Quantitative High Resolution Phase Contrast Imaging of Au-Cu Bimetallic Nanostructures Manish Kumar Singh, Joysurya Basu, B Mukherjee, R K Mandal Microscopy and Microanalysis, 2024 The combination of gold and copper is a potential way to reduce the cost of metallic interconnects and ameliorate the instability of copper [1,2].Through shape-controlled synthesis, the synergy of these two metals can be exploited in a better fashion [3].The phase diagram of Au-Cu is complex in nature with appearance of several intermetallic phases such as Au 3 Cu, AuCu and AuCu 3 at lower temperatures ( 400C).Several new phases are also reported in Au-Cu system at nanometric length scale [4][5][6].In addition to that, alloying behavior of Au-Cu is not understood well when the temperature is lowered down further.In this investigation, Au-Cu intermetallic nanoparticles have been synthesized by adopting a three-step protocol in a single pot.These nanoparticles at 180C for 1 h led to the formation of single-phase solid solution of Cu in Au.Subsequent heat treatment at 290C for 2 h led to the transformation from random solid solution to intermetallic Au-Cu nanoparticles.From TEM and STEM-EDS results, it has been observed that nanoparticles are composed of Au-Cu homogeneous alloy.To understand the alloying behavior and underlying chemistry of Au-Cu nanostructures, attempts have been made to quantitatively understand the contrast and its interpretation in terms of atom column positions of Au and Cu of high-resolution phase contrast images.Multislice image simulations were performed with varying thickness and defocus values, and they were matched with the experimentally obtained high resolution phase contrast images [7].To understand the electron channeling behavior along Au and Cu atom columns, exit wave analysis have been carried out on high resolution phase contrast images acquired from ordered cubic Cu 3 Au intermetallic nanocrystals along [001] zone axis.Figure 1 shows experimentally recorded high-resolution phase contrast micrograph from an ordered cubic Cu 3 Au along [001] orientation and corresponding projected structure.The exit wave -potential, wave function, amplitude and phases have been retrieved over thickness ranging from 6 nm to 45 nm along Au and Cu atom columns as presented in Figure 2. The exit wave analysis revealed the contrast reversal in phase of Cu atom columns at every 9 nm thickness unlike Au atom columns where phase was observed throughout the entire thickness.Preferential imaging of Cu atom columns could be attributed to its potential and the channeling behavior of the electron wave.
Asymmetric nanoparticle oxidation observed in-situ by the evolution of diffraction contrast Agus R Poerwoprajitno, Nitish Baradwaj, Manish Kumar Singh, C Barry Carter, Dale L Huber, Rajiv Kalia, John Watt Jphys Materials, 2023 The use of transmission electron microscopy (TEM) to observe real-time structural and compositional changes has proven to be a valuable tool for understanding the dynamic behavior of nanomaterials. However, identifying the nanoparticles of interest typically require an obvious change in position, size, or structure, as compositional changes may not be noticeable during the experiment. Oxidation or reduction can often result in subtle volume changes only, so elucidating mechanisms in real-time requires atomic-scale resolution or in-situ electron energy loss spectroscopy, which may not be widely accessible. Here, by monitoring the evolution of diffraction contrast, we can observe both structural and compositional changes in iron oxide nanoparticles, specifically the oxidation from a wüstite-magnetite (FeO@Fe3O4) core–shell nanoparticle to single crystalline magnetite, Fe3O4 nanoparticle. The in-situ TEM images reveal a distinctive light and dark contrast known as the ‘Ashby-Brown contrast’, which is a result of coherent strain across the core–shell interface. As the nanoparticles fully oxidize to Fe3O4, the diffraction contrast evolves and then disappears completely, which is then confirmed by modeling and simulation of TEM images. This represents a new, simplified approach to tracking the oxidation or reduction mechanisms of nanoparticles using in-situ TEM experiments.
