In this work, we study the properties and device applications of MoS2, black phosphorus, MoOx, and NbSe2. We first start with the design, fabrication, and characterization of ultra-high responsivity photodetectors based on mesoscopic multilayer MoS2. The device architecture is comprised of a metal-semiconductor-metal (MSM) photodetector, where Mo was used as the contact metal to suspended MoS2 membranes. The dominant photocurrent mechanism was determined to be the photoconductive effect, while a contribution from the photogating effect was also noted from trap-states that yielded a wide spectral photoresponse from UV-to-IR with an external quantum efficiency (EQE) ~ 104. From time-resolved photocurrent measurements, a fast decay time and response time were obtained with a stream of incoming ON/OFF white light pulses. Another interesting semiconductor 2D material that has attracted special attention due to its small bandgap and ultra-high hole mobility is the black phosphorus. An analysis of the optoelectronic properties and photocurrent generation mechanisms in two-dimensional (2D) multilayer crystallites of black phosphorus (BP) was conducted from 350 K down to cryogenic temperatures using a broad-band white light source. The Mo-BP interface yielded a low Schottky barrier "φ" _"SB" ~ -28.3 meV and a high photoresponsivity R of ~ 2.43 x 105 A/W at a source-drain bias voltage of ~ 0.5 V (300 K, and incident optical power ~ 3.16 μW/cm2). Our report is the first to highlight the empirical use of Mo as a contact metal with BP. From the analysis conducted on the BP devices, the thermally driven photocurrent generation mechanism arising from the photobolometric effect (PBE) dominated the carrier dynamics for T > 181 K since the photocurrent Iph and the bolometric coefficient β undergo a transition in polarity from positive to negative. Our results show the promise of BP to potentially advance thermoelectric and optoelectronic devices stemming from this mono-elemental, direct bandgap 2D van der Waals solid. Another intriguing metallic 2D material is superconducting 2H-NbSe2. Here we present the temperature-dependent Raman spectroscopy and electronic transport on bulk NbSe2, carried out to investigate the scattering mechanisms. We report on the photoresponse of direct probed mesoscopic 2H-NbSe2 as a function of laser energy for lasers at 405 nm, 660 nm, and 1060 nm wavelengths used to irradiate the device, where the modulation from the superconducting-to-normal-state is detected through photomodulation. Additionally, the various oxidation levels of molybdenum oxide have interesting optical and electrical properties as a function of the oxygen vacancy and stoichiometry. The substoichiometric MoOx (2 < x < 3) behaves as a high work function conductor due to its metallic defect band. As a result, one of the potential applications of MoOx is for electrical contacts providing high hole injection or extraction. In this work, we have synthesized MoOx nanosheets via chemical vapor deposition and a four-terminal device was fabricated via e-beam lithography and electronic transport was measured as a function of temperature. Outstanding properties were obtained from our MoOx nanosheets, including a high conductivity of ~ 6,680.3 S cm-1, a superior temperature coefficient of resistance ~ -0.10%, and a high sensitivity based on the bolometric coefficient β of ~ 0.152 mS K-1. In summary, this work pushes the state-of-the-art in enabling 2D van der Waals materials for next-generation high-performance detectors.

abstract: Liquid-phase exfoliation (LPE) is a straightforward and scalable method of producing two-dimensional nanomaterials. The LPE process has typical been applied to layered van der Waals (vdW) solids, such as graphite and transition metal dichalcogenides, which have layers held together by weak van der Waals interactions. However, recent research has shown that solids with stronger bonds and non-layered structures can be converted to solution-stabilized nanosheets via LPE, some of which have shown to have interesting optical, magnetic, and photocatalytic properties. In this work, two classes of non-vdW solids – hexagonal metal diborides and boron carbide – are investigated for their morphological features, their chemical and crystallographic compositions, and their solvent preference for exfoliation. Spectroscopic and microscopic techniques are used to verify the composition and crystal structure of metal diboride nanosheets. Their application as mechanical fillers is demonstrated by incorporation into polymer nanocomposite films of polyvinyl alcohol and by successful integration into liquid photocurable 3D printing resins. Application of Hansen solubility theory to two metal diboride compositions enables extrapolation of their affinities for certain solvents and is also used to find solvent blends suitable for the nanosheets. Boron carbide nanosheets are examined for their size and thickness and their exfoliation planes are computationally analyzed and experimentally investigated using high-resolution transmission electron microscopy. The resulting analyses indicate that the exfoliation of boron carbide leads to multiple observed exfoliation planes upon LPE processing. Overall, these studies provide insight into the production and applications of LPE-produced nanosheets derived from non-vdW solids and suggest their potential application as mechanical fillers in polymer nanocomposites. / Dissertation/Thesis / Doctoral Dissertation Chemistry 2020