Ahmad N. Abbas

High-Performance Chemical Sensing Using Schottky-Contacted Chemical Vapor Deposition Grown Monolayer MoS2 Transistors

Trace chemical detection is important for a wide range of practical applications. Recently emerged two-dimensional (2D) crystals offer unique advantages as potential sensing materials with high sensitivity, owing to their very high surface-to-bulk atom ratios and semiconducting properties. Here, we report the first use of Schottky-contacted chemical vapor deposition grown monolayer MoS2 as high-performance room temperature chemical sensors. The Schottky-contacted MoS2 transistors show current changes by 2-3 orders of magnitude upon exposure to very low concentrations of NO2 and NH3. Specifically, the MoS2 sensors show clear detection of NO2 and NH3 down to 20 ppb and 1 ppm, respectively. We attribute the observed high sensitivity to both well-known charger transfer mechanism and, more importantly, the Schottky barrier modulation upon analyte molecule adsorption, the latter of which is made possible by the Schottky contacts in the transistors and is not reported previously for MoS2 sensors. This study shows the potential of 2D semiconductors as high-performance sensors and also benefits the fundamental studies of interfacial phenomena and interactions between chemical species and monolayer 2D semiconductors.

Black phosphorus gas sensors.

The utilization of black phosphorus and its monolayer (phosphorene) and few-layers in field-effect transistors has attracted a lot of attention to this elemental two-dimensional material. Various studies on optimization of black phosphorus field-effect transistors, PN junctions, photodetectors, and other applications have been demonstrated. Although chemical sensing based on black phosphorus devices was theoretically predicted, there is still no experimental verification of such an important study of this material. In this article, we report on chemical sensing of nitrogen dioxide (NO2) using field-effect transistors based on multilayer black phosphorus. Black phosphorus sensors exhibited increased conduction upon NO2 exposure and excellent sensitivity for detection of NO2 down to 5 ppb. Moreover, when the multilayer black phosphorus field-effect transistor was exposed to NO2 concentrations of 5, 10, 20, and 40 ppb, its relative conduction change followed the Langmuir isotherm for molecules adsorbed on a surface. Additionally, on the basis of an exponential conductance change, the rate constants for adsorption and desorption of NO2 on black phosphorus were extracted for different NO2 concentrations, and they were in the range of 130-840 s. These results shed light on important electronic and sensing characteristics of black phosphorus, which can be utilized in future studies and applications.

Patterning, characterization, and chemical sensing applications of graphene nanoribbon arrays down to 5 nm using helium ion beam lithography.

Bandgap engineering of graphene is an essential step toward employing graphene in electronic and sensing applications. Recently, graphene nanoribbons (GNRs) were used to create a bandgap in graphene and function as a semiconducting switch. Although GNRs with widths of <10 nm have been achieved, problems like GNR alignment, width control, uniformity, high aspect ratios, and edge roughness must be resolved in order to introduce GNRs as a robust alternative technology. Here we report patterning, characterization, and superior chemical sensing of ultranarrow aligned GNR arrays down to 5 nm width using helium ion beam lithography (HIBL) for the first time. The patterned GNR arrays possess narrow and adjustable widths, high aspect ratios, and relatively high quality. Field-effect transistors were fabricated on such GNR arrays and temperature-dependent transport measurements show the thermally activated carrier transport in the GNR array structure. Furthermore, we have demonstrated exceptional NO2 gas sensitivity of the 5 nm GNR array devices down to parts per billion (ppb) levels. The results show the potential of HIBL fabricated GNRs for the electronic and sensing applications.

Black Arsenic–Phosphorus: Layered Anisotropic Infrared Semiconductors with Highly Tunable Compositions and Properties

New layered anisotropic infrared semiconductors, black arsenic-phosphorus (b-AsP), with highly tunable chemical compositions and electronic and optical properties are introduced. Transport and infrared absorption studies demonstrate the semiconducting nature of b-AsP with tunable bandgaps, ranging from 0.3 to 0.15 eV. These bandgaps fall into the long-wavelength infrared regime and cannot be readily reached by other layered materials.

Chemical Vapor Deposition Growth of Monolayer WSe2 with Tunable Device Characteristics and Growth Mechanism Study.

