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Iron-assisted growth of anisotropic ZnO nanostructures
Anisotropic nanostructures offer a promising pathway to modulate structure-function relationships of materials. However, the correlation between growth direction of high-quality anisotropic nanostructures, the synthesis conditions and mechanisms controlling their growth, and their magnetic and optical properties remain underexplored. In this study, we developed an iron-assisted anisotropic growth method to form zinc oxide nanostructures on the O-polar (0001̄) surface, resulting in two distinct ZnO-based nanostructures: hand-shaped nanostructures and truncated hexagonal nanopyramids. In contrast to most reports of anisotropic nanostructure synthesis, which primarily focus on morphology control through ligand-ligand interactions, the current study probes the effects of doping on anisotropic growth, and how doping, along with ligand-ligand interactions and facet-specific ligand binding, control nanostructure morphology. The reaction mechanisms leading to formation of these novel structures were thoroughly probed by systematically manipulating synthesis parameters. A two-step formation mechanism was identified: first, a hexagonal platform forms through an initial homogeneous nucleation process, followed by secondary heterogeneous nucleation, which results in metastable secondary nanostructures growing on the oxygen-rich template. Optical and magnetic properties of these Fe/ZnO nanostructures were characterized. Our findings provide a new strategy that uses a magnetic element as a dopant to build new nanostructures of ZnO with controllable size and shape growing on an oxygen-rich crystal plane. These materials could have applications in novel technologies where both optoelectronic and magnetic properties are of interest.
Metal ion dopant-induced famatinite to chalcostibite phase transformation of copper antimony sulphide colloidal nanostructures: effect on photophysical and pseudocapacitance properties
Here, the strategic doping of transition metal ions into copper antimony sulphide (CAS) semiconducting nanostructures can significantly influence their photophysical and pseudocapacitive properties, for which there are few reports and therefore is the focus of this study. Accordingly, highly crystalline metal ion (Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ and Zn 2+ ) doped off-stoichiometric copper rich/poor, antimony-rich/poor, and sulphur-poor CAS nanostructures (10–23 nm) were grown via colloidal (hot-injection) synthesis using metal diethyldithiocarbamate precursors. Importantly, metal ion doping significantly influences the structure and composition of the off-stoichiometric CAS nanostructures. Data from powder X-ray diffraction, Raman spectroscopy, high-resolution scanning/transmission electron microscopy, and energy dispersive X-ray spectroscopy confirm that the heavier metal ion dopants induce a novel phase transformation from famatinite (fCAS) to chalcostibite (cCAS) nanostructures. The influence of the metal ion dopants is also observed in the optical properties of as-synthesized nanostructures. This involves blue-shifted ultraviolet-visible absorption, reduced Urbach tailing, and tunable bandgaps between 2.17 and 2.38 eV. Also, the doped nanostructures display broad visible-near infrared photoluminescence via a triple radiative pathway with relatively short decay lifetimes between 0.2 and 6.1 ns. This is mediated by electronic transitions involving intrinsic (copper/antimony/sulphur interstitial) and extrinsic (metal ion interstitial) defect states. Additionally, electrodes prepared from Mn 2+ -doped fCAS nanostructures show enhanced pseudocapacitance via Na+ surface adsorption and intercalation relative to undoped fCAS electrodes, while Zn 2+ -doped cCAS electrodes exhibit pseudocapacitance via a combination of Na+ surface adsorption, intercalation, and redox reactions. These electrodes exhibit reduced charge transfer resistance, improved electronic conductivity and notably enhanced specific capacitance (∼222 F g −1 ), and charge transport, as measured in 1 M Na 2 SO 4 electrolyte via cyclic voltammetry and electrochemical impedance spectroscopy. To this end, the discovery of the metal ion-induced phase transformation presents a new avenue for optimizing the functional properties of fCAS and cCAS nanostructures, highlighting the critical role of metal ion-related defects in controlling the optical and electrochemical properties, towards potential solar absorption and energy storage applications.
