Nanoscale Processes Research Articles

Fragmentation of Nickel(II) and Cobalt(II) Bis(acetylacetonate) Complexes Induced by Slow (

Metal acetylacetonate complexes have high potentiality in nanoscale fabrication processes (e.g., focus electron beam-induced deposition) thanks to the versatile character and ease of preparation compounds. In this work, we study and compare the physics and the physicochemistry induced by the interaction of low-energy (<10 eV) electrons with nickel(II) and cobalt(II) bis(acetylacetonate) complexes. The slow particles decompose the molecules via dissociative electron attachment. The nickel(II) and cobalt(II) bis(acetylacetonate) anions and the acetylacetonate negative fragments are the most dominant detected species. The experimental data are completed with density functional theory calculations to provide information on the electronic states of the molecules and the energetics for fragmentation. Finally, it is found that the interaction of low-energy electrons resulting in the decomposition of organometallic complexes in the gas phase is more efficient with the nickel(II) than with the cobalt(II) bis(acetylacetonate) complex. These results are found to be in a relative agreement with the surface experiments.

Mapping and Controlling Liquid Layer Thickness in Liquid-Phase (Scanning) Transmission Electron Microscopy.

Liquid-Phase (Scanning) Transmission Electron Microscopy (LP-(S)TEM) has become an essential technique to monitor nanoscale materials processes in liquids in real-time. Due to the pressure difference between the liquid and the microscope vacuum, bending of the silicon nitride (SiNx ) membrane windows generally occurs. This causes a spatially varying liquid layer thickness that makes interpretation of LP-(S)TEM results difficult due to a locally varying achievable resolution and diffusion limitations. To mediate these difficulties, it is shown: 1) how to quantitatively map liquid layer thickness for any liquid at less than0.01 e- Å-2 total dose; 2) how to dynamically modulate the liquid thickness by tuning the internal pressure in the liquid cell, co-determined by the Laplace pressure and the external pressure. It is demonstrated that reproducible inward bulging of the window membranes can be realized, leading to an ultra-thin liquid layer in the central window area for high-resolution imaging. Furthermore, it is shown that the liquid thickness can be dynamically altered in a programmed way, thereby potentially overcoming the diffusion limitations towards achieving bulk solution conditions. The presented approaches provide essential ways to measure and dynamically adjust liquid thickness in LP-(S)TEM experiments, enabling new experiment designs and better control of solution chemistry.

Dynamics and healing behavior of metallosupramolecular polymers.

Self-healing or healable polymers can recuperate their function after physical damage. This process involves diffusion of macromolecules across severed interfaces until the structure of the interphase matches that of the pristine material. However, monitoring this nanoscale process and relating it to the mechanical recovery remain elusive. We report that studying diffusion across healed interfaces and a correlation of contact time, diffusion depth, and mechanical properties is possible when two metallosupramolecular polymers assembled with different lanthanoid salts are mended. The materials used display similar properties, while the metal ions can be tracked with high spatial resolution by energy-dispersive x-ray spectrum imaging. We find that healing actual defects requires an interphase thickness in excess of 100 nm, 10 times more than previously established for self-adhesion of smooth films of glassy polymers.

Reviewing the cases of Nanoscale Heterogeneity in Ceramics: Boon or Bane?

Size-dependent properties and their enormity of change make the whole domain of nanoscale materials exciting like anything; the fact that such property changes can be achieved with very small fractions of nanomaterials also helps the issue further. The same fact, however, is not so straightforward when it comes to ceramic materials. Ceramic phases changing their stabilities at the nanoscale and ceramic processing being known for complex high temperature operations – are the two key reasons why nanoceramic sector could not always deliver the results in an expected way. Whether it is the unexpected phase, microstructure or local compositional fluctuation/s – all can make a ceramic system heterogeneous at nanoscale. The important objective, however, remains to identify them (i.e., heterogeneities), understand them (i.e., reason/s behind their genesis) and use them (if possible) to advantage. In this review, numerous case studies on the factors influencing the nanoscale heterogeneities in ceramics have been presented. The role of raw materials, their synthesis, and processing factors have been emphasized along with the capability and limitation of conventional analytical tools in examining such complexities. Impacts on selected properties (i.e., as barrier or boon) have been discussed in connection to these heterogeneities. The case studies on nano-heterogeneities have been presented in a non-judgemental way so as to illustrate their impacts in both ways (i.e., either as a barrier or boon). Since heterogeneities in nano-ceramics have not been studied methodically (unlike polymers or metals) over the past, this article is expected to provide a background for starting the same.