Semiconducting transition metal dichalcogenides (TMDCs) have attracted a lot of attention recently, because of their interesting electronic, optical, and mechanical properties. Among large numbers of TMDCs, monolayer of tungsten diselenides (WSe2) is of particular interest since it possesses a direct band gap and tunable charge transport behaviors, which make it suitable for a variety of electronic and optoelectronic applications. Direct synthesis of large domains of monolayer WSe2 and their growth mechanism studies are important steps toward applications of WSe2. Here, we report systematical studies on ambient pressure chemical vapor deposition (CVD) growth of monolayer and few layer WSe2 flakes directly on silica substrates. The WSe2 flakes were characterized using optical microscopy, atomic force microscopy, Raman spectroscopy, and photoluminescence spectroscopy. We investigated how growth parameters, with emphases on growth temperatures and durations, affect the sizes, layer numbers, and shapes of as-grown WSe2 flakes. We also demonstrated that transport properties of CVD-grown monolayer WSe2, similar to mechanically exfoliated samples, can be tuned into either p-type or ambipolar electrical behavior, depending on the types of metal contacts. These results deepen our understandings on the vapor phase growth mechanism of WSe2, and may benefit the uses of these CVD-grown monolayer materials in electronic and optoelectronics.

Screw-Dislocation-Driven Growth of Two-Dimensional Few-Layer and Pyramid-like WSe2 by Sulfur-Assisted Chemical Vapor Deposition

Two-dimensional (2D) layered tungsten diselenides (WSe2) material has recently drawn a lot of attention due to its unique optoelectronic properties and ambipolar transport behavior. However, direct chemical vapor deposition (CVD) synthesis of 2D WSe2 is not as straightforward as other 2D materials due to the low reactivity between reactants in WSe2 synthesis. In addition, the growth mechanism of WSe2 in such CVD process remains unclear. Here we report the observation of a screw-dislocation-driven (SDD) spiral growth of 2D WSe2 flakes and pyramid-like structures using a sulfur-assisted CVD method. Few-layer and pyramid-like WSe2 flakes instead of monolayer were synthesized by introducing a small amount of sulfur as a reducer to help the selenization of WO3, which is the precursor of tungsten. Clear observations of steps, helical fringes, and herringbone contours under atomic force microscope characterization reveal the existence of screw dislocations in the as-grown WSe2. The generation and propagation mechanisms of screw dislocations during the growth of WSe2 were discussed. Back-gated field-effect transistors were made on these 2D WSe2 materials, which show on/off current ratios of 10(6) and mobility up to 44 cm(2)/(V·s).

Reversible Semiconducting-to-Metallic Phase Transition in Chemical Vapor Deposition Grown Monolayer WSe2 and Applications for Devices

Two-dimensional (2D) semiconducting monolayer transition metal dichalcogenides (TMDCs) have stimulated lots of interest because they are direct bandgap materials that have reasonably good mobility values. However, contact between most metals and semiconducting TMDCs like 2H phase WSe2 are highly resistive, thus degrading the performance of field effect transistors (FETs) fabricated with WSe2 as active channel materials. Recently, a phase engineering concept of 2D MoS2 materials was developed, with improved device performance. Here, we applied this method to chemical vapor deposition (CVD) grown monolayer 2H-WSe2 and demonstrated semiconducting-to-metallic phase transition in atomically thin WSe2. We have also shown that metallic phase WSe2 can be converted back to semiconducting phase, demonstrating the reversibility of this phase transition. In addition, we fabricated FETs based on these CVD-grown WSe2 flakes with phase-engineered metallic 1T-WSe2 as contact regions and intact semiconducting 2H-WSe2 as active channel materials. The device performance is substantially improved with metallic phase source/drain electrodes, showing on/off current ratios of 10(7) and mobilities up to 66 cm(2)/V·s for monolayer WSe2. These results further suggest that phase engineering can be a generic strategy to improve device performance for many kinds of 2D TMDC materials.