The Development of Metal Oxide Chemical Sensing Nanostructures
This paper discusses sensor development based on metal oxide nanostructures and microsystems technology. While nanostructures such as nanowires show significant potential as enabling materials for chemical sensors, a number of significant technical challenges remain. This paper discusses development to address each of these technical barriers: 1) Improved contact and integration of the nanostructured materials with microsystems in a sensor structure; 2) Control of nanostructure crystallinity to allow control of the detection mechanism; and 3) Widening the range of gases that can be detected by fabricating multiple nanostructured materials. A sensor structure composed of three nanostructured oxides aligned on a single microsensor has been fabricated and tested. Results of this testing are discussed and future development approaches are suggested. It is concluded that while this work lays the foundation for further development, these are the beginning steps towards realization of repeatable, controlled sensor systems using oxide based nanostructures.
Nanostructure Diffraction Gratings for Integrated Spectroscopy and Sensing
The present disclosure pertains to metal or dielectric nanostructures of the subwavelength scale within the grating lines of optical diffraction gratings. The nanostructures have surface plasmon resonances or non-plasmon optical resonances. A linear photodetector array is used to capture the resonance spectra from one of the diffraction orders. The combined nanostructure super-grating and photodetector array eliminates the use of external optical spectrometers for measuring surface plasmon or optical resonance frequency shift caused by the presence of chemical and biological agents. The nanostructure super-gratings can be used for building integrated surface enhanced Raman scattering (SERS) spectrometers. The nanostructures within the diffraction grating lines enhance Raman scattering signal light while the diffraction grating pattern of the nanostructures diffracts Raman scattering light to different directions of propagation according to their wavelengths. Therefore, the nanostructure super-gratings allows for the use of a photodetector array to capture the surface enhanced Raman scattering spectra.
Nanostructure Diffraction Gratings for Integrated Spectroscopy and Sensing
The present disclosure pertains to metal or dielectric nanostructures of the subwavelength scale within the grating lines of optical diffraction gratings. The nanostructures have surface plasmon resonances or non-plasmon optical resonances. A linear photodetector array is used to capture the resonance spectra from one of the diffraction orders. The combined nanostructure super-grating and photodetector array eliminates the use of external optical spectrometers for measuring surface plasmon or optical resonance frequency shift caused by the presence of chemical and biological agents. The nanostructure super-gratings can be used for building integrated surface enhanced Raman scattering (SERS) spectrometers. The nanostructures within the diffraction grating lines enhance Raman scattering signal light while the diffraction grating pattern of the nanostructures diffracts Raman scattering light to different directions of propagation according to their wavelengths. Therefore, the nanostructure super-gratings allows for the use of a photodetector array to capture the surface enhanced Raman scattering spectra.
Effect of growth dynamics on the structural, photophysical and pseudocapacitance properties of famatinite copper antimony sulphide colloidal nanostructures (including nanosheets)
Facile phase selective synthesis of copper antimony sulphide (CAS) nanostructures is important because of their tunable photoconductive and electrochemical properties. In this study, off-stoichiometric famatinite phase CAS (fCAS) quasi-spherical and quasi-hexagonal colloidal nanostructures (including nanosheets) of sizes, 2.4–18.0 nm were grown under variable conditions of temperature (60–200 °C), time and oleylamine capping ligand concentration using copper(II) acetylacetonate and antimony(III) diethyldithiocarbamate precursors. Data from powder X-ray diffraction, Raman spectroscopy and high-resolution scanning/transmission electron microscopy confirm the tetragonal structure of the famatinite phase. X-ray photoelectron spectroscopy, transmission electron microscopy and scanning electron microscopy-energy dispersive X-ray spectroscopy data suggest a correlation of particle size, morphology and composition of the off-stoichiometric fCAS nanostructures with growth temperature and time, and oleylamine concentration. The off-stoichiometric Cu 3-a Sb 1+b S 4±c (a, b, c – mole fractions) nanostructures being severely copper-deficient and antimony-rich, exhibit shallow-lying acceptor copper vacancy states, deep-lying donor states of antimony interstitials, sulphur vacancies and antimony-copper antisites and shallow-lying acceptor surface trapping states. Further, these electronic states are likely implicated in tunable UV-visible absorption and bandgaps between 2.3 and 2.8 eV, and broad visible-NIR photoluminescence with fast recombination of radiative lifetimes between 0.2 and 6.2 ns, confirmed from absorption, steady-state and time-resolved photoluminescence spectroscopies. Additionally, cyclic voltammetry and electrochemical impedance spectroscopy confirm that electrodes of the fCAS nanostructures display slightly variable pseudocapacitance of charge-storage primarily via possible sodium ion intercalation with a high specific capacitance of ~84 F g -1 obtained at a scan rate of 5 mV s -1 . Overall, these results show the influence of composition, in particular point defects, phase quality and morphology on the optical and pseudocapacitance properties of fCAS nanostructures, suitable as solar absorbers or electrodes for energy storage devices.
