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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 MoS2clusters 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 MoS2with large edges and defect densities on the basal plane of rGO supported MoS2structures, which are considered as active sites for HER catalysis. In addition, MoS2nanostructures on the surface of the porous rGO network show robust physical interactions, such as van der Waals and π–π interactions between MoS2and 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.

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 PbI6octahedra 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 (1011Ω cm) but a lower resistivity parallel to them (107Ω 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.

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 MoS2as 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.

We report valence‐band electronic structure evolution of graphene oxide (GO) upon its thermal reduction. The degree of oxygen functionalization was controlled by annealing temperature, and an electronic structure evolution was monitored using real‐time ultraviolet photoelectron spectroscopy. We observed a drastic increase in the density of states around the Fermi level upon thermal annealing at ∼600 °C. The result indicates that while there is an apparent bandgap for GO prior to a thermal reduction, the gap closes after an annealing around that temperature. This trend of bandgap closure was correlated with the electrical, chemical, and structural properties to determine a set of GO material properties that is optimal for optoelectronics. The results revealed that annealing at a temperature of ∼500 °C leads to the desired properties, demonstrated by a uniform and an order of magnitude enhanced photocurrent map of an individual GO sheet compared to an as‐synthesized counterpart.

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.

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.

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 E11bright 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 E11exciton 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.

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.

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 MoS2consist 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) MoS2nanosheets. These results suggest potential for exploiting molecular scale electronic device designs in atomically thin 2D layers.

Point sources exhibit low threshold electron emission due to local field enhancement at the tip. The development and implementation of tip emitters have been hampered by the need to position them sufficiently apart to achieve field enhancement, limiting the number of emission sites and therefore the overall current. Here we report low threshold field (< 0.1 V/μm) emission of multiple electron beams from atomically thin edges of reduced graphene oxide (rGO). Field emission microscopy measurements show evidence for interference from emission sites that are separated by a few nanometers, suggesting that the emitted electron beams are coherent. On the basis of our high-resolution transmission electron microscopy, infrared spectroscopy, and simulation results, field emission from the rGO edge is attributed to a stable and unique aggregation of oxygen groups in the form of cyclic edge ethers. Such closely spaced electron beams from rGO offer prospects for novel applications and understanding the physics of linear electron sources.

We report flexible and metal-free light-emitting electrochemical cells (LECs) using exclusively solution-processed organic materials and illustrate interesting design opportunities offered by such conformable devices with transparent electrodes. Flexible LEC devices based on chemically derived graphene (CDG) as the cathode and poly(3,4-ethylenedioxythiophene) mixed with poly(styrenesulfonate) as the anode exhibit a low turn-on voltage for yellow light emission (V= 2.8 V) and a good efficiency 2.4 (4.0) cd/A at a brightness of 100 (50) cd/m2. We also find that CDG is electrochemically inert over a wide potential range (+1.2 to −2.8 V vsferrocene/ferrocenium) and exploit this property to demonstrate planar LEC devices with CDG as both the anode and the cathode.

The emerging field of “organic” or “plastic” electronics has brought low-voltage, ultrathin, and energy-efficient lighting and displays to market as organic light-emitting diode (OLED) televisions and displays in cameras and mobile phones. Despite using carbon-based materials as the light-emitting layer, previous efficient organic electronic light-emitting devices have required at least one metal electrode. Here, we utilize chemically derived graphene for the transparent cathode in an all-plastic sandwich-structure device, similar to an OLED, called a light-emitting electrochemical cell (LEC). Using a screen-printable conducting polymer as a partially transparent anode and a micrometer-thick active layer solution-deposited from a blend of a light-emitting polymer and a polymer electrolyte, we demonstrate a light-emitting device based solely on solution-processable carbon-based materials. Our results demonstrate that low-voltage, inexpensive, and efficient light-emitting devices can be made without using metals. In other words, electronics can truly be “organic”.

The deposition of atomically thin highly uniform chemically derived graphene (CDG) films on 300 mm SiO2/Si wafers is reported. We demonstrate that the very thin films can be lifted off to form uniform membranes that can be free-standing or transferred onto any substrate. Detailed maps of thickness using Raman spectroscopy and atomic force microscopy height profiles reveal that the film thickness is very uniform and highly controllable, ranging from 1−2 layers up to 30 layers. After reduction using a variety of methods, the CDG films are transparent and electrically active with FET devices yielding high mobilities of ∼15 cm2/(V s) and sheet resistance of ∼1 kΩ/sq at ∼70% transparency.

Transport properties of progressively reduced graphene oxide (GO) are described. Evolution of the electronic properties reveals that as-synthesized GO undergoes insulator−semiconductor−semimetal transitions with reduction. The apparent transport gap ranges from 10 to 50 meV and approaches zero with extensive reduction. Measurements at varying degrees of reduction reveal that transport in reduced GO occurs via variable-range hopping and further reduction leads to an increased number of available hopping sites.

Field emission from heavily phosphorus-doped homoepitaxial (111) diamonds after surface modifications are discussed. To develop a model for emission, we applied X-ray photoelectron spectroscopy (XPS) to characterize surface properties of H-plasma treated, oxidized and carbon-reconstructed surfaces. In addition, reflection high energy electron diffraction (RHEED) is used to evaluate atomic arrangements. Atomic force microscopy (AFM) is used to investigate surface morphologies. From AFM, no major difference is observed between H-terminated, oxidized and carbon reconstructed surfaces. Field emission proper- ties of carbon reconstructed surfaces show a lower threshold than hydrogen-terminated or oxidized surfaces. (© 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

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.

Quantum Efficiency Enhancement Phototube with accelerator technology relevant antimonide photocathodes (K2CsSb) deposited on atomically thin two‐dimensional (2D) crystal layers such as graphene. Quantum efficiency enhancement occurs in a reflection mode, when a 2D crystal is placed in between the photocathodes and optically reflective substrates. More details can be found in article number 1900501by Hisato Yamaguchi, and co‐workers.

Quantum efficiency (QE) enhancement in accelerator technology relevant to antimonide photocathodes (K2CsSb) is achieved by interfacing them with atomically thin 2D crystal layers. The enhancement occurs in a reflection mode, when a 2D crystal is placed in between the photocathodes and optically reflective substrates. Specifically, the peak QE at 405 nm (3.1 eV) increases by a relative 10%, whereas the long wavelength response at 633 nm (2.0 eV) increases by a relative 36% on average and up to 80% at localized “hot spot” regions when photocathodes are deposited onto graphene‐coated stainless steel. There is a similar effect for photocathodes deposited on hexagonal boron nitride monolayer coatings using nickel substrates. The enhancement does not occur when reflective substrates are replaced with optically transparent sapphire. Optical transmission, X‐ray diffraction (XRD), and X‐ray fluorescence (XRF) revealed that thickness, crystal orientation, quality, and elemental stoichiometry of photocathodes do not appreciably change due to 2D crystal coatings. These results suggest that optical interactions are responsible for the QE enhancements when 2D crystal sublayers are present on reflective substrates, and provide a pathway toward a simple method of QE enhancement in semiconductor photocathodes by an atomically thin 2D crystal on substrates. Quantum efficiency (QE) enhancement in accelerator technology relevant to antimonide photocathodes (K2CsSb) is achieved by interfacing them with atomically thin 2D crystal layers. The enhancement occurs in a reflection mode, when a 2D crystal is placed in between the photocathodes and optically reflective substrates.