Nanoscale deformation and crack processes of kaolinite under water impact using molecular dynamics simulations

The mechanisms of deformation or crack of nanoscale clay particles under water impact is important yet not investigated thoroughly. Hydraulic fracturing method is used for shale gas extraction, since large amount of water is injected into deep shale formations to crack rocks and release trapped gas. In this work, the microscopic deformation and crack processes of kaolinite (Kaol) pores under high-pressure water impact are investigated using molecular dynamics simulations. Two modes of water impact are adopted. These modes are distinguished by the directions of extra force which is exerted on water clusters to crack the Kaol rock. The results show that Kaol with two distinct basal surfaces exhibit different deformation features under these two impact ways. The falling apart of SiO tetrahedral or AlOH octahedral units leads to cracks or apertures. An integrated arrangement of small SiO tetrahedral units is observed while AlOH octahedral units are not. After cracking, water cluster enters the pore space and adsorbs onto the polyhedral units of Kaol, especially surrounded by close-packed SiO tetrahedral units. In addition, the changes of mechanical equivalent stress during the deformation and crack process are analyzed. This work provides a molecular explanation of the microscopic mechanisms and processes of rock cracking, and guidance for hydraulic fracturing fluid improvement.

Effects of solid/liquid interface on size-dependent specific heat capacity of nanoscale water films: Insight from molecular simulations

The thermophysical properties of an evaporative thin water film that is near the triple line may change because of the effects of size, geometry, interface, temperature, etc. However, the factor-dependence of the properties was seldom considered for the corresponding nanoscale transport phenomena or processes. In this work, the effects of the interface and temperature on the thickness-dependent specific heat capacities of nanoscale water films are investigated by comparing the values of the freestanding film between vacuum, the sessile film on a copper plate, and the confined film between two copper plates. It is found that the specific heat capacities of the thin water films decrease exponentially with reducing thickness, with the confined film having the highest value, followed by the sessile film and the freestanding film, at the same film thickness. The solid/liquid interface presents a substantial impact on the increase in the specific heat capacity, demonstrated by the analysis of density profile, vibration density of state of hydrogen atoms of water molecules, radial distribution function, and interface energy, compared between the films of different types. The analysis of the temperature effect by comparing the vibration densities of state in different regions of the films at different temperatures shows that the temperature has a negligible influence as compared to the size and interface effects. Therefore, the form of a thin water film will greatly affect its thermophysical properties, including specific heat capacity, which should be considered in applications such as evaporation of thin water film, nanoconfinement transfer in membrane, and interface separation of porous media.

Bacterial Antifouling Characteristics of Helicene-Graphene Films.

Herein, we describe interfacially-assembled [7]helicene films that were deposited on graphene monolayer using the Langmuir-Schaefer deposition by utilizing the interactions of nonplanar (helicene) and planar (graphene) π–π interactions as functional antifouling coatings. Bacterial adhesion of Staphylococcus aureus on helicene—graphene films was noticeably lower than that on bare graphene, up to 96.8% reductions in bacterial adhesion. The promising bacterial antifouling characteristics of helicene films was attributed to the unique molecular geometry of helicene, i.e., nano-helix, which can hinder the nanoscale bacterial docking processes on a surface. We envision that helicene—graphene films may eventually be used as protective coatings against bacterial antifouling on the electronic components of clinical and biomedical devices.

Spin waves in Y&lt;sub&gt;3&lt;/sub&gt;Fe&lt;sub&gt;5&lt;/sub&gt;O&lt;sub&gt;12&lt;/sub&gt;-CoFeB spin-wave directional coupler

