MoS2) under photoexcitation using correlated scanning photocurrent microscopy and photoluminescence imaging. We examined the effect of local phase transformation underneath the metal electrodes on the generation of photocurrent across the channel length with diffraction-limited spatial resolution. While maximum photocurrent generation occurs at the Schottky contacts of semiconducting (2H-phase) MoS2, after the metallic phase transformation (1T-phase), the photocurrent peak is observed toward the center of the device channel, suggesting a strong reduction of native Schottky barriers. Analysis using the bias and position dependence of the photocurrent indicates that the Schottky barrier heights are a few millielectron volts for 1T- and ∼ 200 meV for 2H-contacted devices. We also demonstrate that a reduction of native Schottky barriers in a 1T device enhances the photoresponsivity by more than 1 order of magnitude, a crucial parameter in achieving high-performance optoelectronic devices. The obtained results pave a way for the fundamental understanding of intrinsic optoelectronic properties of atomically thin TMDs where ohmic contacts are necessary for achieving high-efficiency devices with low power consumption.

Electronic structure and chemical nature of oxygen dopant states in carbon nanotubes.

We performed low temperature photoluminescence (PL) studies on individual oxygen-doped single-walled carbon nanotubes (SWCNTs) and correlated our observations to electronic structure simulations. Our experiment reveals multiple sharp asymmetric emission peaks at energies 50-300 meV red-shifted from that of the E11 bright exciton peak. Our simulation suggests an association of these peaks with deep trap states tied to different specific chemical adducts. In addition, oxygen doping is also observed to split the E11 exciton into two or more states with an energy splitting <40 meV. We attribute these states to dark states that are brightened through defect-induced symmetry breaking. While the wave functions of these brightened states are delocalized, those of the deep-trap states are strongly localized and pinned to the dopants. These findings are consistent with our experimental observation of asymmetric broadening of the deep trap emission peaks, which can result from interaction between pinned excitons and one-dimensional phonons. Exciton pinning also increases the sensitivity of the deep traps to the local dielectric environment, leading to a large inhomogeneous broadening. Observations of multiple spectral features on single nanotubes indicate the possibility of different chemical adducts coexisting on a given nanotube.

Chemically exfoliated ReS2 nanosheets.

The production of two-dimensional rhenium disulfide (ReS2) nanosheets by exfoliation using lithium intercalation is demonstrated. The vibrational and photoluminescence properties of the exfoliated nanosheets are investigated, and the local atomic structure is studied by scanning and transmission electron microscopy. The catalytic activity of the nanosheets in a hydrogen evolution reaction (HER) is also investigated. The electrochemical properties of the exfoliated ReS2 nanosheets include low overpotentials of ∼100 mV and low Tafel slopes of 75 mV dec(-1) for HER and are attributed to the atomic structure of the superlattice 1T' phase. The presence of bandgap photoluminescence demonstrates that the nanosheets retain their semiconducting nature. ReS2 nanosheets produced by this method provide unique photocatalytic properties that are superior to those of other two-dimensional systems.

Evolution of the electronic band structure and efficient photo-detection in atomic layers of InSe.

Atomic layers of two-dimensional (2D) materials have recently been the focus of extensive research. This follows from the footsteps of graphene, which has shown great potential for ultrathin optoelectronic devices. In this paper, we present a comprehensive study on the synthesis, characterization, and thin film photodetector application of atomic layers of InSe. Correlation between resonance Raman spectroscopy and photoconductivity measurements allows us to systematically track the evolution of the electronic band structure of 2D InSe as its thickness approaches few atomic layers. Analysis of photoconductivity spectra suggests that few-layered InSe has an indirect band gap of 1.4 eV, which is 200 meV higher than bulk InSe due to the suppressed interlayer electron orbital coupling. Temperature-dependent photocurrent measurements reveal that the suppressed interlayer interaction also results in more localized pz-like orbitals, and these orbitals couple strongly with the in-plane E' and E″ phonons. Finally, we measured a strong photoresponse of 34.7 mA/W and fast response time of 488 µs for a few layered InSe, suggesting that it is a good material for thin film optoelectronic applications.

Development of an amorphous selenium-based photodetector driven by a diamond cold cathode.

Amorphous-selenium (a-Se) based photodetectors are promising candidates for imaging devices, due to their high spatial resolution and response speed, as well as extremely high sensitivity enhanced by an internal carrier multiplication. In addition, a-Se is reported to show sensitivity against wide variety of wavelengths, including visible, UV and X-ray, where a-Se based flat-panel X-ray detector was proposed. In order to develop an ultra high-sensitivity photodetector with a wide detectable wavelength range, a photodetector was fabricated using a-Se photoconductor and a nitrogen-doped diamond cold cathode. In the study, a prototype photodetector has been developed, and its response to visible and ultraviolet light are characterized.

Enhanced catalytic activity in strained chemically exfoliated WS2 nanosheets for hydrogen evolution.

Efficient evolution of hydrogen through electrocatalysis at low overpotentials holds tremendous promise for clean energy. Hydrogen evolution can be easily achieved by electrolysis at large potentials that can be lowered with expensive platinum-based catalysts. Replacement of Pt with inexpensive, earth-abundant electrocatalysts would be significantly beneficial for clean and efficient hydrogen evolution. To this end, promising results have been reported using 2H (trigonal prismatic) XS2 (where X = Mo or W) nanoparticles with a high concentration of metallic edges. The key challenges for XS2 are increasing the number and catalytic activity of active sites. Here we report monolayered nanosheets of chemically exfoliated WS2 as efficient catalysts for hydrogen evolution with very low overpotentials. Analyses indicate that the enhanced electrocatalytic activity of WS2 is associated with the high concentration of the strained metallic 1T (octahedral) phase in the as-exfoliated nanosheets. Our results suggest that chemically exfoliated WS2 nanosheets are interesting catalysts for hydrogen evolution.

Coherent atomic and electronic heterostructures of single-layer MoS2.

Nanoscale heterostructures with quantum dots, nanowires, and nanosheets have opened up new routes toward advanced functionalities and implementation of novel electronic and photonic devices in reduced dimensions. Coherent and passivated heterointerfaces between electronically dissimilar materials can be typically achieved through composition or doping modulation as in GaAs/AlGaAs and Si/NiSi or heteroepitaxy of lattice matched but chemically distinct compounds. Here we report that single layers of chemically exfoliated MoS(2) consist of electronically dissimilar polymorphs that are lattice matched such that they form chemically homogeneous atomic and electronic heterostructures. High resolution scanning transmission electron microscope (STEM) imaging reveals the coexistence of metallic and semiconducting phases within the chemically homogeneous two-dimensional (2D) MoS(2) nanosheets. These results suggest potential for exploiting molecular scale electronic device designs in atomically thin 2D layers.