Chemical Etching of Screw Dislocated Transition Metal Dichalcogenides.

Chemical etching can create novel structures inaccessible by growth and provide complementary understanding on the growth mechanisms of complex nanostructures. Screw dislocation-driven growth influences the layer stackings of transition metal dichalcogenides (MX2) resulting in complex spiral morphologies. Herein, we experimentally and theoretically study the etching of screw dislocated WS2 and WSe2 nanostructures using H2O2 etchant. The kinetic Wulff constructions and Monte Carlo simulations establish the etching principles of single MX2 layers. Atomic force microscopy characterization reveals diverse etching morphology evolution behaviors around the dislocation cores and along the exterior edges, including triangular, hexagonal, or truncated hexagonal holes and smooth or rough edges. These behaviors are influenced by the edge orientations, layer stackings, and the strain of screw dislocations. Ab initio calculation and kinetic Monte Carlo simulations support the experimental observations and provide further mechanistic insights. This knowledge can help one to understand more complex structures created by screw dislocations through etching.

Chemically Derived Kirigami of WSe2.

Layered metal dichalcogenides have shown intriguing physical phenomena depending on their complex layer stackings and unique architectures. Here, we report novel microscale kirigami structures of multilayered WSe2 formed by a simple chemical vapor deposition and etching method. Scanning electron microscopy and atomic force microscopy reveal the unusual structure features of curved concave edges, panhandles, and sawtooth corners of these intricate multilayer architectures that result from etching. The structure-symmetry relationship and layer stackings of these WSe2 kirigami were elucidated by second-harmonic generation imaging and micro-Raman spectroscopy. We propose an etching model in which the etching behaviors of WSe2 multilayers are governed by the layer stacking of the bottom trilayer, which can successfully explain the formation process of WSe2 kirigami. This chemical etching approach could be applied to other metal dichalcogenide materials and open up new possibilities for creating novel and complex platforms for studying the rich physical properties in two-dimensional materials.

Stabilization of the Metastable Lead Iodide Perovskite Phase via Surface Functionalization.

Metastable structural polymorphs can have superior properties and applications to their thermodynamically stable phases, but the rational synthesis of metastable phases is a challenge. Here, a new strategy for stabilizing metastable phases using surface functionalization is demonstrated using the example of formamidinium lead iodide (FAPbI3) perovskite, which is metastable at room temperature (RT) but holds great promises in solar and light-emitting applications. We show that, through surface ligand functionalization during direct solution growth at RT, pure FAPbI3 in the cubic perovskite phase can be stabilized in nanostructures and thin films at RT without cation or anion alloying. Surface characterizations reveal that long-chain alkyl or aromatic ammonium (LA) cations bind to the surface of perovskite structure. Calculations show that such functionalization reduces the surface energy and plays a dominant role in stabilizing the metastable perovskite phase. Excellent photophysics and optically pumped lasing from the stabilized single-crystal FAPbI3 nanoplates with low thresholds were demonstrated. High-performance solar cells can be fabricated with such directly synthesized stabilized phase-pure FAPbI3 with a lower bandgap. Our results offer new insights on the surface chemistry of perovskite materials and provide a new strategy for stabilizing metastable perovskites and metastable polymorphs of solid materials in general.

Molecular Design of Polymer Heterojunctions for Efficient Solar-Hydrogen Conversion.

Semiconducting photocatalytic solar-hydrogen conversion (SHC) from water is a great challenge for renewable fuel production. Organic semiconductors hold great promise for SHC in an economical and environmentally benign manner. However, organic semiconductors available for SHC are scarce and less efficient than most inorganic ones, largely due to their intrinsic Frenkel excitons with high binding energy. In this study the authors report polymer heterojunction (PHJ) photocatalysts consisting of polyfluorene family polymers and graphitic carbon nitride (g-C3 N4 ) for efficient SHC. A molecular design strategy is executed to further promote the exciton dissociation or light harvesting ability of these PHJs via alternative approaches. It is revealed that copolymerizing electron-donating carbazole unit into the poly(9,9-dioctylfluorene) backbone promotes exciton dissociation within the poly(N-decanyl-2,7-carbazole-alt-9,9-dioctylfluorene) (PCzF)/g-C3 N4 PHJ, achieving an enhanced apparent quantum yield (AQY) of 27% at 440 nm over PCzF/g-C3 N4 . Alternatively, copolymerizing electron-accepting benzothiadiazole unit extended the visible light response of the obtained poly(9,9-dioctylfluorene-alt-benzothiadiazole)/g-C3 N4 PHJ, leading to an AQY of 13% at 500 nm. The present study highlights that constructing PHJs and adapting a rational molecular design of PHJs are effective strategies to exploit more of the potential of organic semiconductors for efficient solar energy conversion.