The spin-wave coupling device is used as a connection unit to solve the connection problem between spin-wave devices. However, the current size is too large in comparison with the nano-scale process, which is caused by the low efficiency of the spin wave within it. Therefore, we propose the spin-wave directional coupler based on Y&lt;sub&gt;3&lt;/sub&gt;Fe&lt;sub&gt;5&lt;/sub&gt;O&lt;sub&gt;12&lt;/sub&gt;-CoFeB coupling which can improve the current dilemma to a certain extent. By filling the gap layer of two spin-wave waveguides (Y&lt;sub&gt;3&lt;/sub&gt;Fe&lt;sub&gt;5&lt;/sub&gt;O&lt;sub&gt;12&lt;/sub&gt;) placed in parallel with CoFeB material, it is found that the dispersion relationship of the spin wave changes in the data calculation of the micromagnetic simulation software Mumax&lt;sup&gt;3&lt;/sup&gt;. The existence of CoFeB makes the transmission efficiency of the spin wave between the two waveguides higher than in the case without any filling, the enhancement effect is about 4 times where coupling length is reduced from the original 2000 nm to 500 nm, which is conducive to the miniaturization and integration of the spin-wave directional coupler design. From the perspective of the entire device, further analysis indicates that owing to the high saturation magnetization of CoFeB (approximately 8 times that of Y&lt;sub&gt;3&lt;/sub&gt;Fe&lt;sub&gt;5&lt;/sub&gt;O&lt;sub&gt;12&lt;/sub&gt;), the effective field in the Y&lt;sub&gt;3&lt;/sub&gt;Fe&lt;sub&gt;5&lt;/sub&gt;O&lt;sub&gt;12&lt;/sub&gt;-CoFeB directional coupler is greatly enhanced, which leads the spin wave dispersion curve in the waveguide to change. At the same time, the energy of the entire system also increases several times, which is mainly caused by the increase of dipole energy and exchange energy. Then a greater contribution of dipole energy is obtained by changing the size of the device. After that, we study the relationship between the coupling length and the device size and the external magnetic field, then draw a general rule which can play a role in designing any directional couplers with similar structures. Finally, our view points are given from the different spin wave excitation frequencies, gap layer filling materials, internal roughness of the directional coupler, and spin wave lifetime by considering the problems that may occur in practical applications with the Y&lt;sub&gt;3&lt;/sub&gt;Fe&lt;sub&gt;5&lt;/sub&gt;O&lt;sub&gt;12&lt;/sub&gt;-CoFeB directional coupler. In conclusion, our proposed Y&lt;sub&gt;3&lt;/sub&gt;Fe&lt;sub&gt;5&lt;/sub&gt;O&lt;sub&gt;12&lt;/sub&gt;-CoFeB directional coupler structure can effectively enhance the coupling efficiency, and it can also provide a new idea for the application of the interaction between composite materials.

Zero-point magnetic exchange interactions

Quantum fluctuations are ubiquitous in physics. Ranging from conventional examples like the harmonic oscillator to intricate theories on the origin of the universe, they alter virtually all aspects of matter -- including superconductivity, phase transitions and nanoscale processes. As a rule of thumb, the smaller the object, the larger their impact. This poses a serious challenge to modern nanotechnology, which aims total control via atom-by-atom engineered devices. In magnetic nanostructures, high stability of the magnetic signal is crucial when targeting realistic applications in information technology, e.g. miniaturized bits. Here, we demonstrate that zero-point spin-fluctuations are paramount in determining the fundamental magnetic exchange interactions that dictate the nature and stability of the magnetic state. Hinging on the fluctuation-dissipation theorem, we establish that quantum fluctuations correctly account for the large overestimation of the interactions as obtained from conventional static first-principles frameworks, filling in a crucial gap between theory and experiment [1,2]. Our analysis further reveals that zero-point spin-fluctuations tend to promote the non-collinearity and stability of chiral magnetic textures such as skyrmions -- a counter-intuitive quantum effect that inspires practical guidelines for designing disruptive nanodevices.

Tutorial: Design of High-Speed Nano-Scale CMOS Mixed-Voltage Digital I/O Buffer With High Reliability to PVTL Variations

Ever since the reliability issues caused by I/O (input/output) compatibility among chips fabricated using different processes were raised during mid-2000, on-silicon mixed-voltage I/O buffer with wide voltage tolerance has been considered a better solution than using signal level converters to shrink PCB size, number of discretes, and power consumption. However, various external voltages on I/O pad result in body effect, leakage, hot-carrier degradation, and gate-oxide overstress in stacked transistors of mixed-voltage I/O. What even worse is that slew rate (SR) was also found deteriorated by PVT (Process, Voltage, Temperature) variations. A complete mixed-voltage I/O buffer design flow using nano-scale CMOS processes will be introduced in this tutorial based on previously developed buffers. Besides circuit design methodology, the reliability design consideration for the buffers, including ESD, PVT detection, and slew rate auto-adjustment will be discussed as well.

Removal of Heavy Metals from Wastewaters: A Challenge from Current Treatment Methods to Nanotechnology Applications.

