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At least 775 records · Page 43

Visualizing Current Flow at the Mesoscale in Disordered Assemblies of Touching Semiconductor Nanocrystals

The transport of electrons through assemblies of nanocrystals is important to performance in optoelectronic applications for these materials. Previous work has primarily focused on single nanocrystals or transitions between pairs of nanocrystals. There is a gap in knowledge of how large numbers of nanocrystals in an assembly behave collectively, and how this collective behavior manifests at the mesoscale. In this work, the variable range hopping (VRH) transport of electrons in disordered assemblies of touching, heavily doped ZnO nanocrystals was visualized at the mesoscale as a function of temperature both theoretically, using the model of Skinner, Chen and Shklovskii (SCS), and experimentally, with conductive atomic force microscopy on ultrathin films only a few particle layers thick. Agreement was obtained between the model and experiments, with a few notable exceptions. The SCS model predicts that a single network within the nanocrystal assembly, comprised of sites connected by small resistances, dominates conduction - namely the optimum band from variable range hopping theory. However, our experiments revealed that in addition to the optimum band, there are subnetworks that appear as additional peaks in the resistance histogram of conductive atomic force microscopy (CAFM) maps. Furthermore, the connections of these subnetworks to the optimum band change in time, such that some subnetworks become connected to the optimum band while others become disconnected and isolated from the optimum band; this observation appears to be an experimental manifestation of the ‘blinking’ phenomenon in our images of mesoscale transport.

Chen, Qinyi↗

Influence of ion-to-atom ratio on the microstructure of evaporated molybdenum thin films grown using low energy argon ions

The authors report the effect of argon ion to molybdenum atom ratio (r) on the microstructure of low energy (70 eV) argon ion assisted electron beam evaporated Mo thin films. Surface roughness, morphology, and crystallinity of Mo films are found to strongly depend on “r.” Increase of “r” from 0 to 100 induces gradual loss in crystallinity, reduction in surface roughness and systematic increase in density of the film. For “r” ∼ 100, average atomic density of the film approaches the bulk value (97%) with lowest surface roughness. Further, increasing “r” up to 170 reduces the atomic density, increases roughness, and increase in crystallinity induced by low energy Ar ion beam. The observed surface roughness and grain size determined by x-ray reflectivity and glancing incidence x-ray diffraction correlate well with atomic force microscopy measurements. This study demonstrates that for r = 100 one gets lowest roughness Mo film with highest density and nearly amorphous microstructure. The growth model is discussed by structural zone model.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Hydrothermal synthesis of molybdenum trioxide, characterization and photocatalytic activity

Highlights: • α-MoO{sub 3} micro-belts were synthesized hydrothermally. • Micro-belts were found very rich in surface oxygen vacancies. • CR-F3BS photocatalytic degradation was promising. • The cytotoxicity and mutagenicity were reduced significantly of CR-F3BS. - Abstract: α-MoO{sub 3} micro-belts were synthesized via hydrothermal technique and characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), atomic force microscopy (AFM), energy dispersive X-ray analysis (EDX) and particle size analyzer. Photo-catalytic activity was evaluated by degrading Coralene Red F3BS (CR-F3BS) dye and process variables i.e., pH, photocatalyst dose, concentration of CR-F3BS and UV exposure time were optimized using response surface methodology (RSM) under central composite design (CCD). Under optimized conditions, up to 95% degradation of CR-F3BS (10 mg/L) was achieved for 120 min UV irradiation time at pH 7 using 2.75 g/L catalyst dose. The obtained RSM model revealed a satisfactory correlation between experimental and predicted CR-F3BS degradation values. Ames and heamolytic tests revealed that the toxicity was reduced significantly as a result of photo-catalytic treatment. In view of promising efficiency, α-MoO{sub 3} micro-belts could possibly be used for the degradation of dyes in textile effluents.

