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At least 19 records

High-Throughput Top-Down and Bottom-Up Processes for Forming Single-Nanotube Based Architectures for 3D Electronics

We have developed manufacturable approaches to form single, vertically aligned carbon nanotubes, where the tubes are centered precisely, and placed within a few hundred nm of 1-1.5 micron deep trenches. These wafer-scale approaches were enabled by chemically amplified resists and inductively coupled Cryo-etchers for forming the 3D nanoscale architectures. The tube growth was performed using dc plasma-enhanced chemical vapor deposition (PECVD), and the materials used for the pre-fabricated 3D architectures were chemically and structurally compatible with the high temperature (700 C) PECVD synthesis of our tubes, in an ammonia and acetylene ambient. Tube characteristics were also engineered to some extent, by adjusting growth parameters, such as Ni catalyst thickness, pressure and plasma power during growth. Such scalable, high throughput top-down fabrication techniques, combined with bottom-up tube synthesis, should accelerate the development of PECVD tubes for applications such as interconnects, nano-electromechanical (NEMS), sensors or 3D electronics in general.

plasma-enhanced chemical vapor deposition (PECVD),

High-Throughput Processes and Structural Characterization of Single-Nanotube Based Devices for 3D Electronics

We have developed manufacturable approaches to form single, vertically aligned carbon nanotubes, where the tubes are centered precisely, and placed within a few hundred nm of 1-1.5 micron deep trenches. These wafer-scale approaches were enabled by chemically amplified resists and inductively coupled Cryo-etchers to form the 3D nanoscale architectures. The tube growth was performed using dc plasmaenhanced chemical vapor deposition (PECVD), and the materials used for the pre-fabricated 3D architectures were chemically and structurally compatible with the high temperature (700 C) PECVD synthesis of our tubes, in an ammonia and acetylene ambient. The TEM analysis of our tubes revealed graphitic basal planes inclined to the central or fiber axis, with cone angles up to 30 deg. for the particular growth conditions used. In addition, bending tests performed using a custom nanoindentor, suggest that the tubes are well adhered to the Si substrate. Tube characteristics were also engineered to some extent, by adjusting growth parameters, such as Ni catalyst thickness, pressure and plasma power during growth.

top-down fabrication

Atomic-scale insights into topotactic transformations in an extra-large-pore zeolite using time-resolved 3D electron diffraction

Understanding the atomic-scale structural dynamics of phase transformations is crucial for developing materials and tailoring their properties. However, many materials are obtained as polycrystalline powders with large unit cells and/or complex structures, making it challenging to investigate detailed structural changes using conventional X-ray diffraction techniques. Here we employ time-resolved three-dimensional electron diffraction to reveal the topotactic reactions and transformations that convert the extra-large-pore silicate zeolite ECNU-45 into ECNU-46. ECNU-45 features three-dimensional interconnecting 24 × 10 × 10-ring channels, while ECNU-46 consists of one-dimensional 24-ring channels connected to 10-ring pockets. ECNU-45 and ECNU-46 are both examples of pure silicate zeolites with pore openings larger than 22-ring. Our findings indicate changes at six distinct tetrahedral silicon sites, involving atom displacement, addition and removal of framework atoms through bond breakage and formation. This work presents the synthesis of zeolites and also provides atomic-level insights into the dynamic processes of topotactic reactions. Our results have implications for advancing materials engineering and understanding complex solid-state reactions at an atomic scale.