Removing heavy metals from wastewaters is a challenging process that requires constant attention and monitoring, as heavy metals are major wastewater pollutants that are not biodegradable and thus accumulate in the ecosystem. In addition, the persistent nature, toxicity and accumulation of heavy metal ions in the human body have become the driving force for searching new and more efficient water treatment technologies to reduce the concentration of heavy metal in waters. Because the conventional techniques will not be able to keep up with the growing demand for lower heavy metals levels in drinking water and wastewaters, it is becoming increasingly challenging to implement technologically advanced alternative water treatments. Nanotechnology offers a number of advantages compared to other methods. Nanomaterials are more efficient in terms of cost and volume, and many process mechanisms are better and faster at nanoscale. Although nanomaterials have already proved themselves in water technology, there are specific challenges related to their stability, toxicity and recovery, which led to innovations to counteract them. Taking into account the multidisciplinary research of water treatment for the removal of heavy metals, the present review provides an updated report on the main technologies and materials used for the removal of heavy metals with an emphasis on nanoscale materials and processes involved in the heavy metals removal and detection.

On the applicability of continuum scale models for ultrafast nanoscale liquid-vapor phase change

Continuum methods are efficient in modeling multi-phase flow at large time and length scales, however, their applicability to nanoscale systems and processes is questionable. When mean free path and average time between atomic collisions are comparable to the characteristic length and time scales of interest, the continuum hypothesis approaches its spatial and temporal limit. Here we discuss the implications of modeling such a limiting problem involving liquid-vapor phase change using continuum equations of mass, momentum, and energy conservation. Our results indicate that, continuum conservation laws can correctly represent the dynamics of the specific problem of interest provided appropriate constitutive relations are used at liquid-vapor interfaces. We show that with the Schrage relation for phase change rates and a physically motivated expression for temperature jump, interfacial phenomena can be described quite accurately.

Chemical and physical transformations of carbon-based nanomaterials observed by liquid phase transmission electron microscopy

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Liquid phase transmission electron microscopy for imaging of nanoscale processes in solution

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Three-dimensional spatiotemporal tracking of nano-objects diffusing in water-filled optofluidic microstructured fiber

Abstract Three-dimensional (3D) tracking of nano-objects represents a novel pathway for understanding dynamic nanoscale processes within bioanalytics and life science. Here we demonstrate 3D tracking of diffusing 100 nm gold nanosphere within a water-filled optofluidic fiber via elastic light scattering–based position retrieval. Specifically, the correlation between intensity and position inside a region of a fiber-integrated microchannel has been used to decode the axial position from the scattered intensity, while image processing–based tracking was used in the image plane. The 3D trajectory of a diffusing gold nanosphere has been experimentally determined, while the determined diameter analysis matches expectations. Beside key advantages such as homogenous light-line illumination, low-background scattering, long observation time, large number of frames, high temporal and spatial resolution and compatibility with standard microscope, the particular properties of operating with water defines a new bioanalytical platform that is highly relevant for medical and life science applications.

The Sensitivity of the Pair-Angle Distribution Function to Protein Structure

The continued development of X-ray free-electron lasers and serial crystallography techniques has opened up new experimental frontiers. Nanoscale dynamical processes such as crystal growth can now be probed at unprecedented time and spatial resolutions. Pair-angle distribution function (PADF) analysis is a correlation-based technique that has the potential to extend the limits of current serial crystallography experiments, by relaxing the requirements for crystal order, size and number density per exposure. However, unlike traditional crystallographic methods, the PADF technique does not recover the electron density directly. Instead it encodes substantial information about local three-dimensional structure in the form of three- and four-body correlations. It is not yet known how protein structure maps into the many-body PADF correlations. In this paper, we explore the relationship between the PADF and protein conformation. We calculate correlations in reciprocal and real space for model systems exhibiting increasing degrees of order and secondary structural complexity, from disordered polypeptides, single alpha helices, helix bundles and finally a folded 100 kilodalton protein. These models systems inform us about the distinctive angular correlations generated by bonding, polypeptide chains, secondary structure and tertiary structure. They further indicate the potential to use angular correlations as a sensitive measure of conformation change that is complementary to existing structural analysis techniques.

Thermal-stability resonators for visible light full-spectrum perfect absorbers

Perfect light absorption is desirable for applications in the devices related to photo-electrical effects, photo-thermal process and photo-chemical/catalysis solutions, etc. In this work, we propose and demonstrate a feasible way to achieve broadband perfect absorption in the full visible range based on the refractory material resonators. This structure shows excellent absorption efficiency with the average absorption up to 94% in the wavelength range from 380 nm to 760 nm (the visible region), suggesting the impressive capability of energy harvesting. The photonic cavity mode and the dipolar plasmon resonance by the half-cylinder cavity structure are the main contributions for the broadband absorption. The full-spectrum visible light absorption is observed to be maintained in a wide angle range under the oblique illumination. The high absorption is also retained under different polarization states. Moreover, the resonant materials such as titanium dioxide (TiO2) and titanium nitride (TiN) have impressive thermal stability due to their high melting points. These findings pave new insights on the refractory perfect visible light absorber for nano-scale photo-thermal process, micro-fluidic thermal disinfect and local high-temperature process, etc.