36 MATERIALS SCIENCE↗

Structural effects of field emission from GaN nanofilms on SiC substrates

GaN nanofilms (NFs) with different structures are grown on SiC substrates by pulsed laser deposition under different conditions. The synthesized GaN NFs are studied by X-ray diffraction, field-emission (FE) scanning electron microscopy, X-ray photoelectron spectroscopy, and atomic force microscopy. The GaN NFs are composed of diversified GaN nanoparticles with a diameter of 9–38 nm, thickness of 10–50 nm, and roughness of 0.22–13.03 nm. FE from the GaN NFs is structure dependent, which is explained by stress changing the band gap of the NFs. By structure modulation, the turn-on field of GaN NFs can be as low as 0.66 V/μm at a current density of 1 μA/cm{sup 2}, with a current density of up to 1.1 mA/cm{sup 2} at a field of 4.18 V/μm. Fowler-Nordheim curves of some samples contain multiple straight lines, which originate from the structural change and diversification of GaN nanoparticles under an applied field. Overall, our results suggest that GaN NFs with excellent FE properties can be prepared on SiC substrates, which provides a new route to fabricate high-efficiency FE nanodevices.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Metal-oxide-semiconductor capacitors and Schottky diodes studied with scanning microwave microscopy at 18 GHz

We measured the DC and RF impedance characteristics of micrometric metal-oxide-semiconductor (MOS) capacitors and Schottky diodes using scanning microwave microscopy (SMM). The SMM consisting of an atomic force microscopy (AFM) interfaced with a vector network analyser (VNA) was used to measure the reflection S11 coefficient of the metallic MOS and Schottky contact pads at 18 GHz as a function of the tip bias voltage. By controlling the SMM biasing conditions, the AFM tip was used to bias the Schottky contacts between reverse and forward mode. In reverse bias direction, the Schottky contacts showed mostly a change in the imaginary part of the admittance while in forward bias direction the change was mostly in the real part of the admittance. Reference MOS capacitors which are next to the Schottky diodes on the same sample were used to calibrate the SMM S11 data and convert it into capacitance values. Calibrated capacitance between 1–10 fF and 1/C{sup 2} spectroscopy curves were acquired on the different Schottky diodes as a function of the DC bias voltage following a linear behavior. Additionally, measurements were done directly with the AFM-tip in contact with the silicon substrate forming a nanoscale Schottky contact. Similar capacitance-voltage curves were obtained but with smaller values (30–300 aF) due to the corresponding smaller AFM-tip diameter. Calibrated capacitance images of both the MOS and Schottky contacts were acquired with nanoscale resolution at different tip-bias voltages.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Toward Electrochemical Studies on the Nanometer and Atomic Scales: Progress, Challenges, and Opportunities

Electrochemical reactions and ionic transport underpin the operation of a broad range of devices and applications, from energy storage and conversion to information technologies, as well as biochemical processes, artificial muscles, and soft actuators. Understanding the mechanisms governing function of these applications requires probing local electrochemical phenomena on the relevant time and length scales. Here, we discuss the challenges and opportunities for extending electrochemical characterization probes to the nanometer and ultimately atomic scales, including challenges in down-scaling classical methods, the emergence of novel probes enabled by nanotechnology and based on emergent physics and chemistry of nanoscale systems, and the integration of local data into macroscopic models. Scanning probe microscopy (SPM) methods based on strain detection, potential detection, and hysteretic current measurements are discussed. We further compare SPM to electron beam probes and discuss the applicability of electron beam methods to probe local electrochemical behavior on the mesoscopic and atomic levels. Similar to a SPM tip, the electron beam can be used both for observing behavior and as an active electrode to induce reactions. We briefly discuss new challenges and opportunities for conducting fundamental scientific studies, matter patterning, and atomic manipulation arising in this context.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Analysis of the degradation induced by focused ion Ga{sup 3+} beam for the realization of piezoelectric nanostructures

Piezoelectric nanostructures (islands of dimensions in the lateral size range 50-500 nm) have been fabricated by focused Ga{sup 3+} ion beam (FIB) etching on PbZr{sub 0.54}Ti{sub 0.46}O{sub 3} thin films obtained by magnetron sputtering. The degradation induced by the etching process is investigated through the evolution of electromechanical activity measured by means of local piezoelectric hysteresis loops produced by piezoresponse force microscopy. The analysis of surface potential is performed by kelvin force microscopy and the measurement of current-voltage curves is carried out by conducting atomic force microscopy. Two kinds of structures, namely one based on crystallized films and the other based on amorphous ones, were studied. In this latter case, the amorphous films are postannealed after etching to obtain crystallized structure. For the structures based on the crystallized and then etched films, no piezoelectric signal was registered that evidences a serious degradation of material induced by Ga{sup 3+} ion implantation. For the structures based on the films etched in amorphous state and then crystallized, the piezoresponse signal was near to that of the reference films (crystallized and not etched) whatever were the ion dose and the island dimensions. Even for very small lateral size (50 nm), no size effect was observed. The island shapes fabricated by Ga{sup 3+} FIB etching process (islands with less than 50 nm lateral size) show a limitation of FIB processing and electron beam lithography seems to be necessary.