Low Temperature Growth of Nanostructured Diamond Films on Metals
The field of nanocrystalline diamond and tetrahedral amorphous carbon films has been the focus of intense experimental activity in the last few years for applications in field emission display devices, optical windows, and tribological coatings, The choice of substrate used in most studies has typically been silicon. For metals, however, the thermal expansion mismatch between the diamond film and substrate gives rise to thermal stress that often results in delamination of the film. To avoid this problem in conventional CVD deposition low substrate temperatures (less than 700 C) have been used, often with the incorporation of oxygen or carbon monoxide to the feedgas mixture. Conventionally grown CVD diamond films are also rough and would require post-deposition polishing for most applications. Therefore, there is an obvious need to develop techniques for deposition of well-adhered, smooth nano-structured diamond films on metals for various tribological applications. In our work, nanostructured diamond films are grown on a titanium alloy substrate using a two-step deposition process. The first step is performed at elevated temperature (820 C) for 30 minutes using a H2/CH4/N2 gas mixture in order to grow a thin (approx. 600 nm) nanostructured diamond layer and improve film adhesion. The remainder of the deposition involves growth at low temperature (less than 600 C) in a H2/CH4/O2 gas mixture. Laser reflectance Interferometry (LRI) pattern during growth of a nanostructured diamond film on Ti-6Al-4V alloy. The first 30 minutes are at a high temperature of 820 C and the rest of the film is grown at a low temperature of 580 T. The fringe pattern is observed till the very end due to extremely low surface roughness of 40 nm. The continuation of the smooth nanostructured diamond film growth during low temperature deposition is confirmed by in-situ laser reflectance interferometry and by post-deposition micro-Raman spectroscopy and surface profilometry. Similar experiments performed without the starting nanostructured diamond layer resulted in poorly adhered films with a more crystalline appearance and a higher surface roughness. This low temperature deposition of nanostructured diamond films on metals offers advantages in cases where high residual thermal stress leads to delamination at high temperatures.
Chemical Sensors Based on Metal Oxide Nanostructures
This paper is an overview of sensor development based on metal oxide nanostructures. While nanostructures such as nanorods show significan t potential as enabling materials for chemical sensors, a number of s ignificant technical challenges remain. The major issues addressed in this work revolve around the ability to make workable sensors. This paper discusses efforts to address three technical barriers related t o the application of nanostructures into sensor systems: 1) Improving contact of the nanostructured materials with electrodes in a microse nsor structure; 2) Controling nanostructure crystallinity to allow co ntrol of the detection mechanism; and 3) Widening the range of gases that can be detected by using different nanostructured materials. It is concluded that while this work demonstrates useful tools for furt her development, these are just the beginning steps towards realizati on of repeatable, controlled sensor systems using oxide based nanostr uctures.