Ferroelectricity in Si-Doped Hafnia: Probing Challenges in Absence of Screening Charges.

The ability to develop ferroelectric materials using binary oxides is critical to enable novel low-power, high-density non-volatile memory and fast switching logic. The discovery of ferroelectricity in hafnia-based thin films, has focused the hopes of the community on this class of materials to overcome the existing problems of perovskite-based integrated ferroelectrics. However, both the control of ferroelectricity in doped-HfO2 and the direct characterization at the nanoscale of ferroelectric phenomena, are increasingly difficult to achieve. The main limitations are imposed by the inherent intertwining of ferroelectric and dielectric properties, the role of strain, interfaces and electric field-mediated phase, and polarization changes. In this work, using Si-doped HfO2 as a material system, we performed a correlative study with four scanning probe techniques for the local sensing of intrinsic ferroelectricity on the oxide surface. Putting each technique in perspective, we demonstrated that different origins of spatially resolved contrast can be obtained, thus highlighting possible crosstalk not originated by a genuine ferroelectric response. By leveraging the strength of each method, we showed how intrinsic processes in ultrathin dielectrics, i.e., electronic leakage, existence and generation of energy states, charge trapping (de-trapping) phenomena, and electrochemical effects, can influence the sensed response. We then proceeded to initiate hysteresis loops by means of tip-induced spectroscopic cycling (i.e., “wake-up”), thus observing the onset of oxide degradation processes associated with this step. Finally, direct piezoelectric effects were studied using the high pressure resulting from the probe’s confinement, noticing the absence of a net time-invariant piezo-generated charge. Our results are critical in providing a general framework of interpretation for multiple nanoscale processes impacting ferroelectricity in doped-hafnia and strategies for sensing it.

Mechanism for H2 diffusion in sII hydrates by molecular dynamics simulations

Among the many different types of molecules that form clathrate hydrates, H2 is unique as it can easily diffuse into and out of clathrate cages, a process that involves the physical-chemical interactions between guest (H2) and host (water) molecules, and is unlike any other molecular system. The dynamic and nano-scale process of H2 diffusion into binary structure II hydrates, where the large cages are occupied by larger molecules, was studied using molecular dynamics simulation. As the H2 molecules diffused from one cage to another, two types of diffusion processes were observed: (i) when moving between a pair of large cages, the H2 molecules pass through the central part of the hexagonal rings; (ii) however, when the H2 molecules move from a large cage to a small one, it requires one of the pentagonal rings to partially break, as this allows the H2 molecule to pass through the widened space. While the diffusion of H2 molecules between large cages was found to occur more frequently, the presence of SF6 molecules in the large cages was found to inhibit diffusion. Therefore, in order to attain higher H2 storage capacities in binary hydrates, it is suggested that there is an optimal number of large cages that should be occupied by SF6 molecules.

A Comprehensive Review of Integrated Hall Effects in Macro-, Micro-, Nanoscales, and Quantum Devices.

A comprehensive review of the main existing devices, based on the classic and new related Hall Effects is hereby presented. The review is divided into sub-categories presenting existing macro-, micro-, nanoscales, and quantum-based components and circuitry applications. Since Hall Effect-based devices use current and magnetic field as an input and voltage as output. researchers and engineers looked for decades to take advantage and integrate these devices into tiny circuitry, aiming to enable new functions such as high-speed switches, in particular at the nanoscale technology. This review paper presents not only an historical overview of past endeavors, but also the remaining challenges to overcome. As part of these trials, one can mention complex design, fabrication, and characterization of smart nanoscale devices such as sensors and amplifiers, towards the next generations of circuitry and modules in nanotechnology. When compared to previous domain-limited text books, specialized technical manuals and focused scientific reviews, all published several decades ago, this up-to-date review paper presents important advantages and novelties: Large coverage of all domains and applications, clear orientation to the nanoscale dimensions, extended bibliography of almost one hundred fifty recent references, review of selected analytical models, summary tables and phenomena schematics. Moreover, the review includes a lateral examination of the integrated Hall Effect per sub-classification of subjects. Among others, the following sub-reviews are presented: Main existing macro/micro/nanoscale devices, materials and elements used for the fabrication, analytical models, numerical complementary models and tools used for simulations, and technological challenges to overcome in order to implement the effect in nanotechnology. Such an up-to-date review may serve the scientific community as a basis for novel research oriented to new nanoscale devices, modules, and Process Development Kit (PDK) markets.