36 MATERIALS SCIENCE↗

Effect of Electronic Excitation on Thin Film Growth

The effect of nanosecond pulsed laser excitation on surface diffusion during growth of Ge on Si(100) at 250 degrees C was studied. In Situ reflection high-energy electron diffraction (RHEED) was used to measure the surface diffusion coefficient while ex situ atomic force microscopy (AFM) was used to probe the structure and morphology of the grown quantum dots. The results show that laser excitation of the substrate increases the surface diffusion during growth of Ge on Si(100), changes the growth morphology, improves crystalline structure of the grown quantum dots, and decreases their size distribution. A purely electronic mechanism of enhanced surface diffusion of the deposited Ge is proposed. Ge quantum dots were grown on Si(100)-(2x1) by pulsed laser deposition at various substrate temperatures using a femtosecond Ti:sapphire laser. In-situ reflection high-energy electron diffraction and ex-situ atomic force microscopy were used to analyze the fim structure and morphology. The morphology of germanium islands on silicon was studied at differect coverages. The results show that femtosecond pulsed laser depositon reduces the minimum temperature for epitaxial growth of Ge quantum dots to ~280 degrees C, which is 120 degrees C lower then previously observed in nanosecond pulsed laser deposition and more than 200 degrees C lower than that reported for molecular beam epitaxy and chemical vapor deposition.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Hydrogen bonded trimesic acid networks on Cu(111) reveal how basic chemical properties are imprinted in HR-AFM images

High resolution non-contact atomic force microscopy measurements characterize assemblies of trimesic acid molecules on Cu(111) and the link group interactions, providing the first fingerprints utilizing CO-based probes for this widely studied paradigm for hydrogen bond driven molecular self assembly. The enhanced submolecular resolution offered by this technique uniquely reveals key aspects of the competing interactions. Accurate comparison between full-density-based modeled images and experiment allows to identify key structural elements in the assembly in terms of the electron-withdrawing character of the carboxylic groups, interactions of those groups with Cu atoms in the surface, and the valence electron density in the intermolecular region of the hydrogen bonds. This study of trimesic acid assemblies on Cu(111) combining high resolution atomic force microscopy measurements with theory and simulation forges clear connections between fundamental chemical properties of molecules and key features imprinted in force images with submolecular resolution.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Epitaxially Grown Single-Crystalline SrTiO 3 Membranes Using a Solution-Processed, Amorphous SrCa 2 Al 2 O 6 Sacrificial Layer

Water-soluble sacrificial layers based on epitaxially-grown, single crystalline (Ca, Sr, Ba) 3 Al 2 O 6 layer are widely used for creating free-standing perovskite oxide membranes. However, obtaining these sacrificial layers with intricate stoichiometry remains a challenge, especially for molecular beam epitaxy (MBE). In this study, we demonstrate the hybrid MBE growth of epitaxial, single crystalline SrTiO 3 films using a solution processed, amorphous SrCa 2 Al 2 O 6 sacrificial layer onto SrTiO 3 (001) substrates. Prior to the growth, the oxygen plasma exposure was used to first create the crystalline SrCa 2 Al 2 O 6 layer with well-defined surface crystallinity. Utilizing reflection high energy electron diffraction, x-ray diffraction, and atomic force microscopy, we observe an atomic layer-by-layer growth of epitaxial, single crystalline SrTiO 3 film on the SrCa 2 Al 2 O 6 layer with atomically smooth surfaces. The SrCa 2 Al 2 O6 layer was subsequently dissolved in de-ionized water to create free-standing SrTiO3 membranes that were transferred onto a metal-coated Si wafer. Membranes created with Sr-deficiency revealed ferroelectric-like behavior measured using piezo force microscopy whereas stoichiometric films remained paraelectric-like. Furthermore, these findings underscore the viability of using ex-situ deposited amorphous SrCa2Al2O6 for epitaxial, single crystalline growth, as well as the importance of point defects in determining the ferroic properties in membranes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluation of Surface Damage of Organic Films due to Irradiation with Energetic Ion Beams

The surface of L-leucine films irradiated with an Ar{sub 5000} cluster ion beam (5 keV) was characterized by using the X-ray reflective (XRR) measurement method, atomic force microscopy (AFM) and ellipsometry. No significant damage was detected on the surface of the L-leucine films irradiated with the Ar cluster ion beam. Therefore, the large cluster-low-energy (about 1 eV/atom) beam would be suitable for low-damage etching of organic materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Facet-dependent growth and dissolution of hematite resulting from autocatalytic interactions with Fe(II) and oxalic acid