Self-Sorting vs Coassembly in Peptide Amphiphile Supramolecular Nanostructures
The functionality of supramolecular nanostructures can be expanded if systems containing multiple components are designed to either self-sort or mix into coassemblies. This is critical to gain the ability to craft self-assembling materials that integrate functions, and our understanding of this process is in its early stages. Here, in this work, we have utilized three different peptide amphiphiles with the capacity to form β-sheets within supramolecular nanostructures and found binary systems that self-sort and others that form coassemblies. This was measured using atomic force microscopy to reveal the nanoscale morphology of assemblies and confocal laser scanning microscopy to determine the distribution of fluorescently labeled monomers. We discovered that PA assemblies with opposite supramolecular chirality self-sorted into chemically distinct nanostructures. In contrast, the PA molecules that formed a mixture of right-handed, left-handed, and flat nanostructures on their own were able to coassemble with the other PA molecules. We attribute this phenomenon to the energy barrier associated with changing the handedness of a β-sheet twist in a coassembly of two different PA molecules. This observation could be useful for designing biomolecular nanostructures with dual bioactivity or interpenetrating networks of PA supramolecular assemblies.
Formation of distinctive nanostructured metastable polymorphs mediated by kinetic transition pathways in germanium
High-pressure β -Sn germanium may transform into diverse metastable allotropes with distinctive nanostructures and unique physical properties via multiple pathways under decompression. However, the mechanism and transition kinetics remain poorly understood. Here, we investigate the formation of metastable phases and nanostructures in germanium via controllable transition pathways of β -Sn Ge under rapid decompression at different rates. High-resolution transmission electron microscopy reveals three distinct metastable phases with the distinctive nanostructures: an almost perfect st12 Ge crystal, nanosized bc8/r8 structures with amorphous boundaries, and amorphous Ge with nanosized clusters (0.8–2.5 nm). Fast in situ x-ray diffraction and x-ray absorption measurements indicate that these nanostructured products form in certain pressure regions via distinct kinetic pathways and are strongly correlated with nucleation rates and electronic transitions mediated by compression rate, temperature, and stress. This work provides deep insight into the controllable synthesis of metastable materials with unique crystal symmetries and nanostructures for potential applications.
Integration of Nanostructures into Microsensor Devices on Whole Wafers
Chemical sensors are used in a wide variety of applications, such as environmental monitoring, fire detection, emission monitoring, and health monitoring. The fabrication of chemical sensors involving nanostructured materials holds the potential for the development of sensor systems with unique properties and improved performance. However, the fabrication and processing of nanostructures for sensor applications currently are limited in the ability to control their location on the sensor, which in turn hinders the progress for batch fabrication. This report discusses the advantages of using nanomaterials in sensor designs, some of the challenges encountered with the integration of nanostructures into microsensor / devices, and then briefly describes different methods attempted by other groups to address this issue. Finally, this report will describe how our approach for the controlled alignment of nanostructures onto a sensor platform was applied to demonstrate an approach for the mass production of sensors with nanostructures.
Single-Molecule Fluorescence Investigations of Solute Transport Dynamics in Nanostructured Membrane Separation Materials
Many materials used for membrane separations comprise of nanoscale structures such as pores and domains. Such nanostructures often control the solute permeability and selectivity of separation membranes. Thus, for future development of highly efficient separation membranes, it is important to understand the structural and chemical properties of these nanostructures, and also their influences on solute transport dynamics. For the last two decades, single-molecule fluorescence techniques have been used to measure the detailed dynamics of solute molecules diffusing in various nanostructured materials, giving valuable insights into molecular transport mechanisms influenced by nanoscale material heterogeneity. This Perspective will discuss recent single-molecule fluorescence studies on solute diffusion in materials relevant to membrane separations, including dense polymer films and nanoporous materials. These studies have revealed the formation and properties of nanostructures, and unique transport dynamics of solute molecules manipulated by their confinement and partitioning to the nanostructures, which play key roles in membrane separations. Furthermore, this Perspective will also point out scientific challenges toward thorough understanding of molecular-level mechanisms in membrane separations.
