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Aravamudhan, Shyam

Publications and source records attributed to Aravamudhan, Shyam.

8 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Phase Transformation and Water Adsorption Behavior of As‐Deposited and Annealed Ru Metal Thin Films Prepared by Atomic Layer Deposition

ABSTRACT Surfaces play a central role in catalytic processes, and understanding the transformation of ruthenium metal into ruthenium oxide during annealing is essential for tailoring functional catalytic interfaces. In this study, we systematically investigate ≈22 nm thick Ru metal films deposited by atomic layer deposition (ALD) at 300°C, focusing on their chemical composition, structural evolution, and surface hydration behavior following post‐deposition annealing in air from 400 to 600°C. Lab‐based and synchrotron X‐ray photoelectron spectroscopy (XPS) reveal a gradual conversion from metallic Ru to fully oxidized Ru 4+ with increasing annealing temperature, accompanied by a corresponding increase in lattice oxygen. X‐ray diffraction (XRD) shows amorphous Ru oxide phases at 400°C and 500°C that evolve into crystalline RuO 2 at 600°C, while atomic force microscopy (AFM) indicates enhanced grain growth and surface roughening upon annealing. Ambient‐pressure XPS (AP‐XPS) under controlled H 2 O vapor environments (1–17 Torr) demonstrates that samples annealed at 400°C and 500°C exhibit initially high hydroxyl coverage that decreases with increasing water vapor pressure, concurrent with a rise in molecular H 2 O adsorption. In contrast, the crystalline RuO 2 surface formed at 600°C maintains stable hydroxylation and supports increased water uptake. Overall, this work provides fundamental insight into Ru oxide–H 2 O interactions and establishes design principles for engineering oxide surfaces optimized for electrocatalytic applications.

APXPS↗
DOE OSTI2025

Transformation of TiN to TiNO Films via In-Situ Temperature-Dependent Oxygen Diffusion Process and Their Electrochemical Behavior

Titanium oxynitride (TiNO) thin films represent a multifaceted material system applicable in diverse fields, including energy storage, solar cells, sensors, protective coatings, and electrocatalysis. This study reports the synthesis of TiNO thin films grown at different substrate temperatures using pulsed laser deposition. A comprehensive structural investigation was conducted by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Non-Rutherford backscattering spectrometry (N-RBS), and X-ray absorption spectroscopy (XAS), which facilitated a detailed analysis that determined the phase, composition, and crystallinity of the films. Structural control was achieved via temperature-dependent oxygen in-diffusion, nitrogen out-diffusion, and the nucleation growth process related to adatom mobility. The XPS analysis indicates that the TiNO films consist of heterogeneous mixtures of TiN, TiNO, and TiO2 phases with temperature-dependent relative abundances. The correlation between the structure and electrochemical behavior of the thin films was examined. The TiNO films with relatively higher N/O ratio, meaning less oxidized, were more electrochemically active than the films with lower N/O ratio, i.e., more oxidized films. Films with higher oxidation levels demonstrated enhanced crystallinity and greater stability under electrochemical polarization. These findings demonstrate the importance of substrate temperature control in tailoring the properties of TiNO film, which is a fundamental part of designing and optimizing an efficient electrode material.

Cherono, Sheilah↗
DOE OSTI2024

Effect of Substrate Temperature on the Electrochemical and Supercapacitance Properties of Pulsed Laser-Deposited Titanium Oxynitride Thin Films

Electrocatalytically active titanium oxynitride (TiNO) thin films were fabricated on commercially available titanium metal plates using a pulsed laser deposition method for energy storage applications. The elemental composition and nature of bonding were analyzed using X-ray photoelectron spectroscopy (XPS) to reveal the reacting species and active sites responsible for the enhanced electrochemical performance of the TiNO electrodes. Symmetric supercapacitor devices were fabricated using two TiNO working electrodes separated by an ion-transporting layer to analyze their real-time performance. The galvanostatic charge–discharge studies on the symmetric cell have indicated that TiNO films deposited on the polycrystalline titanium plates at lower temperatures are superior to TiNO films deposited at higher temperatures in terms of storage characteristics. For example, TiNO films deposited at 300 °C exhibited the highest specific capacity of 69 mF/cm 2 at 0.125 mA/cm 2 with an energy density of 7.5 Wh/cm 2 . The performance of this supercapacitor (300 °C TiNO) device is also found to be ~22% better compared to that of a 500 °C TiNO supercapacitor with a capacitance retention ability of 90% after 1000 cycles. Furthermore, the difference in the electrochemical storage and capacitance properties is attributed to the reduced leaching away of oxygen from the TiNO films by the Ti plate at lower deposition temperatures, leading to higher oxygen content in the TiNO films and, consequently, a high redox activity at the electrode/electrolyte interface.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2024

