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    CVD Synthesis of MoS2 Using a Direct MoO2 Precursor: A Study on the Effects of Growth Temperature on Precursor Diffusion and Morphology Evolutions
    (2023-07-01)
    Somphonsane, Ratchanok
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    Chiawchan, Tinna
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    Bootsa-ard, Waraporn
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    Ramamoorthy, Harihara
    In this study, the influence of growth temperature variation on the synthesis of MoS<inf>2</inf> using a direct MoO<inf>2</inf> precursor was investigated. The research showed that the growth temperature had a strong impact on the resulting morphologies. Below 650 °C, no nucleation or growth of MoS<inf>2</inf> occurred. The optimal growth temperature for producing continuous MoS<inf>2</inf> films without intermediate-state formation was approximately 760 °C. However, when the growth temperatures exceeded 800 °C, a transition from pure MoS<inf>2</inf> to predominantly intermediate states was observed. This was attributed to enhanced diffusion of the precursor at higher temperatures, which reduced the local S:Mo ratio. The diffusion equation was analyzed, showing how the diffusion coefficient, diffusion length, and concentration gradients varied with temperature, consistent with the experimental observations. This study also investigated the impact of increasing the MoO<inf>2</inf> precursor amount, resulting in the formation of multilayer MoS<inf>2</inf> domains at the outermost growth zones. These findings provide valuable insights into the growth criteria for the effective synthesis of clean and large-area MoS<inf>2</inf>, thereby facilitating its application in semiconductors and related industries.
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    Investigation of the high-field transport, Joule-heating-driven conductivity improvement and low-field resistivity behaviour in lightly-reduced free-standing graphene oxide papers
    (2022-06-16)
    Thamkrongart, Krongtham
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    Ramamoorthy, Harihara
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    Buapan, Kanokwan
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    Chiawchan, Tinna
    ;
    Somphonsane, Ratchanok
    Free-standing reduced graphene oxide (rGO) has been gaining popularity for its use in supercapacitors and battery applications due its facile synthesis, multi-layered structure, and high-current carrying capacity. Pertinent to the successful implementation of such applications, however, is the need to develop a thorough understanding of the electrical properties of such materials when subject to high applied electric fields. In this work, we undertake a detailed study of high-field electrical properties of mm-scale, lightly-reduced, rGO papers. Our results reveal that the I-V curves exhibit substantial nonlinearity with associated hysteresis that depends strongly on the applied electric field. The nonlinear behaviour which was interpreted using conventional transport models of Fowler-Nordheim tunnelling and space charge limited conduction revealed that while these models provided good qualitative fits to our data, they were quantitatively lacking, thus leaving the issue of high-field transport mechanisms in rGO open for debate. Careful I-V cycling experiments with measurement time-delay introduced between cycles revealed that the observed hysteresis contained recoverable and non-recoverable parts that we identified as arising from charge trapping and Joule heating effects, respectively. Time-dependent measurements showed that these effects were characterized by two distinct time scales. Importantly, the Joule heating was found to cause a permanent conductivity improvement in the rGO via the 'current annealing' effect by effectively eliminating oxygenated groups from the rGO. The analysis of the electrical breakdown in our samples resembled a thermal runaway-like event that resulted in premature damage to the rGO. Finally, we investigated the low-field resistivity in the 80 K-300 K temperature range. The reduced activation energy analysis revealed a robust power law behaviour below 230 K, while deviating from this trend at higher temperatures. For samples that received current annealing treatment, a reduced value for the power law exponent was obtained, confirming the effective lowering of disordered regions.
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    Cvd synthesis of intermediate state-free, large-area and continuous mos2 via single-step vapor-phase sulfurization of moo2 precursor
    (2021-10-01)
    Chiawchan, Tinna
    ;
    Ramamoorthy, Harihara
    ;
    Buapan, Kanokwan
    ;
    Somphonsane, Ratchanok
    The low evaporation temperature and carcinogen classification of commonly used molybdenum trioxide (MoO3) precursor render it unsuitable for the safe and practical synthesis of molybdenum disulfide (MoS2). Furthermore, as evidenced by several experimental findings, the associated reaction constitutes a multistep process prone to the formation of uncontrolled amounts of intermediate MoS2−yOy phase mixed with the MoS2 crystals. Here, molybdenum dioxide (MoO2), a chemically more stable and safer oxide than MoO3, was utilized to successfully grow cm-scale continuous films of monolayer MoS2. A high-resolution optical image stitching approach and Raman line mapping were used to confirm the composition and homogeneity of the material grown across the substrate. A detailed examination of the surface morphology of the continuous film revealed that, as the gas flow rate increased by an order of magnitude, the grain-boundary separation dramatically reduced, implying a transition from a kinetically to thermodynamically controlled growth. Importantly, the single-step vapor-phase sulfurization (VPS) reaction of MoO2 was shown to suppress intermediate state formations for a wide range of experimental parameters investigated and is completely absent, provided that the global S:Mo loading ratio is set higher than the stoichiometric ratio of 3:1 required by the VPS reaction.