Intermetallics Based on Sodium Chalcogenides Promote Stable Electrodeposition–Electrodissolution of Sodium Metal Anodes Yixian Wang, Hui Dong, Naman Katyal, Bairav S. Vishnugopi, Manish K. Singh, Hongchang Hao, Yijie Liu, Pengcheng Liu, Partha P. Mukherjee, Graeme Henkelman, John Watt, David Mitlin Advanced Energy Materials, 2023 Sodiophilic micro‐composite films of sodium‐chalcogenide intermetallics (Na2Te and Na2S) and Cu particles are fabricated onto commercial copper foam current collectors (Na2Te@CF and Na2S@CF). For the first time a controllable capacity thermal infusion process is demonstrated. Enhanced wetting by the metal electrodeposition leads to state‐of‐the‐art electrochemical performance. For example, Na2Te@CF‐based half‐cells demonstrate stable cycling at 6 mA cm−2 and 6 mAh cm−2, corresponding to 54 µm of Na electrodeposited/electrodissolved by geometric area. Sodium metal batteries with Na3V2 (PO4)3 cathodes are stable at 30C (7 mA cm−2) and for 10 000 cycles at 5C and 10C. Cross‐sectional cryogenic focused ion beam (cryo‐FIB) microscopy details deposited and remnant dissolved microstructures. Sodium metal electrodeposition onto Na2Te@CF is dense, smooth, and free of dendrites or pores. On unmodified copper foam, sodium grows in a filament‐like manner, not requiring cycling to achieve this geometry. Substrate–metal interaction critically affects the metal–electrolyte interface, namely the thickness and morphology of the solid electrolyte interphase. Density functional theory and mesoscale simulations provide insight into support‐adatom energetics, nucleation response, and early‐stage morphological evolution. On Na2Te sodium atomic dispersion is thermodynamically more stable than isolated clusters, leading to conformal adatom coverage of the surface.
Mycosynthesis of Zinc Oxide Nanoparticles Exhibits Fungal Species Dependent Morphological Preference Nathan G. Brady, Shamus L. O'Leary, Garrett C. Moormann, Manish K. Singh, John Watt, George D. Bachand Small, 2023 Filamentous fungi can synthesize a variety of nanoparticles (NPs), a process referred to as mycosynthesis that requires little energy input, do not require the use of harsh chemicals, occurs at near neutral pH, and do not produce toxic byproducts. While NP synthesis involves reactions between metal ions and exudates produced by the fungi, the chemical and biochemical parameters underlying this process remain poorly understood. Here, the role of fungal species and precursor salt on the mycosynthesis of zinc oxide (ZnO) NPs is investigated. This data demonstrates that all five fungal species tested are able to produce ZnO structures that can be morphologically classified into i) well‐defined NPs, ii) coalesced/dissolving NPs, and iii) micron‐sized square plates. Further, species‐dependent preferences for these morphologies are observed, suggesting potential differences in the profile or concentration of the biochemical constituents in their individual exudates. This data also demonstrates that mycosynthesis of ZnO NPs is independent of the anion species, with nitrate, sulfate, and chloride showing no effect on NP production. These results enhance the understanding of factors controlling the mycosynthesis of ceramic NPs, supporting future studies that can enable control over the physical and chemical properties of NPs formed through this “green” synthesis method.
ε-Poly-l-lysine conjugated gold nanorod probe to monitor antimicrobial activity and mechanism of action by surface-enhanced Raman spectroscopy Manish Kumar Singh, Anant K. Singh, Tyren J. Dunmore, Jagriti Singh Journal of Raman Spectroscopy, 2023 Antimicrobial peptides have been demonstrated to display an immediate response to a large set of pathogenic activity against viruses, bacteria, and fungi by virtue of their local binding with phospholipid phosphatidylserines to exert cytotoxic effect. Plasmonic nanostructures are particularly appealing in medical diagnostics and therapeutics owing to their biocompatibility and ease of surface modification. The current article reports a development of ε‐poly‐l‐lysine modified gold nanorod (PLL‐AuNR) Raman‐active system that can be used to target pathogenic bacteria along with rapid monitoring of antimicrobial action from environmental samples. Result indicates a remarkable change in Raman enhancement factor from 1.49 × 104 to 2.17 × 107 after addition of Salmonella, Bacillus subtilis, and Escherichia coli bacteria in PLL‐AuNR colloid, enabling a large optical window to monitor the process of pathogenic action. Antimicrobial assay with PLL‐AuNR reveals significantly high cytotoxic values of ~92% in E. coli, ~90% in B. subtilis, and ~87% in Salmonella compared with their respective responses in bare PLL, which shows ~37% in E. coli, ~32% in B. subtilis, and ~27% in Salmonella, which proportionally collaborates with change in surface‐enhanced Raman spectroscopy (SERS) intensity beyond 10 min of incubation time. Major experimental design parameters and possible mechanism that relates unusual plasmonic enhancement and antimicrobial action of PLL‐AuNR system have also been discussed.
