Nanoscale metal–insulator–metal (MIM) diodes consisting of a nanoscale-thickness insulator layer sandwiched between two dissimilar metal layers offer the potential for very high frequency alternating current to direct current signal rectification. Active nanoscale tuning of electronic tunneling through the insulator layer to form point contact diodes has previously been limited to barriers composed of soft organic films due to the force limitations of conductive-atomic force microscopy. In this paper, MIM diodes with oxide-based insulators are formed in situ with sub-nanometer depth precision and characterized using a nanoindenter equipped with electrical testing capabilities. Simultaneous measurement of both electrical and nano-mechanical information is accomplished in an MIM stack of the form Nb/Nb2O5/boron-doped diamond nanoindenter tip. Using this technique, we show that the diode behavior can be electromechanically tuned over a range of more than 1 V at equivalent currents via small changes in indentation depth and the results can be modeled using a Fowler–Nordheim approximation.

In2Se3, Cu2Se, and CuInSe2 thin films have been successfully fabricated using novel metal organic decomposition (MOD) precursors and atmospheric pressure-based deposition and processing. The phase evolution of the binary (In-Se and Cu-Se) and ternary (Cu-In-Se) MOD precursor films was examined during processing to evaluate the nature of the phase and composition changes. The In-Se binary precursor exhibits two specific phase regimes: (i) a cubic-InxSey phase at processing temperatures between 300 and 400 °C and (ii) the γ-In2Se3 phase for films annealed above 450 °C. Both phases exhibit a composition of 40 at.% indium and 60 at.% selenium. The binary Cu-Se precursor films show more diverse phase behavior, and within a narrow temperature processing range a number of Cu-Se phases, including CuSe2, CuSe, and Cu2Se, can be produced and stabilized. The ternary Cu-In-Se precursor can be used to produce relatively dense CuInSe2 films at temperatures between 300 and 500 °C. Layering the binary precursors together has provided an approach to producing CuInSe2 thin films; however, the morphology of the layered binary structure exhibits a significant degree of porosity. An alternative method of layering was explored where the Cu-Se binary was layered on top of an existing indium-gallium-selenide layer and processed. This method produced highly dense and large-grained (>3 µm) CuInSe2 thin films. This has significant potential as a manufacturable route to CIGS-based solar cells.

Single walled carbon nanotubes (SWNT) were synthesized by methane CVD on a supported mixed transition metal (Fe/Mo) catalyst. Gas feed composition and reaction temperature were varied to identify the threshold conditions for the growth of SWNT. These reaction conditions closely approximate pseudo-equilibrium conditions with some active reaction intermediate (likely chemisorbed carbon atoms) that proceeds to nucleate and grow SWNT. This value also serves as an estimated upper limit of the free energy of formation ΔG*(T)SWNT since the active intermediate proceeds to form SWNT through a process that is thought to be essentially irreversible. The difference relative to graphite is in good agreement with literature values predicted from simulations for SWNT nuclei containing approximately 80 atoms, while considerably larger than that predicted for bulk 5, 5 SWNT. Our estimate over the range 700 to 1000 °C of 16.1 to 13.9 kJ/mol is considerably greater than the free energy of formation for diamond (between 5.8 and 6.9 kJ/mol from 700 to 925 °C).

Hydrogen adsorption has been observed with a binding energy of ∼ 50 kJ /mol on as-synthesized carbon multi-wall nanotubes (MWNTs). The MWNTs are virtually free of non-nanotube carbon impurities but contain residual iron catalyst particles. The MWNTs are also highly graphitic. No hydrogen adsorption is observed at near ambient temperatures for purified MWNTs that are free of iron particles. However, hydrogen adsorption is also not observed on bare iron particles even following reduction in the presence of hydrogen at 775 K. These results imply that a special synergy occurs when small iron particles or atoms are in intimate contact with sp2-hybridized aromatic carbon. Interestingly, reducing the as-synthesized MWNTs in H2 at 573 K results in an increased hydrogen capacity. Understanding this hydrogen storage mechanism could facilitate the economical engineering of a hydrogen storage material that meets the United States Department of Energy targets for vehicular fuel cell applications. Recent theoretical studies have shown that an iron ad atom forms a complex with a C36 fullerene and shares charge with four carbon atoms of a bent five-membered ring. Three H2 ligands then coordinate with the iron forming a stable 18-electron organometallic complex. Here the binding energy of the molecular hydrogen ligands is ∼43 kJ /mol. These theoretical results could possibly explain the unique hydrogen storage properties of MWNTs that are grown with an iron catalyst.

