Water splitting has been widely considered to be an efficient way to generate sustainable and renewable energy resources in fuel cells, metal–air batteries and other energy conversion devices. Exploring efficient electrocatalysts to expedite the anodic oxygen evolution reaction (OER) is a crucial task that needs to be addressed in order to boost the practical application of water splitting. Intensive efforts have been devoted to develop mixed transition metal based chalcogenides as effective OER electrocatalysts. Herein, we have reported synthesis of a series of mixed metal selenides containing Co, Ni and Cu employing combinatorial electrodeposition, and systematically investigated how the transition metal doping affects the OER catalytic activity in alkaline medium. Energy dispersive spectroscopy (EDS) was performed to detect the elemental compositions and confirm the feasibility of compositional control of 66 metal selenide thin films. It was observed that the OER catalytic activity is sensitive to the concentration of Cu in the catalysts, and the catalyst activity tended to increase with increasing Cu concentration. However, increasing the Cu concentration beyond a certain limit led to decrease in catalytic efficiency, and copper selenide by itself, although catalytically active, showed higher onset potential and overpotential for OER compared to the ternary and quaternary mixed metal selenides. Interestingly, the best quaternary composition (Co 0.21 Ni 0.25 Cu 0.54 ) 3 Se 2 showed similar crystal structure as its parent compound of Cu 3 Se 2 with slight decrease in lattice spacings of (101) and (210) lattice planes (0.0222 Å and 0.0148 Å, respectively) evident from the powder X-ray diffraction pattern. (Co 0.21 Ni 0.25 Cu 0.54 ) 3 Se 2 thin film exhibited excellent OER catalytic activity and required an overpotential of 272 mV to reach a current density of 10 mA cm −2 , which is 54 mV lower than Cu 3 Se 2 , indicating a synergistic effect of transition metal doping in enhancing catalytic activity.
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Chemical vapor transport synthesis, characterization and compositional tuning of ZrSxSe2−x for optoelectronic applications
ZrS2, ZrSe2 and mixed alloy ZrSxSe2−x materials were achieved through chemical vapor transport. The incongruent
melting system of Zr-S-Se formed crystalline layered flakes as a transport product that grew up to 2 cm in
lateral size with cm-scale flakes consistently obtained for the entire compositional range exhibiting visible
hexagonal features. Bulk flakes of the series ZrSxSe2−x (x=0, 0.15, 0.3, 0.6, 1.05, 1.14, 1.51, 1.8 and 2) were
analyzed through Raman spectroscopy revealing significant convolution of primary bonding modes and shifting
of Raman features as a function of increasing sulfur composition. Additionally, activation of new modes not
present in the pure compounds are observed as effects which result from disorder introduced into the crystal due
to the random mixing of S-Se in the alloying process. Further structural characterization was performed via x-ray
diffraction (XRD) on the layered flakes to evaluate the progression of layer spacing function of alloy composition
which was found to range between 6.24 Å for ZrSe2 and 5.85 Å for ZrS2. Estimation of the compositional ratios of
the alloy flakes through energy dispersive spectroscopy (EDS) large-area mapping verified the relation of the
targeted source stoichiometry represented in the layered flakes. Atomic-resolution high angle annular dark field
(HAADF)-scanning transmission electron microscopy (STEM) imaging was performed on the representative Zr
(S0.5Se0.5)2 alloy to validate the 1T atomic structure and observe the arrangement of the chalcogenide columns
stacks. Additionally, selected area diffraction pattern generated from the [0 0 0 1] zone axis revealed the in-plane
lattice parameter to be approximately 3.715 Å.
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- Award ID(s):
- 1654107
- NSF-PAR ID:
- 10231550
- Date Published:
- Journal Name:
- Journal of crystal growth
- Volume:
- 542
- ISSN:
- 0022-0248
- Page Range / eLocation ID:
- 125609
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Germanium alloyed with α-tin (GeSn) transitions to a direct bandgap semiconductor of significance for optoelectronics. It is essential to localize the carriers within the active region for improving the quantum efficiency in a GeSn based laser. In this work, epitaxial GeSn heterostructure material systems were analyzed to determine the band offsets for carrier confinement: (i) a 0.53% compressively strained Ge 0.97 Sn 0.03 /AlAs; (ii) a 0.81% compressively strained Ge 0.94 Sn 0.06 /Ge; and (iii) a lattice matched Ge 0.94 Sn 0.06 /In 0.12 Al 0.88 As. The phonon modes in GeSn alloys were studied using Raman spectroscopy as a function of Sn composition, that showed Sn induced red shifts in wavenumbers of the Ge–Ge longitudinal optical phonon mode peaks. The material parameter b representing strain contribution to Raman shifts of a Ge 0.94 Sn 0.06 alloy was determined as b = 314.81 ± 14 cm −1 . Low temperature photoluminescence measurements were performed at 79 K to determine direct and indirect energy bandgaps of E g,Γ = 0.72 eV and E g,L = 0.66 eV for 0.81% compressively strained Ge 0.94 Sn 0.06 , and E g,Γ = 0.73 eV and E g,L = 0.68 eV for lattice matched Ge 0.94 Sn 0.06 epilayers. Chemical effects of Sn atomic species were analyzed using X-ray photoelectron spectroscopy (XPS), revealing a shift in Ge 3d core level (CL) spectra towards the lower binding energy affecting the bonding environment. Large valence band offset of Δ E V = 0.91 ± 0.1 eV and conduction band offset of Δ E C,Γ–X = 0.64 ± 0.1 eV were determined from the Ge 0.94 Sn 0.06 /In 0.12 Al 0.88 As heterostructure using CL spectra by XPS measurements. The evaluated band offset was found to be of type-I configuration, needed for carrier confinement in a laser. In addition, these band offset values were compared with the first-principles-based calculated Ge/InAlAs band alignment, and it was found to have arsenic up-diffusion limited to 1 monolayer of epitaxial GeSn overlayer, ruling out the possibility of defects induced modification of band alignment. Furthermore, this lattice matched GeSn/InAlAs heterostructure band offset values were significantly higher than GeSn grown on group IV buffer/substrates. Therefore, a lattice matched GeSn/InAlAs material system has large band offsets offering superior carrier confinement to realize a highly efficient GeSn based photonic device.more » « less
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Abstract Large area highly crystalline MoS2and WS2thin films were successfully grown on different substrates using radio-frequency magnetron sputtering technique. Structural, morphological and thermoelectric transport properties of MoS2,and WS2thin films have been investigated systematically to fabricate high-efficient thermal energy harvesting devices. X-ray diffraction data revealed that crystallites of MoS2and WS2films are highly oriented in 002 plane with uniform grain size distribution confirmed through atomic force microscopy study. Surface roughness increases with substrate temperature and it plays a big role in electron and phonon scattering. Interestingly, MoS2films also display low thermal conductivity at room temperature and strongly favors achievement of higher thermoelectric figure of merit value of up to 1.98. Raman spectroscopy data shows two distinct MoS2vibrational modes at 380 cm−1for E12gand 410 cm−1for A1g. Thermoelectric transport studies further demonstrated that MoS2films show p-type thermoelectric characteristics, while WS2is an n-type material. We demonstrated high efficient pn-junction thermoelectric generator device for waste heat recovery and cooling applications.
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1016/j.jcrysgro.2020.125609