Cryo-FIB for TEM investigation of soft matter and beam sensitive energy materials Daniel M Long, Manish Kumar Singh, Kathryn A Small, John Watt Nanotechnology, 2022 Primarily driven by structural biology, the rapid advances in cryogenic electron microscopy techniques are now being adopted and applied by materials scientists. Samples that inherently have electron transparency can be rapidly frozen (vitrified) in amorphous ice and imaged directly on a cryogenic transmission electron microscopy (cryo-TEM), however this is not the case for many important materials systems, which can consist of layered structures, embedded architectures, or be contained within a device. Cryogenic focused ion beam (cryo-FIB) lift-out procedures have recently been developed to extract intact regions and interfaces of interest, that can then be thinned to electron transparency and transferred to the cryo-TEM for characterization. Several detailed studies have been reported demonstrating the cryo-FIB lift-out procedure, however due to its relative infancy in materials science improvements are still required to ensure the technique becomes more accessible and routinely successful. Here, we review recent results on the preparation of cryo-TEM lamellae using cryo-FIB and show that the technique is broadly applicable to a range of soft matter and beam sensitive energy materials. We then present a tutorial that can guide the materials scientist through the cryo-FIB lift-out process, highlighting recent methodological advances that address the most common failure points of the technique, such as needle attachment, lift-out and transfer, and final thinning.
Sensing performance of sub-100-nm vanadium oxide films for room temperature thermal detection applications Ethan A. Scott, Manish K. Singh, John P. Barber, Christina M. Rost, Sergei Ivanov, John Watt, Douglas Pete, Peter Sharma, Tzu-Ming Lu, C. Thomas Harris Applied Physics Letters, 2022 Vanadium oxide films are widely employed as thermal detectors in uncooled infrared detection systems due to their high temperature coefficient of resistance near room temperature. One strategy toward maximizing detectivity and reducing the thermal time constant in these systems is to minimize the system platform dimensions. This approach necessitates thinner film thicknesses (≪100 nm), for which there is little information regarding thermal sensing performance. Herein, we report on the sensitivity of reactively sputtered vanadium oxide thin film resistive thermometers nominally ranging from 100 to 25 nm and assess the influence of thermal annealing. We demonstrate that films in this minimum limit of thickness maintain a high temperature coefficient while additionally providing an enhancement in characteristics of the noise equivalent power.
Exfoliation and cracking in MoS 2 following in-situ lithiation C Ghosh, MK Singh, AM Dongare, C Barry Carter Journal of Materials Science 60 (3), 1381-1397 , 2025 2025
Asymmetric Nanoparticle Oxidation Observed In-Situ by the Evolution of Diffraction Contrast. AR Poerwoprajitno, N Baradwaj, MK Singh, CB Carter, DL Huber, R Kalia, ... Microscopy & Microanalysis 30 , 2024 2024
Quantitative High Resolution Phase Contrast Imaging of Au-Cu Bimetallic Nanostructures MK Singh, J Basu, B Mukherjee, RK Mandal Microscopy and Microanalysis 30 (Supplement_1), ozae044. 137 , 2024 2024
The Study of Crystallization Kinetics and Chemical Changes in Ge 4 Sb 4 Te 5 through Transmission Electron Microscope MK Singh, C Ghosh, J Watt, C Barry Carter, H Silva Microscopy and Microanalysis 30 (Supplement_1), ozae044. 838 , 2024 2024 Citations: 1
Asymmetric nanoparticle oxidation observed in-situ by the evolution of diffraction contrast AR Poerwoprajitno, N Baradwaj, MK Singh, CB Carter, DL Huber, R Kalia, ... Journal of Physics: Materials 6 (4), 045013 , 2023 2023 Citations: 3