Inorganic chemistry

Carbon Nanofibers Synthesized on Selective Substrates for Nonvolatile Memory and 3D Electronics

A plasma-enhanced chemical vapor deposition (PECVD) growth technique has been developed where the choice of starting substrate was found to influence the electrical characteristics of the resulting carbon nanofiber (CNF) tubes. It has been determined that, if the tubes are grown on refractory metallic nitride substrates, then the resulting tubes formed with dc PECVD are also electrically conducting. Individual CNFs were formed by first patterning Ni catalyst islands using ebeam evaporation and liftoff. The CNFs were then synthesized using dc PECVD with C2H2:NH3 = [1:4] at 5 Torr and 700 C, and approximately equal to 200-W plasma power. Tubes were grown directly on degenerately doped silicon <100> substrates with resistivity rho approximately equal to 1-5 meterohm-centimeter, as well as NbTiN. The approximately equal to 200-nanometer thick refractory NbTiN deposited using magnetron sputtering had rho approximately equal to 113 microohm-centimeter and was also chemically compatible with CNF synthesis. The sample was then mounted on a 45 beveled Al holder, and placed inside a SEM (scanning electron microscope). A nanomanipulator probe stage was placed inside the SEM equipped with an electrical feed-through, where tungsten probes were used to make two-terminal electrical measurements with an HP 4156C parameter analyzer. The positive terminal nanoprobe was mechanically manipulated to physically contact an individual CNF grown directly on NbTiN as shown by the SEM image in the inset of figure (a), while the negative terminal was grounded to the substrate. This revealed the tube was electrically conductive, although measureable currents could not be detected until approximately equal to 6 V, after which point current increased sharply until compliance (approximately equal to 50 nA) was reached at approximately equal to 9.5 V. A native oxide on the tungsten probe tips may contribute to a tunnel barrier, which could be the reason for the suppressed transport at low biases. Currents up to approximately 100 nA could be cycled, which are likely to propagate via the tube surface, or sidewalls, rather than the body, which is shown by the I-V in figure (a). Electrical conduction via the sidewalls is a necessity for dc NEMS (nanoelectromechanical system) applications, more so than for the field emission applications of such tubes. During the tests, high conductivity was expected, because both probes were shorted to the substrate, as shown by curve 1 in the I-V characteristic in figure (b). When a tube grown on NbTiN was probed, the response was similar to the approximately equal to 100 nA and is represented by curve 2 in figure (b), which could be cycled and propagated via the tube surface or the sidewalls. However, no measureable currents for the tube grown directly on Si were observed as shown by curve 3 in figure (b), even after testing over a range of samples. This could arise from a dielectric coating on the sidewalls for tubes on Si. As a result of the directional nature of ion bombardment during dc PECVD, Si from the substrate is likely re-sputtered and possibly coats the sidewalls.

Kaul, Anupama B.

The photoelectron spectroscopy of ZnCl2

The ionization energies (IEs) corresponding to the Cl ligand electrons and the Zn 3d electrons in ZnCl2, computed using large Gaussian basis sets and a high level of correlation treatment, are presented. The IEs for the Cl ligand electrons are in excellent agreement with those determined from photoelectron spectra. The IEs corresponding to the Zn 3d electrons agree with experiment relatively well in absolute magnitude, but differ in order. The vibrational frequencies of the ground state agree very well with experiment, and predictions are made for the corresponding frequencies in the positive ion.

Bauschlicher, Charles W., Jr.

Multimodal Nanoscale Mapping of Local Structure and CO 2 Adsorption in Metal–Organic Frameworks

Diamine functionalization of the metal−organic framework Mg 2 (dobpdc) (dobpdc 4− = 4,4′-dioxidobiphenyl-3,3′-dicarboxylate) significantly enhances its selectivity for CO 2 capture from flue gases and air. The structure and CO 2 capacity of such materials are typically assessed using bulk techniques that rely on averaging signal over large ensembles of unit cells, obscuring local heterogeneities, such as variations in CO 2 occupancy across individual nanocrystals. To resolve this limitation, we demonstrate a multimodal, nanoscale characterization of Mg 2 (dobpdc) appended with 1,3-diaminopropane. By employing recently developed characterization techniques at progressively smaller length scales, we uncover insights from correspondingly smaller populations of unit cells. First, we use parallel-beam 3D electron diffraction (3D ED) to identify a prominent expansion in lattice parameters upon desorption of CO 2 , as observed at the level of single nanocrystals. Second, we use convergent-probe 4D scanning transmission electron microscopy (4D-STEM) to quantify associated differences in lattice strain as a function of gas loading and diamine appending. These measurements sample small subvolumes within individual nanocrystals. Finally, we apply infrared scattering scanning near-field optical microscopy (IR s- SNOM) to confirm variable CO 2 chemisorption across adsorption sites at the surface of single nanocrystals. This multimodal, multiscale approach allows us to map heterogeneity within individual nanocrystals. Collectively, these findings emphasize the importance of local, nanoscale characterization of metal−organic frameworks in revealing previously unresolvable features that impact their performance.