Complex and Noncentrosymmetric Stacking of Layered Metal Dichalcogenide Materials Created by Screw Dislocations.

The interesting and tunable properties of layered metal dichalcogenides heavily depend on their phase and layer stacking. Here, we show and explain how the layer stacking and physical properties of WSe2 are influenced by screw dislocations. A one-to-one correlation of atomic force microscopy and high- and low-frequency Raman spectroscopy of many dislocated WSe2 nanoplates reveals variations in the number and shapes of dislocation spirals and different layer stackings that are determined by the number, rotation, and location of the dislocations. Plates with triangular dislocation spirals form noncentrosymmetric stacking that gives rise to strong second-harmonic generation and enhanced photoluminescence, plates with hexagonal dislocation spirals form the bulk 2H layer stacking commonly observed, and plates containing mixed dislocation shapes have intermediate noncentrosymmetric stackings with mixed properties. Multiple dislocation cores and other complexities can lead to more complex stackings and properties. These previously unobserved properties and layer stackings in WSe2 will be interesting for spintronics and valleytronics.

Color-Pure Violet-Light-Emitting Diodes Based on Layered Lead Halide Perovskite Nanoplates.

Violet electroluminescence is rare in both inorganic and organic light-emitting diodes (LEDs). Low-cost and room-temperature solution-processed lead halide perovskites with high-efficiency and color-tunable photoluminescence are promising for LEDs. Here, we report room-temperature color-pure violet LEDs based on a two-dimensional lead halide perovskite material, namely, 2-phenylethylammonium (C6H5CH2CH2NH3(+), PEA) lead bromide [(PEA)2PbBr4]. The natural quantum confinement of two-dimensional layered perovskite (PEA)2PbBr4 allows for photoluminescence of shorter wavelength (410 nm) than its three-dimensional counterpart. By converting as-deposited polycrystalline thin films to micrometer-sized (PEA)2PbBr4 nanoplates using solvent vapor annealing, we successfully integrated this layered perovskite material into LEDs and achieved efficient room-temperature violet electroluminescence at 410 nm with a narrow bandwidth. This conversion to nanoplates significantly enhanced the crystallinity and photophysical properties of the (PEA)2PbBr4 samples and the external quantum efficiency of the violet LED. The solvent vapor annealing method reported herein can be generally applied to other perovskite materials to increase their grain size and, ultimately, improve the performance of optoelectronic devices based on perovskite materials.

Measurement of Ultrafast Excitonic Dynamics of Few-Layer MoS2 Using State-Selective Coherent Multidimensional Spectroscopy.

We report the first coherent multidimensional spectroscopy study of a MoS2 film. A four-layer sample of MoS2 was synthesized on a silica substrate by a simplified sulfidation reaction and characterized by absorption and Raman spectroscopy, atomic force microscopy, and transmission electron microscopy. State-selective coherent multidimensional spectroscopy (CMDS) on the as-prepared MoS2 film resolved the dynamics of a series of diagonal and cross-peak features involving the spin-orbit split A and B excitonic states and continuum states. The spectra are characterized by striped features that are similar to those observed in CMDS studies of quantum wells where the continuum states contribute strongly to the initial excitation of both the diagonal and cross-peak features, while the A and B excitonic states contributed strongly to the final output signal. The strong contribution from the continuum states to the initial excitation shows that the continuum states are coupled to the A and B excitonic states and that fast intraband relaxation is occurring on a sub-70 fs time scale. A comparison of the CMDS excitation signal and the absorption spectrum shows that the relative importance of the continuum states is determined primarily by their absorption strength. Diagonal and cross-peak features decay with a 680 fs time constant characteristic of exciton recombination and/or trapping. The short time dynamics are complicated by coherent and partially coherent pathways that become important when the excitation pulses are temporally overlapped. In this region, the coherent dynamics create diagonal features involving both the excitonic states and continuum states, while the partially coherent pathways contribute to cross-peak features.