Deposition, Characterization, and Thin-Film-Based Chemical Sensing of Ultra-long Chemically Synthesized Graphene Nanoribbons

Bottom-up synthesis of graphene nanoribbons (GNRs) is an essential step toward utilizing them in electronic and sensing applications due to their defined edge structure and high uniformity. Recently, structurally perfect GNRs with variable lengths and edge structures were created using various chemical synthesis techniques. Nonetheless, issues like GNR deposition, characterization, electronic properties, and applications are not fully explored. Here we report optimized conditions for deposition, characterization, and device fabrication of individual and thin films of ultra-long chemically synthesized GNRs. Moreover, we have demonstrated exceptional NO2 gas sensitivity of the GNR film devices down to parts per billion (ppb) levels. The results lay the foundation for using chemically synthesized GNRs for future electronic and sensing applications.

Step-Edge-Guided Nucleation and Growth of Aligned WSe2 on Sapphire via a Layer-over-Layer Growth Mode.

Two-dimensional (2D) materials beyond graphene have drawn a lot of attention recently. Among the large family of 2D materials, transitional metal dichalcogenides (TMDCs), for example, molybdenum disulfides (MoS2) and tungsten diselenides (WSe2), have been demonstrated to be good candidates for advanced electronics, optoelectronics, and other applications. Growth of large single-crystalline domains and continuous films of monolayer TMDCs has been achieved recently. Usually, these TMDC flakes nucleate randomly on substrates, and their orientation cannot be controlled. Nucleation control and orientation control are important steps in 2D material growth, because randomly nucleated and orientated flakes will form grain boundaries when adjacent flakes merge together, and the formation of grain boundaries may degrade mechanical and electrical properties of as-grown materials. The use of single crystalline substrates enables the alignment of as-grown TMDC flakes via a substrate-flake epitaxial interaction, as demonstrated recently. Here we report a step-edge-guided nucleation and growth approach for the aligned growth of 2D WSe2 by a chemical vapor deposition method using C-plane sapphire as substrates. We found that at temperatures above 950 °C the growth is strongly guided by the atomic steps on the sapphire surface, which leads to the aligned growth of WSe2 along the step edges on the sapphire substrate. In addition, such atomic steps facilitate a layer-over-layer overlapping process to form few-layer WSe2 structures, which is different from the classical layer-by-layer mode for thin-film growth. This work introduces an efficient way to achieve oriented growth of 2D WSe2 and adds fresh knowledge on the growth mechanism of WSe2 and potentially other 2D materials.

High-Performance WSe2 Field-Effect Transistors via Controlled Formation of In-Plane Heterojunctions.

Monolayer WSe2 is a two-dimensional (2D) semiconductor with a direct band gap, and it has been recently explored as a promising material for electronics and optoelectronics. Low field-effect mobility is the main constraint preventing WSe2 from becoming one of the competing channel materials for field-effect transistors (FETs). Recent results have demonstrated that chemical treatments can modify the electrical properties of transition metal dichalcogenides (TMDCs), including MoS2 and WSe2. Here, we report that controlled heating in air significantly improves device performance of WSe2 FETs in terms of on-state currents and field-effect mobilities. Specifically, after being heated at optimized conditions, chemical vapor deposition grown monolayer WSe2 FETs showed an average FET mobility of 31 cm(2)·V(-1)·s(-1) and on/off current ratios up to 5 × 10(8). For few-layer WSe2 FETs, after the same treatment applied, we achieved a high mobility up to 92 cm(2)·V(-1)·s(-1). These values are significantly higher than FETs fabricated using as-grown WSe2 flakes without heating treatment, demonstrating the effectiveness of air heating on the performance improvements of WSe2 FETs. The underlying chemical processes involved during air heating and the formation of in-plane heterojunctions of WSe2 and WO3-x, which is believed to be the reason for the improved FET performance, were studied by spectroscopy and transmission electron microscopy. We further demonstrated that, by combining the air heating method developed in this work with supporting 2D materials on the BN substrate, we achieved a noteworthy field-effect mobility of 83 cm(2)·V(-1)·s(-1) for monolayer WSe2 FETs. This work is a step toward controlled modification of the properties of WSe2 and potentially other TMDCs and may greatly improve device performance for future applications of 2D materials in electronics and optoelectronics.