Defects and Defect Engineering of Two-Dimensional Transition Metal Dichalcogenide (2D TMDC) Materials

As layered materials, transition metal dichalcogenides (TMDCs) are promising two-dimensional (2D) materials. Interestingly, the characteristics of these materials are transformed from bulk to monolayer. The atomically thin TMDC materials can be a good alternative to group III–V and graphene because of their emerging tunable electrical, optical, and magnetic properties. Although 2D monolayers from natural TMDC materials exhibit the purest form, they have intrinsic defects that limit their application. However, the synthesis of TMDC materials using the existing fabrication tools and techniques is also not immune to defects. Additionally, it is difficult to synthesize wafer-scale TMDC materials for a multitude of factors influencing grain growth mechanisms. While defect engineering techniques may reduce the percentage of defects, the available methods have constraints for healing defects at the desired level. Thus, this holistic review of 2D TMDC materials encapsulates the fundamental structure of TMDC materials, including different types of defects, named zero-dimensional (0D), one-dimensional (1D), and two-dimensional (2D). Moreover, the existing defect engineering methods that relate to both formation of and reduction in defects have been discussed. Finally, an attempt has been made to correlate the impact of defects and the properties of these TMDC materials.

2D materials↗
DOE OSTI2023

Towards Low-Temperature CVD Synthesis and Characterization of Mono- or Few-Layer Molybdenum Disulfide

Molybdenum disulfide (MoS 2 ) transistors are a promising alternative for the semiconductor industry due to their large on/off current ratio (>10 10 ), immunity to short-channel effects, and unique switching characteristics. MoS 2 has drawn considerable interest due to its intriguing electrical, optical, sensing, and catalytic properties. Monolayer MoS 2 is a semiconducting material with a direct band gap of ~1.9 eV, which can be tuned. Commercially, the aim of synthesizing a novel material is to grow high-quality samples over a large area and at a low cost. Although chemical vapor deposition (CVD) growth techniques are associated with a low-cost pathway and large-area material growth, a drawback concerns meeting the high crystalline quality required for nanoelectronic and optoelectronic applications. This research presents a lower-temperature CVD for the repeatable synthesis of large-size mono- or few-layer MoS 2 using the direct vapor phase sulfurization of MoO 3 . The samples grown on Si/SiO 2 substrates demonstrate a uniform single-crystalline quality in Raman spectroscopy, photoluminescence (PL), scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and scanning transmission electron microscopy. These characterization techniques were targeted to confirm the uniform thickness, stoichiometry, and lattice spacing of the MoS 2 layers. The MoS 2 crystals were deposited over the entire surface of the sample substrate. With a detailed discussion of the CVD setup and an explanation of the process parameters that influence nucleation and growth, this work opens a new platform for the repeatable synthesis of highly crystalline mono- or few-layer MoS 2 suitable for optoelectronic application.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Bandgap recovery of monolayer MoS 2 using defect engineering and chemical doping

Two-dimensional transition metal dichalcogenide materials have created avenues for exciting physics with unique electronic and photonic applications. Among these materials, molybdenum disulfide is the most known due to extensive research in understanding its electronic and optical properties. In this paper, we report on the successful growth and modification of monolayer MoS 2 (1L MoS 2 ) by controlling carrier concentration and manipulating bandgap in order to improve the efficiency of light emission. Atomic size MoS 2 vacancies were created using a Helium Ion Microscope, then the defect sites were doped with 2,3,5,6-tetrafluro7,7,8,8-tetracyanoquinodimethane (F4TCNQ). The carrier concentration in intrinsic (as-grown) and engineered 1L MoS 2 was calculated using Mass Action model. The results are in a good agreement with Raman and photoluminescence spectroscopy as well as Kelvin probe force microscopy characterizations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Quantification of defects engineered in single layer MoS 2

Atomic defects are controllably introduced in suspended single layer molybdenum disulfide (1L MoS 2 ) using helium ion beam. Vacancies exhibit one missing atom of molybdenum and a few atoms of sulfur. Quantification was done using a Scanning Transmission Electron Microscope (STEM) with an annular detector. Experimentally accessible inter-defect distance was employed to measure the degree of crystallinity in 1L MoS 2 . A correlation between the appearance of an acoustic phonon mode in the Raman spectra and the inter-defect distance was established, which introduces a new methodology for quantifying defects in two-dimensional materials such as MoS 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