The ability to simultaneously monitor the flux of iron atoms within the solution and solid phases can provide considerable insight into mechanisms of iron oxide mineral transformations. The autocatalytic interaction between hematite and Fe(II)-oxalate has long been of interest for its environmental and industrial relevance. In this study we take advantage of iron isotopic labelling and mass-sensitive imaging at the single particle scale to determine how changes in solution composition correlate with the morphologic evolution of faceted, micrometer-sized hematite platelets. Net dissolution is confirmed through analyses of aqueous iron chemistry, as well as by quantitative atomic force microscopy. Isotopic mapping techniques show that Fe(II) readily adsorbs to (001) and (012) surfaces in the absence of oxalate, but when oxalate is present selective dissolution of the (001) surface prevails and 57Fe deposition via recrystallization is not observed. Comparison between particle microtopographies following reaction with Fe(II), oxalate, and Fe(II)-oxalate show substantially different behavior, consistent with distinct mechanisms of interaction with hematite surfaces. The extensive characterization conducted on the coupled solution/solid dynamics in this system provides new insight for distinguishing crystal growth, dissolution, and recrystallization processes.

Taylor, Sandra D. [BATTELLE (PACIFIC NW LAB)]↗

Charge transfer of single laser crystallized intrinsic and phosphorus-doped Si-nanocrystals visualized by Kelvin probe force microscopy

Isolated intrinsic and phosphorus doped (P-doped) Si-nanocrystals (Si-NCs) on n- and p-Si substrates are fabricated by excimer laser crystallization techniques. The formation of Si-NCs is confirmed by atomic force microscopy (AFM) and conductive AFM measurements. Kelvin probe force microscopy (KPFM) is then carried out to visualize the trapped charges in a single Si-NC dot which derives from the charge transfer between Si-NCs and Si substrates due to their different Fermi levels. The laser crystallized P-doped Si-NCs have a similar Fermi level around the mid-gap to the intrinsic counterparts, which might be caused by the inactivated impurity atoms or the surface states-related Fermi level pinning. A clear rise of the Fermi level in P-doped Si-NCs is observed after a short time thermal annealing treatment, indicating the activation of dopants in Si-NCs. Moreover, the surface charge quantity can be estimated using a simple parallel plate capacitor model for a quantitative understanding of the KPFM results at the nanoscale.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Synergetic effects of K + and Mg 2+ ion intercalation on the electrochemical and actuation properties of the two-dimensional Ti 3 C 2 MXene

Two-dimensional materials, such as MXenes, are attractive candidates for energy storage and electrochemical actuators due to their high volume changes upon ion intercalation. Of special interest for boosting energy storage is the intercalation of multivalent ions such as Mg 2+ , which suffers from sluggish intercalation and transport kinetics due to its ion size. By combining traditional electrochemical characterization techniques with electrochemical dilatometry and contact resonance atomic force microscopy, the synergetic effects of the pre-intercalation of K + ions are demonstrated to improve the charge storage of multivalent ions, as well as tune the mechanical and actuation properties of the Ti 3 C 2 MXene. Our results have important implications for quantitatively understanding the charge storage processes in intercalation compounds and provide a new path for studying the mechanical evolution of energy storage materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrostatic properties of two-dimensional WSe{sub 2} nanostructures

Recently, two-dimensional transition metal dichalcogenides have intrigued much attention due to their promising applications in optoelectronics. The electrostatic property investigation of WSe{sub 2} nanostructures is essential for device application. Here, the interlayer screening effects of WSe{sub 2} nanoplates with different thicknesses were investigated by measuring surface potential employing Kelvin probe force microscopy. Simultaneously, charges can be injected into WSe{sub 2} nanoplate by means of conducting atomic force microscopy to tune the electrostatic properties of WSe{sub 2} nanostructures. Our experimental results have some important implications for improving performance of WSe{sub 2}-based optoelectronic devices through interface or surface engineering.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Advanced Topographic Characterization of Variously Prepared Niobium Surfaces and Linkage to RF Losses