Intermetallics based on sodium chalcogenides promote stable electrodeposition–electrodissolution of sodium metal anodes Y Wang, H Dong, N Katyal, BS Vishnugopi, MK Singh, H Hao, Y Liu, P Liu, ... Advanced energy materials 13 (27), 2204402 , 2023 2023 Citations: 57
Mycosynthesis of Zinc Oxide Nanoparticles Exhibits Fungal Species Dependent Morphological Preference (Small 15/2023) NG Brady, SL O'Leary, GC Moormann, MK Singh, J Watt, GD Bachand Small 19 (15), 2370101 , 2023 2023
Mycosynthesis of zinc oxide nanoparticles exhibits fungal species dependent morphological preference NG Brady, SL O'Leary, GC Moormann, MK Singh, J Watt, GD Bachand Small 19 (15), 2205799 , 2023 2023 Citations: 8
Cryo-FIB for TEM investigation of soft matter and beam sensitive energy materials DM Long, MK Singh, KA Small, J Watt Nanotechnology 33 (50), 503001 , 2022 2022 Citations: 24
Sensing performance of sub-100-nm vanadium oxide films for room temperature thermal detection applications EA Scott, MK Singh, JP Barber, CM Rost, S Ivanov, J Watt, D Pete, ... Applied Physics Letters 121 (20) , 2022 2022 Citations: 7
Optimization of gold germanium (Au0. 17Ge0. 83) thin films for high sensitivity resistance thermometry EA Scott, CM Smyth, MK Singh, TM Lu, P Sharma, D Pete, J Watt, ... Journal of Applied Physics 132 (6) , 2022 2022 Citations: 9
Rice extract-assisted green synthesis of Au nanoparticles: catalytic and sers activities MK Singh, A Verma, J Basu, I Sinha, P Chettri, A Tripathi, A Tiwari, ... Surface Review and Letters 29 (07), 2250090 , 2022 2022 Citations: 4
Characterizing Li in partially lithiated layer materials using atomic‐resolution imaging, modeling, and simulation C Ghosh, MK Singh, S Parida, A Dobley, AM Dongare, CB Carter Journal of the American Ceramic Society 105 (2), 1581-1595 , 2022 2022 Citations: 2
ε‐poly‐L‐lysine conjugated AuNR probe to monitor antimicrobial activity and mechanism of action by Surface Enhanced Raman Spectroscopy MK Singh, AK Singh, TJ Dunmore, J Singh Journal of Raman Spectroscopy , 2022 2022 Citations: 5
Microstructural Evolution of Chessboard like Nanodomains in Mn-doped ZnGaO4 Spinel A Pal, AKL Das, M Singh, C Ghosh, P Kotula, CB Carter, J Basu Microscopy and Microanalysis 27 (S1), 2418-2419 , 2021 2021 Citations: 1
Decrypting commensurate modulation, superstructure and inversion domain boundary in bismuth transition metal oxide through transmission electron microscopy S Choudhury, V Mohan, H Ghosh, A Pal, M Singh, R Mandal, J Basu Microscopy and Microanalysis 27 (S1), 3402-3404 , 2021 2021
TEM Studies of Nanoscale Phase Transformation during in-situ reaction of Li with 2D Materials (MoS2, WS2, Graphite) C Ghosh, MK Singh, S Parida, MT Janish, PG Kotula, A Dobley, ... Microscopy and Microanalysis 27 (S1), 338-340 , 2021 2021
In-situ TEM Studies of Structural Modification in WS 2 during Intercalation of Li and Na M Singh, C Ghosh, S Parida, MT Janish, P Kotula, A Dobley, A Dongare, ... Microscopy and Microanalysis 27 (S1), 654-656 , 2021 2021 Citations: 1
Investigation of Phase Transformations in Ge 4 Sb 4 Te 5 film using Transmission Electron Microscopy M Singh, C Ghosh, P Kotula, B Miller, J Watt, H Silva, C Barry Carter Microscopy and Microanalysis 27 (S1) , 2021 2021 Citations: 1
Reversible Phase Transformations during In-Situ Heating of Uncapped Ge2Sb2Te5 Films C Ghosh, M Singh, P Kotula, H Silva, C Barry Carter Microscopy and Microanalysis 27 (S1) , 2021 2021
MOST CITED SCHOLAR PUBLICATIONS
Mechano-chemical synthesis, thermal stability and phase evolution in AlCoCrFeNiMn high entropy alloy V Shivam, J Basu, Y Shadangi, MK Singh, NK Mukhopadhyay Journal of Alloys and Compounds 757, 87-97 , 2018 2018 Citations: 144
Green synthesis of silver nanoparticle-reduced graphene oxide using Psidium guajava and its application in SERS for the detection of methylene blue P Chettri, VS Vendamani, A Tripathi, MK Singh, AP Pathak, A Tiwari Applied Surface Science 406, 312-318 , 2017 2017 Citations: 127