Karstens, Sarah L. [University of California, Berk

Scalable fabrication of Chip-integrated 3D-nanostructured electronic devices via DNA-programmable assembly

DNA-based self-assembly methods have demonstrated powerful and unique capabilities to encode nanomaterial structures through the prescribed placement of inorganic and biological nanocomponents. However, the challenge of selectively growing DNA superlattices on specific locations of surfaces and their integration with conventional nanofabrication has hindered the fabrication of three-dimensional (3D) DNA-assembled functional devices. Here, we present a scalable nanofabrication technique that combines bottom-up and top-down approaches for selective growth of 3D DNA superlattices on gold microarrays. This approach allows for the fabrication of self-assembled 3D-nanostructured electronic devices. DNA strands are bound onto the gold arrays, which anchor DNA origami frames and promote ordered framework growth on the specific areas of the surface, enabling control of the lateral placement and orientation of superlattices. DNA frameworks selectively grown on the pads are subsequently templated to nanoscale silica and tin oxide (SnO x ) that follow the architecture, as confirmed by structural and chemical characterizations. The fabricated SnO x superlattices are integrated into devices that demonstrate photocurrent response.

36 MATERIALS SCIENCE

On the bonding in Mn2(+)

Qualitative calculations are presented on the Mn2(+) ion. These yield a 12Sigma(g)(+) ground state, in agreement with experiment, in which the 3d electrons are ferromagnetically coupled. The 2Sigma(u)(+) state of Mu2(+) is found to lie 0.44 eV higher in energy; the 3d electrons on each center are high-spin coupled, but the interatomic coupling is antiferromagnetic. The large splitting between the 12Sigma(g)(+) and 2Sigma(u)(+) states is shown to be due to the intraatomic 4s-3d exchange energy, which is an order of magnitude larger than the weak interatomic 3d-3d interaction. The Mn2(+) ion is compared and contrasted with the Mn2 neutral species, where the analogous 11Sigma(u)(+) and 1Sigma(g)(+) states are reversed in order, but almost degenerate.

Bauschlicher, Charles W., Jr.

The dissociation of H2 on the Ni(100) surface

The dissociation of H2 on the (100) surface of Ni is investigated using a cluster model. The mechanism for dissocation of H2 directly above a Ni atom has little to no barrier and involves the Ni 3d electrons; elimination of the Ni 3d interaction with the H2 increases the barrier to more than 50 kcal/mol. The dissociation at the bridge site, treated without the Ni 3d interaction, leads to a barrier of about 30 kcal/mol, leading to the conclusion that the dissociation of H2 at any site on a Ni(100) surface requires strong 3d participation. The results are quantitatively different if the Ni 4p orbitals are not included. The effects of cluster size on the results are also discussed.

Siegbahn, P. E. M.

Solar Wind Halo Formation by the Scattering of the Strahl via Direct Cluster/PEACE Observations of the 3D Velocity Distribution Function

It has been suggested by a number of authors that the solar wind electron halo can be formed by the scattering of the strahl. On frequent occasions we have observed in electron angular skymaps (Phi/Theta-plots) of the electron 3D velocity distribution functions) a bursty-filament of particles connecting the strahl to the solar wind core-halo. These are seen over a very limited energy range. When the magnetic field is well off the nominal solar wind flow direction such filaments are inconsistent with any local forces and are probably the result of strong scattering. Furthermore, observations indicates that the strahl component is frequently and significantly anisotropic (Tper/Tpal approx.2). This provides a possible free energy source for the excitation of whistler waves as a possible scattering mechanism. The empirical observational evidence between the halo and the strahl suggests that the strahl population may be, at least in part, the source of the halo component.