The hydrogen storage properties of carbon single-wall and multi-wall nanotubes (SWNTs and MWNTs), graphitic nanofibers, and other nanostructured carbons have recently become the subject of considerable debate. Reported capacities range from ∼ 0–60 wt%. Hot wire chemical vapor deposition (HWCVD) has recently been adapted for a continuous growth process for high-density carbon MWNTs. Multi-wall nanotube growth is optimized in 1:5 CH4:Ar at 150 Torr with reactor temperatures of 400 and 550°C for static and flowing gases, respectively. Ferrocene is employed to provide a gas-phase catalyst. Highly graphitic nanotubes can be continuously deposited with iron content as low as 15 wt% and carbon impurities below thermal gravimetric analysis detection limits. The MWNTs are simply purified to ∼99.5 wt% with minimal structural damage and with a 75 wt% yield. Hydrogen adsorption is observed for low pressures at near ambient temperatures on the as-synthesized MWNTs containing iron nanoparticles. However, no hydrogen adsorption, is observed at near ambient temperatures for the purified MWNTs or for purified MWNTs that were subsequently combined with iron micro/nano-particles via sonication. These results indicate that an intimate metal/graphitic carbon interaction is required for unanticipated hydrogen adsorption at near ambient conditions.

Composite thin films of 60 wt% Ba0.6Sr0.4TiO3 and 40 wt% MgO were produced by Pulsed Laser Deposition. The biaxial texture of the BST component on the MgO substrate has been established with XRD. All as-deposited films had an enlarged BST out-of-plane lattice parameter. A more relaxed lattice constant as well as higher degree of texture has been obtained in the films deposited at higher temperature and lower deposition rate. Post-deposition annealing in flowing oxygen results in a further relaxation and alignment of the BST lattice. The as-deposited films were not tunable at room temperature. The greatest dielectric tuning was achieved in films annealed at 1200 °C. The observed difference in tunability for the films annealed at different temperatures may result from a spatial redistribution of BST material on the substrate surface during annealing.

An inductive heating system was used to control the temperature of the target during laser synthesis of SWNTs. The position of the target relative to the heating coil, the type of catalyst metals and the synthesis temperatures were all varied in attempts to gain more control over the types of carbon single wall nanotubes grown. Raman spectroscopy results suggest that narrower diameter distributions are produced when the gas-phase species are rapidly condensed. TEM analysis of the raw soot shows that many tube ends are present and that the tubes are short due to incomplete growth. This investigation shows that it is possible to gain further control over SWNT diameter distributions through fine control of the reaction environment made possible with inductive heating.

We grew BaxSr1−xTiO3 (BST) films on MgO single crystal substrates by pulsed laser deposition (PLD). We report the in-plane (a) and out-of-plane (c) lattice parameters of BST films deposited in a range of O2 deposition pressures [P(02)], as measured by asymmetric rocking curve diffraction. As P(O2) increases, the films' biaxial strain changes from compression (a < c), to cubic (a = c), and then to tension (a > c). Furthermore, both a and c are larger than the lattice constant for bulk BST of the same composition. This indicates the presence of a hydrostatic strain component in addition to the biaxial component. From the measured lattice parameters, we calculate the total residual strain in terms of biaxial and hydrostatic components. We also examine the effects of a post-deposition anneal. Characterizing residual strain and understanding its origin(s) are important since strain affects the dielectric properties of BST films and thereby the properties of devices which incorporate them.