Intermetallics based on sodium chalcogenides promote stable electrodeposition–electrodissolution of sodium metal anodes Y Wang, H Dong, N Katyal, BS Vishnugopi, MK Singh, H Hao, Y Liu, P Liu, ... Advanced energy materials 13 (27), 2204402 , 2023 2023 Citations: 57
Crystallite size induced bandgap tuning in WO3 derived from nanocrystalline tungsten S Bandi, D Vidyasagar, S Adil, MK Singh, J Basu, AK Srivastav Scripta Materialia 176, 47-52 , 2020 2020 Citations: 56
Influence of synthesis route on structural, optical, and electrical properties of TiO2 V Pawar, M Kumar, PK Dubey, MK Singh, ASK Sinha, P Singh Applied Physics A 125 (9), 1-14 , 2019 2019 Citations: 43
Auto-combustion synthesis and properties of Ce0.85Gd0.15O1.925 for intermediate temperature solid oxide fuel cells electrolyte NK Singh, P Singh, MK Singh, D Kumar, O Parkash Solid State Ionics 192 (1), 431-434 , 2011 2011 Citations: 34
Synthesis and characterization of Sn reinforced Al-Cu-Fe quasicrystalline matrix nanocomposite by mechanical milling Y Shadangi, V Shivam, MK Singh, K Chattopadhyay, J Basu, ... Journal of Alloys and Compounds 797, 1280-1287 , 2019 2019 Citations: 31
Defect mediated magnetic transitions in Fe and Mn-doped MoS2 MK Singh, P Chettri, A Tripathi, A Tiwari, B Mukherjee, RK Mandal Physical Chemistry Chemical Physics 20 (23), 15817-15823 , 2018 2018 Citations: 30
Phase evolution and structural modulation during in situ lithiation of MoS2, WS2 and graphite in TEM C Ghosh, MK Singh, S Parida, MT Janish, A Dobley, AM Dongare, ... Scientific Reports 11 (1), 1-16 , 2021 2021 Citations: 27
Synthesis of anisotropic Au–Cu alloy nanostructures and its application in SERS for detection of methylene blue MK Singh, P Chettri, J Basu, A Tripathi, B Mukherjee, A Tiwari, RK Mandal Materials Research Express 7 (1), 015052 , 2020 2020 Citations: 25
Cryo-FIB for TEM investigation of soft matter and beam sensitive energy materials DM Long, MK Singh, KA Small, J Watt Nanotechnology 33 (50), 503001 , 2022 2022 Citations: 24
Kinetically constraint zero-and one-dimensional heteroepitaxial island growth Z Li, MK Singh, ES Tok, JPY Tan, M Lin, YL Foo Applied Physics Letters 90 (10) , 2007 2007 Citations: 22
Role of Oxygen on Chemical Segregation in Uncapped Ge 2 Sb 2 Te 5 Thin Films on Silicon Nitride S Tripathi, P Kotula, MK Singh, C Ghosh, G Bakan, H Silva, CB Carter ECS Journal of Solid State Science and Technology 9 (5), 054007 , 2020 2020 Citations: 21
Porous and highly conducting cathode material PrBaCo2O6− δ: bulk and surface studies of synthesis anomalies AS Bangwal, PK Jha, PK Dubey, MK Singh, ASK Sinha, V Sathe, PA Jha, ... Physical Chemistry Chemical Physics 21 (27), 14701-14712 , 2019 2019 Citations: 21
Synthesis of rod-shaped Au-Cu intermetallic nanoparticles and SERS detection MK Singh, P Chettri, J Basu, A Tripathi, B Mukherjee, A Tiwari, RK Mandal Materials Letters 249, 33-36 , 2019 2019 Citations: 20
Effects on surface-enhanced Raman scattering from copper nanoparticles synthesized by laser ablation R Rawat, A Tiwari, MK Singh, RK Mandal, AP Pathak, A Tripathi Radiation Effects and Defects in Solids 175 (3-4), 332-341 , 2020 2020 Citations: 18
Growth morphology and special diffraction characteristics of multifaceted gold nanoparticles MK Singh, B Mukherjee, RK Mandal Micron 94, 46-52 , 2017 2017 Citations: 14
In situ TEM study of crystallization and chemical changes in an oxidized uncapped Ge2Sb2Te5 film MK Singh, C Ghosh, B Miller, PG Kotula, S Tripathi, J Watt, G Bakan, ... Journal of Applied Physics 128 (12) , 2020 2020 Citations: 13
Eriochrome Black T sensing using silver nanoparticle-reduced graphene oxide composite via luminescent “turn-off” mechanism and its biosorption on guava (Psidium guajava) leaf … P Chettri, MK Singh, A Tripathi, AP Pathak, RK Mandal, A Tiwari Graphene Technology 4 (1), 41-51 , 2019 2019 Citations: 12
Localized surface plasmon behavior of Ag-Cu alloy nanoparticles stabilized by rice-starch and gelatin MK Singh, P Manda, AK Singh, RK Mandal AIP Advances 5 (10) , 2015 2015 Citations: 12