Figueroa-Vinas, Adolfo

On the nature of the bonding in Cu2 - An ab initio viewpoint

The bonding in Cu2 has been calculatively investigated. A CASSCF calculation is performed where the two 4s electrons are distributed in all possible ways among the 4s and 4p orbitals. The CAS results have a 3d population of 9.99. The corresponding orbitals between the CAS core orbitals at r(e) and the atomic SCF core orbitals show an overlap of 13.9992 out of a possible 14, with all of the change in sigma space. Thus, the CAS results show virtually no change in the d orbitals relative to the atom and can be considered as showing only a single bond. The reduction in 3d population, the decrease in r(e), and the increase in D(e) upon correlating the 3d shell indicates that the 3d electrons are slightly involved in the bonding, but there is no indication of the formation of a triple bond.

Bauschlicher, C. W., Jr.

Design of Experiment for the Measurement of Aerosol Droplet Size Distribution of Temperature-Controlled Thermally Atomized Printed Electronic Inks

In-Space Manufacturing (ISM) centers around NASA’s growing need and ability to produce space technologies on demand in space. As the future of long term presence in space and deep space exploration approach, fundamental questions of our dependence on earth resupply to Low Earth Orbit (LEO) remain unanswered. ISM is leading various effort to evaluate the feasibility of producing essential spares and redundant parts on demand to enable a sustainable space-based supply chain model for part resupply. Among the parts and systems being considered, Avionics form the neural network of modern day aircraft and space vehicles providing a wealth of information ranging from Guidance, Navigation, and Control (GN&C) systems to on board Environmental Control and Life Support (ECLS) systems. Recent advances in the use of Aerosol Jet Technology to print Avionics components ranging from electrical traces on a circuit board to complex transistors and sensors raise the possibility of using such technology to reproduce or recreate electronic parts on demand with the help of custom electronics 3D printers. The challenge herein lies within the ability of such printers to generate and deposit an aerosol of electronic material utilizing processes independent of or enhanced by gravity to ensure controllably identical or improved behavior of the aerosol in an International Space Station (ISS) laboratory and on the ground. The behavior as well as the hazards and properties associated with such aerosols in a microgravity environment must be understood well in order to merit a feasible approach to utilizing them for manufacturing in space. In this report, we outline the experimental setup of a modified conventional vaping device to be used as the ideal gravity independent thermal atomization mechanism to generate aerosol. Our objective is to identify the ideal mass, density, and volume of our aerosolized droplets of ink to conclude that there exist a threshold of aerosolized ink droplet sizes that are indeed independent of the effects of gravity and remain stable after atomization. We use a Malvern Spraytec® Spray Particle Size Analyzer to perform real-time laser diffraction measurement of our ink droplets during atomization. The droplet size between conductive ink, dielectric ink and vegetable glycerin have been measured and contrasted. Furthermore, the mechanism of thermal atomization versus traditional pneumatic and ultrasonic atomization for operation in microgravity have been explored.

Wu, Chih-Hao

Angular distribution of Auger electrons due to 3d-shell impact ionization of krypton

Cross sections for electron impact ionization of krypton due to ejection of a 3d-shell electron have been calculated using screened hydrogenic and Hartree-Slater wavefunctions for the target atom. While the total ionization cross sections in the two approximations are within 10% of each other, the Auger electron angular distribution, related to cross sections for specific magnetic quantum numbers of the 3d electrons, are widely different in the two approximations. The angular distribution due to the Hartree-Slater approximation is in excellent agreement with measurement. The physical reason for the discrepancies in the two approximations is explained.

Omidvar, K.