Masoud Mahjouri-Samani

Patterned arrays of lateral heterojunctions within monolayer two-dimensional semiconductors

The formation of semiconductor heterojunctions and their high-density integration are foundations of modern electronics and optoelectronics. To enable two-dimensional crystalline semiconductors as building blocks in next-generation electronics, developing methods to deterministically form lateral heterojunctions is crucial. Here we demonstrate an approach for the formation of lithographically patterned arrays of lateral semiconducting heterojunctions within a single two-dimensional crystal. Electron beam lithography is used to pattern MoSe2 monolayer crystals with SiO2, and the exposed locations are selectively and totally converted to MoS2 using pulsed laser vaporization of sulfur to form MoSe2/MoS2 heterojunctions in predefined patterns. The junctions and conversion process are studied by Raman and photoluminescence spectroscopy, atomically resolved scanning transmission electron microscopy and device characterization. This demonstration of lateral heterojunction arrays within a monolayer crystal is an essential step for the integration of two-dimensional semiconductor building blocks with different electronic and optoelectronic properties for high-density, ultrathin devices.

Low-Frequency Raman Fingerprints of Two-Dimensional Metal Dichalcogenide Layer Stacking Configurations

The tunable optoelectronic properties of stacked two-dimensional (2D) crystal monolayers are determined by their stacking orientation, order, and atomic registry. Atomic-resolution Z-contrast scanning transmission electron microscopy (AR-Z-STEM) and electron energy loss spectroscopy (EELS) can be used to determine the exact atomic registration between different layers, in few-layer 2D stacks; however, fast optical characterization techniques are essential for rapid development of the field. Here, using two- and three-layer MoSe2 and WSe2 crystals synthesized by chemical vapor deposition, we show that the generally unexplored low frequency (LF) Raman modes (<50 cm(-1)) that originate from interlayer vibrations can serve as fingerprints to characterize not only the number of layers, but also their stacking configurations. Ab initio calculations and group theory analysis corroborate the experimental assignments determined by AR-Z-STEM and show that the calculated LF mode fingerprints are related to the 2D crystal symmetries.

Structure and Formation Mechanism of Black TiO2 Nanoparticles

The remarkable properties of black TiO2 are due to its disordered surface shell surrounding a crystalline core. However, the chemical composition and the atomic and electronic structure of the disordered shell and its relationship to the core remain poorly understood. Using advanced transmission electron microscopy methods, we show that the outermost layer of black TiO2 nanoparticles consists of a disordered Ti2O3 shell. The measurements show a transition region that connects the disordered Ti2O3 shell to the perfect rutile core consisting first of four to five monolayers of defective rutile, containing clearly visible Ti interstitial atoms, followed by an ordered reconstruction layer of Ti interstitial atoms. Our data suggest that this reconstructed layer presents a template on which the disordered Ti2O3 layers form by interstitial diffusion of Ti ions. In contrast to recent reports that attribute TiO2 band-gap narrowing to the synergistic action of oxygen vacancies and surface disorder of nonspecific origin, our results point to Ti2O3, which is a narrow-band-gap semiconductor. As a stoichiometric compound of the lower oxidation state Ti(3+) it is expected to be a more robust atomic structure than oxygen-deficient TiO2 for preserving and stabilizing Ti(3+) surface species that are the key to the enhanced photocatalytic activity of black TiO2.

Interlayer Coupling in Twisted WSe2/WS2 Bilayer Heterostructures Revealed by Optical Spectroscopy

van der Waals (vdW) heterostructures are promising building blocks for future ultrathin electronics. Fabricating vdW heterostructures by stamping monolayers at arbitrary angles provides an additional range of flexibility to tailor the resulting properties than could be expected by direct growth. Here, we report fabrication and comprehensive characterizations of WSe2/WS2 bilayer heterojunctions with various twist angles that were synthesized by artificially stacking monolayers of WS2 and WSe2 grown by chemical vapor deposition. After annealing the WSe2/WS2 bilayers, Raman spectroscopy reveals interlayer coupling with the appearance of a mode at 309.4 cm(-1) that is sensitive to the number of WSe2 layers. This interlayer coupling is associated with substantial quenching of the intralayer photoluminescence. In addition, microabsorption spectroscopy of WSe2/WS2 bilayers revealed spectral broadening and shifts as well as a net ∼10% enhancement in integrated absorption strength across the visible spectrum with respect to the sum of the individual monolayer spectra. The observed broadening of the WSe2 A exciton absorption band in the bilayers suggests fast charge separation between the layers, which was supported by direct femtosecond pump-probe spectroscopy. Density functional calculations of the band structures of the bilayers at different twist angles and interlayer distances found robust type II heterojunctions at all twist angles, and predicted variations in band gap for particular atomistic arrangements. Although interlayer excitons were indicated using femtosecond pump-probe spectroscopy, photoluminescence and absorption spectroscopies did not show any evidence of them, suggesting that the interlayer exciton transition is very weak. However, the interlayer coupling for the WSe2/WS2 bilayer heterojunctions indicated by substantial PL quenching, enhanced absorption, and rapid charge transfer was found to be insensitive to the relative twist angle, indicating that stamping provides a robust approach to realize reliable optoelectronics.