Atomic-scale cryogenic electron microscopy imaging of self-assembled peptoid nanostructures
Amphiphilic polypeptoids with defined sequences, versatile in forming various nanostructures, are ideal for mimicking biomacromolecular structures. The predictive design of nanostructures depends on our understanding of the relationship between molecular structure and the locations of atoms in the nanostructure. Factors of importance include chain conformation, crystal motifs, and the arrangement of the molecules within the nanostructure. Here, this review introduces the cryogenic transmission electron microscopy (cryo-TEM) method, sorting and averaging unit cells in nanosheets for resolution enhancement and identifying structural heterogeneity. The resulting atomic-scale images reveal the presence of two types of crystal motifs. The impact of processing conditions, capping group chemistry, and side chain chemistry on structural heterogeneity and crystal motifs can be quantified. The 3D reconstruction of nanosheets, wherein atomic-scale corrugations were revealed, is introduced in this review. New developments in cryo-TEM, such as phase retrieval reconstruction, hold great promise for atomic-scale imaging of soft nanostructures.
Nanostructure Engineered Chemical Sensors for Hazardous Gas and Vapor Detection
A nanosensor technology has been developed using nanostructures, such as single walled carbon nanotubes (SWNTs) and metal oxides nanowires or nanobelts, on a pair of interdigitated electrodes (IDE) processed with a silicon based microfabrication and micromachining technique. The IDE fingers were fabricated using thin film metallization techniques. Both in-situ growth of nanostructure materials and casting of the nanostructure dispersions were used to make chemical sensing devices. These sensors have been exposed to hazardous gases and vapors, such as acetone, benzene, chlorine, and ammonia in the concentration range of ppm to ppb at room temperature. The electronic molecular sensing in our sensor platform can be understood by electron modulation between the nanostructure engineered device and gas molecules. As a result of the electron modulation, the conductance of nanodevice will change. Due to the large surface area, low surface energy barrier and high thermal and mechanical stability, nanostructured chemical sensors potentially can offer higher sensitivity, lower power consumption and better robustness than the state-of-the-art systems, which make them more attractive for defense and space applications. Combined with MEMS technology, light weight and compact size sensors can be made in wafer scale with low cost.
Nanostructures Exploit Hybrid-Polariton Resonances
Nanostructured devices that exploit the hybrid-polariton resonances arising from coupling among photons, phonons, and plasmons are subjects of research directed toward the development of infrared-spectroscopic sensors for measuring extremely small quantities of molecules of interest. The spectroscopic techniques in question are surface enhanced Raman scattering (SERS) and surface enhanced infrared absorption (SEIRA). An important intermediate goal of this research is to increase the sensitivity achievable by these techniques. The basic idea of the approach being followed in this research is to engineer nanostructured devices and thereby engineer their hybrid-polariton resonances to concentrate infrared radiation incident upon their surfaces in such a manner as to increase the absorption of the radiation for SEIRA and measure the frequency shifts of surface vibrational modes. The underlying hybrid-polariton-resonance concept is best described by reference to experimental devices that have been built and tested to demonstrate the concept. The nanostructure of each such device includes a matrix of silicon carbide particles of approximately 1 micron in diameter that are supported on a potassium bromide (KBr) or poly(tetrafluoroethylene) [PTFE] window. These grains are sputter-coated with gold grains of 40-nm size (see figure). From the perspective of classical electrodynamics, in this nanostructure, that includes a particulate or otherwise rough surface, the electric-field portion of an incident electromagnetic field becomes concentrated on the particles when optical resonance conditions are met. Going beyond the perspective of classical electrodynamics, it can be seen that when the resonance frequencies of surface phonons and surface plasmons overlap, the coupling of the resonances gives rise to an enhanced radiation-absorption or -scattering mechanism. The sizes, shapes, and aggregation of the particles determine the frequencies of the resonances. Hence, the task of designing a nanostructure to exhibit the desired radiation-absorption properties translates, in large part, to selecting particle sizes and shapes to obtain the desired enhanced coupling of energy from photons to plasmons and phonons. To broaden the spectral region(s) of enhanced absorption, one would select a distribution of particle sizes and shapes.