Designing Efficient Solar-Driven Hydrogen Evolution Photocathodes Using Semitransparent MoQxCly (Q = S, Se) Catalysts on Si Micropyramids.

Silicon micropyramids with n(+) pp(+) junctions are demonstrated to be efficient absorbers for integrated solar-driven hydrogen production systems enabling significant improvements in both photocurrent and onset potential. When conformally coated with MoSx Cly , a catalyst that has excellent catalytic activity and high optical transparency, the highest photocurrent density for Si-based photocathodes with earth-abundant catalysts is achieved.

Construction of a Semiconductor-Biological Interface for Solar Energy Conversion: p-Doped Silicon/Photosystem I/Zinc Oxide.

The interface between photoactive biological materials with two distinct semiconducting electrodes is challenging both to develop and analyze. Building off of our previous work using films of photosystem I (PSI) on p-doped silicon, we have deposited a crystalline zinc oxide (ZnO) anode using confined-plume chemical deposition (CPCD). We demonstrate the ability of CPCD to deposit crystalline ZnO without damage to the PSI biomaterial. Using electrochemical techniques, we were able to probe this complex semiconductor-biological interface. Finally, as a proof of concept, a solid-state photovoltaic device consisting of p-doped silicon, PSI, ZnO, and ITO was constructed and evaluated.

Solution growth of single crystal methylammonium lead halide perovskite nanostructures for optoelectronic and photovoltaic applications.

Understanding crystal growth and improving material quality is important for improving semiconductors for electronic, optoelectronic, and photovoltaic applications. Amidst the surging interest in solar cells based on hybrid organic-inorganic lead halide perovskites and the exciting progress in device performance, improved understanding and better control of the crystal growth of these perovskites could further boost their optoelectronic and photovoltaic performance. Here, we report new insights on the crystal growth of the perovskite materials, especially crystalline nanostructures. Specifically, single crystal nanowires, nanorods, and nanoplates of methylammonium lead halide perovskites (CH3NH3PbI3 and CH3NH3PbBr3) are successfully grown via a dissolution-recrystallization pathway in a solution synthesis from lead iodide (or lead acetate) films coated on substrates. These single crystal nanostructures display strong room-temperature photoluminescence and long carrier lifetime. We also report that a solid-liquid interfacial conversion reaction can create a highly crystalline, nanostructured MAPbI3 film with micrometer grain size and high surface coverage that enables photovoltaic devices with a power conversion efficiency of 10.6%. These results suggest that single-crystal perovskite nanostructures provide improved photophysical properties that are important for fundamental studies and future applications in nanoscale optoelectronic and photonic devices.

Efficient photoelectrochemical hydrogen generation using heterostructures of Si and chemically exfoliated metallic MoS2.

We report the preparation and characterization of highly efficient and robust photocathodes based on heterostructures of chemically exfoliated metallic 1T-MoS2 and planar p-type Si for solar-driven hydrogen production. Photocurrents up to 17.6 mA/cm(2) at 0 V vs reversible hydrogen electrode were achieved under simulated 1 sun irradiation, and excellent stability was demonstrated over long-term operation. Electrochemical impedance spectroscopy revealed low charge-transfer resistances at the semiconductor/catalyst and catalyst/electrolyte interfaces, and surface photoresponse measurements also demonstrated slow carrier recombination dynamics and consequently efficient charge carrier separation, providing further evidence for the superior performance. Our results suggest that chemically exfoliated 1T-MoS2/Si heterostructures are promising earth-abundant alternatives to photocathodes based on noble metal catalysts for solar-driven hydrogen production.