Single‐Step Formation of Graphene on Dielectric Surfaces

The direct formation of graphene on various dielectric surfaces is successful via a single-step rapid thermal processing (RTP) of substrates coated with amorphous carbon (C) and nickel (Ni) thin films. High-quality graphene is obtained uniformly on the whole surface of wafers with a controlled number of graphene layers. The monolayer graphene exhibits a low sheet resistance and a high optical transmittance in the visible range.

Transparent, flexible, and solid-state supercapacitors based on graphene electrodes

In this study, graphene-based supercapacitors with optical transparency and mechanical flexibility have been achieved using a combination of poly(vinyl alcohol)/phosphoric acid gel electrolyte and graphene electrodes. An optical transmittance of ∼67% in a wavelength range of 500-800 nm and a 92.4% remnant capacitance under a bending angle of 80° have been achieved for the supercapacitors. The decrease in capacitance under bending is ascribed to the buckling of the graphene electrode in compression. The supercapacitors with high optical transparency, electrochemical stability, and mechanical flexibility hold promises for transparent and flexible electronics.

Surface-enhanced Raman spectroscopy using gold-coated horizontally aligned carbon nanotubes

Gold-coated horizontally aligned carbon nanotube (Au-HA-CNT) substrates were fabricated for surface-enhanced Raman spectroscopy (SERS). The Au-HA-CNT substrates, which are granular in nature, are easy-to-prepare with large SERS-active area. Enhancement factors (EFs) of ∼10(7) were achieved using the Au-HA-CNTs as substrates for rhodamine 6G (R6G) molecules. Maximum enhancement was found when the polarization direction (E-field) of the incident laser beam was parallel to the aligned direction of the HA-CNTs. Simulations using the finite-difference time-domain (FDTD) method were carried out for the granular Au-HA-CNT samples. Enhancement mechanisms and determination of EFs were analyzed. Biological samples, including (13)C- and deuterium (D)-labeled fatty acids and Coccomyxa sp. c-169 microalgae cells, were also measured using this SERS substrate. The limits of detection (LODs) of D- and (13)C-labeled fatty acids on the SERS substrate were measured to be around 10 nM and 20 nM, respectively. Significantly enhanced Raman signals from the microalgae cells were acquired using the SERS substrate.

Laser induced selective removal of metallic carbon nanotubes

Distinguishing between carbon nanotubes (CNTs) according to their individual electronic properties is of significant importance for developing CNT-based electronics and devices. In this study, selective removal of metallic CNTs from CNT mixtures on silicon substrates was investigated using controlled laser irradiation. Free electron movement and eddy currents are induced within the metallic CNTs by the strong electric field and optical near-field effects caused by the laser irradiation. Selective heating of metallic CNTs in air results in selective removal of metallic CNTs when the laser fluence and wavelength are properly selected. Through this process, metallic nanotubes are successfully removed from the CNT mixtures. This technique provides an efficient single-step approach for selective removal of metallic CNTs from CNT mixtures.

Transparent interconnections formed by rapid single-step fabrication of graphene patterns

We developed a process to form transparent interconnections using graphene patterns that were synthesized by laser chemical vapor deposition. The number of graphene layers was tightly controlled by laser scan speed. Graphene patterns were fabricated at a high scan speed of up to 200 μm/s with a single-step process. The process time is about a million times faster than the conventional chemical vapor deposition method. The fabricated graphene patterns on nickel foils were directly transferred to desired positions on patterned electrodes. The position-controlled transfer with rapid single-step fabrication of graphene patterns provides an innovative pathway for graphene-based interconnections.

Tailoring Vacancies Far Beyond Intrinsic Levels Changes the Carrier Type and Optical Response in Monolayer MoSe2−x Crystals

Defect engineering has been a critical step in controlling the transport characteristics of electronic devices, and the ability to create, tune, and annihilate defects is essential to enable the range of next-generation devices. Whereas defect formation has been well-demonstrated in three-dimensional semiconductors, similar exploration of the heterogeneity in atomically thin two-dimensional semiconductors and the link between their atomic structures, defects, and properties has not yet been extensively studied. Here, we demonstrate the growth of MoSe2-x single crystals with selenium (Se) vacancies far beyond intrinsic levels, up to ∼20%, that exhibit a remarkable transition in electrical transport properties from n- to p-type character with increasing Se vacancy concentration. A new defect-activated phonon band at ∼250 cm(-1) appears, and the A1g Raman characteristic mode at 240 cm(-1) softens toward ∼230 cm(-1) which serves as a fingerprint of vacancy concentration in the crystals. We show that post-selenization using pulsed laser evaporated Se atoms can repair Se-vacant sites to nearly recover the properties of the pristine crystals. First-principles calculations reveal the underlying mechanisms for the corresponding vacancy-induced electrical and optical transitions.