Low-Temperature Activation and Coupling of Methane on MgO Nanostructures Embedded in Cu 2 O/Cu(111)
Here, the efficient conversion of methane into valuable hydrocarbons such as ethane and ethylene at relatively low temperatures without deactivation issues is crucial for advancing sustainable energy solutions. Herein, AP-XPS and STM studies show that MgO nanostructures (0.2-0.5 nm wide, 0.4-0.6 Å high) embedded in a Cu 2 O/Cu(111) substrate activate methane at room temperature, mainly dissociating it into CH x (x = 2 or 3) and H adatoms, with minimal conversion to C adatoms. These MgO nanostructures in contact with Cu 2 O/Cu(111) exhibit unique reactivity, enabling C-C coupling into ethane and ethylene at 500 K, a significantly lower temperature than that required for bulk MgO catalysts (>700 K), with negligible carbon deposition and no deactivation. DFT calculations corroborate these experimental findings. The CH 4,gas → *CH 3 +*H reaction is a downhill process on MgO/Cu 2 O/Cu(111) surfaces. The activation of methane is facilitated by an electron transfer from copper to MgO and the existence of Mg and O atoms with a low coordination number in the oxide nanostructures. The formation of O-CH 3 and O-H bonds overcomes the energy necessary for the cleavage of a C-H bond in methane. DFT studies reveal that smaller Mg 2 O 2 model clusters provide stronger binding and lower activation barriers for C-H dissociation in CH 4 , while larger Mg 3 O 3 clusters promote C-C coupling due to weaker *CH 3 binding. All these results emphasize the importance of size when optimizing the catalytic performance of MgO nanostructures in the selective conversion of methane.
Study on the Carbon Nanostructures for Nanosized Si Electrodes
Silicon (Si) has been considered as a next-generation anode material due to natural abundance, low operating potential (<0.5 V vs. Li/Li+), and high theoretical specific capacity of 4200 mAh g-1.[1] However, the electrochemical alloying reaction of Si involves large volume changes of 400% during lithiation and delithiation, causing cracking and pulverization of Si.[1] In addition, solid electrolyte interface (SEI) of Si anode experiences constant changes due to unstable SEI reactivity.[2] Considerable efforts have been made to design nanostructured Si materials to address the issues because nanostructuring can relieve the mechanical strain.[3] However, when compared to micrometer-sized active materials having sufficient electrolyte pathway through interparticle space, the nanoparticle (NP)-based electrodes tend to be densely packed. As mass loading is higher and electrode is thicker, ion transport issue can become more severe in the densely packed electrodes.[4] In this work, we will present studies on engineered porosity impacts performance in Si NP electrodes by altering carbon nanostructures. We explore the extreme limit of effectively non-porous electrodes using quasi-spherical, Si NPs, which result in densely packed electrodes when slurry is prepared with conventional carbon black. We engineer porosity using carbon nanostructures including multi-walled carbon nanotubes and carbon nanorods in place of conventional carbon black to create pore structure in Si NP-based electrodes. These experiments provide a correlation between mass loading, porosity and silicon utilization in Si NP-based electrodes. References: [1] C. K. Chan, H. Peng, G. Liu, K. Mcllwrath, X. F. Zhang, R. A. Huggins, Y. Cui, "High-performance lithium battery anodes using silicon nanowires", Nat. Nanotechnol., 2008, 3, 31, [2] J. D. McBrayer, M.-T. F. Rodrigues, M. C. Schulze, D. P. Abraham, C. A. Apblett, I. Bloom, G. M. Carroll, A. M. Coclasure, C. Fang, K. L. Harrison, G. Liu, S. D. Minteer, N. R. Neale, G. M. Veith, C. S. Johnson, J. T. Vaughey, A. K. Burrel, B. Cunningham, "Calendar aging of silicon-containing batteries", Nat. Energy, 2021, 6, 1164, [3] H. Wu, G. Zheng, N. Liu, T. J. Carney, Y. Yang, Y. Cui, "Engineering Empty space between Si Nanoparticles for Lithium-Ion Battery Anodes", Nano Lett., 2012, 12, 904, [4] X. Zhang, Z. Ju, Y. Zhu, K. J. Takeuchi, E. S. Takeuchi, A. C. Marschilok, G. Yu, "Multiscale Understanding and Architecture Design of High Energy/Power Lithium-Ion Battery Electrodes", Adv. Energy Mater., 2021, 11, 2000808