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    Exploration of the temperature-dependent correlations present in the structural, morphological and electrical properties of thermally reduced free-standing graphene oxide papers
    (2021-09-01)
    Ramamoorthy, Harihara
    ;
    Buapan, Kanokwan
    ;
    Chiawchan, Tinna
    ;
    Thamkrongart, Krongtham
    ;
    Somphonsane, Ratchanok
    We report on a corroborative study of the structural, morphological and electrical property alterations of free-standing graphene oxide (GO) papers subject to thermal reduction. Structural analysis performed using Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and Raman techniques prove that the onset of major structural changes, characterized by removal of oxygen functionalities, occur in the 200–300 °C temperature range. The results are corroborated with related morphological changes observed using Scanning electron microscopy (SEM) and Atomic force microscopy (AFM) imaging. Elemental analysis shows the GO paper reduced at 600 °C to contain an 85 wt. % carbon content and a remnant oxygen level of 13.31 wt. %. At the highest reduction temperatures, we see evidence of vacancy-type defects impeding the overall effectiveness of the reduction process. Detailed electrical resistance measurements and current–voltage (I-V) profiling conducted using four-point probe method reveals a several orders of magnitude drop in the sample resistance once the reduction temperature exceeds 200 °C, in good agreement with the structural and morphological changes. The fundamental insights revealed through these studies will be important for future applications where the electrical and mechanical properties of free-standing GO and reduced graphene oxide (rGO) are exploited in practical devices. Graphical abstract: [Figure not available: see fulltext.].
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    Versatile, Low-Cost, and Portable 2D Material Transfer Setup with a Facile and Highly Efficient DIY Inert-Atmosphere Glove Compartment Option
    (2021-07-20)
    Buapan, Kanokwan
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    Somphonsane, Ratchanok
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    Chiawchan, Tinna
    ;
    Ramamoorthy, Harihara
    Research in van der Waals heterostructures has been rapidly progressing in the past decade, thanks to the art of sequential and deterministic placement of one two-dimensional (2D) material over another. The successful creation of heterostructures however has relied largely on expensive transfer systems that are not easily accessible to researchers. Although a few reports on low-cost systems have recently surfaced, the full functionality, portability features, and overall effectiveness of such systems are still being explored. In this work, we present an "all-in-one"low-cost transfer setup that is compact, lightweight, and portable and which can be quickly installed with a facile and do it yourself (DIY)-style anaerobic glovebox option that performs at par with commercial anaerobic systems. The "installable"glovebox option means the user has the convenience of quickly converting the working environment into an inert one when air-sensitive 2D materials are used. The lowest RH values obtained in our glovebox is <3%, and the O2 levels rapidly drop from 21% to less than 0.1% in just a few minutes of purging the chamber with inert gas. The transfer system is also equipped with a light-weight PID-controlled substrate heating option that can be easily assembled within just a few hours. We test the versatility of our low-cost system by the successful creation of hexagonal boron nitride (hBN)-encapsulated graphene and hBN-encapsulated molybdenum disulphide (MoS2) heterostructures using the hot pickup technique and graphene-hBN, MoS2-hBN, twisted MoS2, and twisted MoS2 on hBN stacks using the wetting technique, and a MoS2-hBN-graphene vertical tunneling heterostructure was formed using a combination approach. The effectiveness of the DIY glovebox is proven with the demonstration of extended stability of freshly exfoliated black phosphorous (BP) flakes, their encapsulation between thin hBN layers, and the formation of electrically contacted BP devices with a protective hBN top layer. At an overall price point of approximately 1000 $, the versatile setup presented here is expected to further contribute to the growth of research in 2D materials, in particular, for researchers initially faced with overcoming a huge entry-level threshold to work in the field of 2D materials and van der Waals heterostructures.