We report the performance of 16-element phased array antennas operating at 30 GHz and ambient temperature. These antennas use BaxSr1−xTiO3(BST)-based phase shifters to produce the beam steering. Ferroelectric phase shifters offer advantages over current semiconductor and ferrite devices including faster switching speeds and lower costs. Also, ferroelectric phase shifters offer higher power handling capability than semiconductor devices and also have high radiation resistance. We made phase shifters from laser-ablated epitaxial BST films as well as from polycrystalline BST-oxide composite films. Although neither the devices nor the materials themselves are fully optimized, phase shifters have shown > 360° of phase shift with < 350 V DC bias (E < 9 V/µm) and ∼8 dB insertion loss. With ferroelectric phase shifters incorporated, antennas show radiation patterns with central-lobe half-power widths of ∼13° and side lobe intensities down by more than 10 dB. Using the phase shifters, the central lobe can be shifted, or “steered,” by ±18° in either direction. These results demonstrate a first step toward a prototype steerable antenna for 20–30 GHz satellite communications as well as other applications.

We report on the use of pulsed laser depositon (PLD) to grow thin films of LiCoO2 on a number of low cost substrates including SnO2 coated Upilex, stainless steel and SnO2 coated glass. Highly textured (001) films grown on CVD deposited SnO2 films on 7059 glass, were obtained at 200 to 500 mTorr O2 and a temperature of 500 C. Similar texture was not obtained on the stainless or Upilex however dense films from crystalline to amorphous were obtained. The films were characterized by x-ray diffraction and Raman spectroscopy.

We report on investigations of V2O5 thin film cathodes prepared by pulsed laser deposition and the phase transformations which occur during electrochemical cycling. Our experimental results on PLD-grown, textured V2O5 crystalline films concur with reports in the literature that there is a voltage threshold above which, cycling appears to be completely reversible and below which, cycling appears to be irreversible. Crystalline films discharged beyond the threshold to 2.0 V vs. Li exhibited an immediate and continuous fade in capacity as well as a ∼90% decrease in XRD peak intensity and a similar decrease in Raman signal intensity in as few as 10 cycles. We have made co-phase material by both electrochemically discharging virgin, crystalline V2O5 and by further discharging previously cycled films which showed irreversible structural changes.

Charge-collection microscopy (CCM)—commonly known as electron-beam-induced current [EBIC] microscopy—in a scanning electron microscope (SEM) was used to obtain charge-collection efficiency profiles of cleaved thin-film ZnO/CdS/CuInXGal-XSe2/Mo photovoltaic devices on glass substrates, with x varied between 0 and 100%. We observed considerable variation in the EBIC peak position, the uniformity (between and within devices), and overall charge-collection profile of the junction as a function of Ga concentration. Whereas using only CuInSe2 (CIS) absorber material results in a rather wide and buried junction in the CIS, the systematic addition of Ga to the p-CuInSe2 matrix affects the conductivity type of the material, thereby creating an increasingly abrupt, uniform, and shallow junction near the heteroface. Although the substitution of Ga for In improves overall device performance up to ∼ X=25% and the Voc continues to improve, the Jsc, FF, and device efficiency degrade with additional Ga.

We present the first report of the synthesis of Cd2SnO4 films by pulsed laser deposition. Controlling the substrate temperature and the ambient atmosphere allowed for the synthesis of films ranging from amorphous to crystalline with some crystalline films exhibiting strong texture. Highly transparent films with large mobilities were obtained for both the amorphous and crystalline films. Sheet resistances of 15.5 Ω/square and mobilities of up to 44.7 cm2/V.s were observed. Typical carrier concentrations showed the crystalline films to be degenerate with carrier concentrations of 5 х 1020cm-3 while amorphous films had carrier concentrations lower by about half. Band gaps for the films ranged between 3.1-3.8 eV. these films are attractive candidates for TCO applications in thin film photovoltaic devices, flat panel displays, electrochromic windows, and as plasma filters for thermophotovoltaic devices.