Superconducting radio frequency (SRF) technology is widely adopted in particle accelerators. The shallow penetration (~ 40 nm) of the RF into superconducting niobium lends great importance to SRF cavity interior surface chemistry and topography. These in turn are strongly influenced by the chemical etching "surface clean-up" that follows fabrication. The principal surface smoothing methods are buffered chemical polish (BCP) and electropolish (EP). The resulting topography is characterized by atomic force microscopy (AFM). The power spectral density (PSD) of AFM data provides a more thorough description of the topography than a single-value roughness measurement. In this work, one dimensional average PSD functions derived from topography of BCP and EP with different controlled starting conditions and durations have been fitted with a combination of power law, K-correlation, and shifted Gaussian models to extract characteristic parameters at different spatial harmonic scales. While the simplest characterizations of these data are not new, the systematic tracking of scale-specific roughness as a function of processing is new and offers feedback for tighter process prescriptions more knowledgably targeted at beneficial niobium topography for SRF applications. Process development suffers because the cavity interior surface cannot be viewed directly without cutting out pieces, rendering the cavities unavailable for further study. Here we explore replica techniques as an alternative, providing imprints of cavity internal surface that can be readily examined. A second matter is the topography measurement technique used. Atomic force microscopy (AFM) has proven successful, but too time intensive for routine use. We therefore introduce white light interferometry (WLI) approach as an alternative. We examined real surfaces and their replicas, using AFM and WLI. We find that the replica/WLI is promising to provide the large majority of desired information, so that use of the time-intensive AFM approach can be limited to where it is genuinely necessary. The prevalent idea is that sharp features could lead to magnetic quench or enhance the thermal quench. In this report, a calculation on magnetic field is numerically given on fine structure by finite element and conformal mapping methods. Corresponding RF Ohmic loss will be simulated. A certain thermal tolerant will be calculated. A Q~E curve will be predicted from this model. A perturbation model is utilized to calculate rough surface additional RF loss based on PSD statistical analysis. This model will not consider that superconductor will become normal at field higher than transition field. Therefore, it is only expected to explain mid-field Q performance. One can calculate the RF power dissipation ratio between rough surface and ideal smooth surface within this field range. Additionally, the resistivity of Nb is temperature and magnetic field dependent from classic thermal feedback model theory. Combining with topographic PSD analysis and Rs temperature and field dependency, a middle field Q slope model could be modeled and the contribution from topography can be simulated.

Xu, Chen↗

Tuning crystallization pathways through sequence engineering of biomimetic polymers

Two-step nucleation pathways in which disordered, amorphous, or dense liquid states precede the appearance of crystalline phases have been reported for a wide range of materials, but the dynamics of such pathways are poorly understood. Moreover, whether these pathways are general features of crystallizing systems or a consequence of system-specific structural details that select for direct versus two-step processes is unknown. Using atomic force microscopy to directly observe crystallization of sequence-defined polymers, we show that crystallization pathways are indeed sequence dependent. When a short hydrophobic region is added to a sequence that directly forms crystalline particles, crystallization instead follows a two-step pathway that begins with the creation of disordered clusters of 10–20 molecules and is characterized by highly non-linear crystallization kinetics in which clusters transform into ordered structures that then enter the growth phase. The results shed new light on non-classical crystallization mechanisms and have implications for the design of self-assembling polymer systems.

36 MATERIALS SCIENCE↗

Silk Flexible Electronics: From Bombyx mori Silk Ag Nanoclusters Hybrid Materials to Mesoscopic Memristors and Synaptic Emulators

Functionalization of flexible materials based on mesoscopic reconstruction is a key strategy in fabricating biocompatible flexible electronics. This work is to acquire new mesoscopic bioelectronic hybrid materials of silk fibroin (SF)-Ag nanoclusters (AgNCs@BSA; BSA: bovine serum albumin), which enhance significantly the performance of silk memristors. It is to build AgNCs@BSA into SF mesoscopic networks by templated ß-crystallization. Atomic force microscopy potential probing indicates that AgNCs@BSA serve as electronic potential wells that change completely the transport behavior of charge particles within the SF films. This leads to significant enhancement in the switching speed (˜10 ns), very good switching stability, extremely low set/reset voltages (0.3/-0.18 V) of SF meso-hybrid memristors, compared with the original and other organic memristors, and displays unique synapse characteristics and the capability of synapse learning. Classical density functional theory Poisson–Nernst–Planck simulations indicate that the enhanced performance is subject to the low potential paths interconnecting the AgNCs@BSA, which guide charges' transport (Ag+) and deposition in SF films.

Shi, Chenyang↗