Here, we present an in-depth study of metal–insulator interfaces within granular metal (GM) films and correlate their interfacial interactions with structural and electrical transport properties. Nominally 100 nm thick GM films of Co and Mo dispersed within yttria-stabilized zirconia (YSZ), with volumetric metal fractions (φ) from 0.2–0.8, were grown by radio frequency co-sputtering from individual metal and YSZ targets. Scanning transmission electron microscopy and DC transport measurements find that the resulting metal islands are well-defined with 1.7–2.6 nm average diameters and percolation thresholds between φ = 0.4–0.5. The room temperature conductivities for the φ = 0.2 samples are several orders of magnitude larger than previously-reported for GMs. X-ray photoemission spectroscopy indicates both oxygen vacancy formation within the YSZ and band-bending at metal–insulator interfaces. The higher-than-predicted conductivity is largely attributed to these interface interactions. In agreement with recent theory, interactions that reduce the change in conductivity across the metal–insulator interface are seen to prevent sharp conductivity drops when the metal concentration decreases below the percolation threshold. These interface interactions help interpret the broad range of conductivities reported throughout the literature and can be used to tune the conductivities of future GMs.
AlGaN-channel high electron mobility transistors (HEMTs) were operated as visible- and solar-blind photodetectors by using GaN nanodots as an optically active floating gate. The effect of the floating gate was large enough to switch an HEMT from the off-state in the dark to an on-state under illumination. This opto-electronic response achieved responsivity > 108 A/W at room temperature while allowing HEMTs to be electrically biased in the offstate for low dark current and low DC power dissipation. The influence of GaN nanodot distance from the HEMT channel on the dynamic range of the photodetector was investigated, along with the responsivity and temporal response of the floating gate HEMT as a function of optical intensity. The absorption threshold was shown to be controlled by the AlN mole fraction of the HEMT channel layer, thus enabling the same device design to be tuned for either visible- or solar-blind detection.
The room temperature electronic transport properties of 1 μm thick Bi0.4Sb1.6Te3 (BST) films correlate with overall microstructural quality. Films with homogeneous composition are deposited onto fused silica substrates, capped with SiN to prevent both oxidation and Te loss, and postannealed to temperatures ranging from 200 to 450 °C. BST grain sizes and (00l) orientations improve dramatically with annealing to 375 °C, with smaller increases to 450 °C. Tiny few-nanometer-sized voids in the as-deposited film grain boundaries coalesce into larger void sizes up to 300 nm with annealing to 350 °C; the smallest voids continue coalescing with annealing to 450 °C. These voids are decorated with few-nanometer-sized Sb clusters that increase in number with increasing annealing temperatures, reducing the Sb content of the remaining BST film matrix. Resistivity decreases linearly with increasing temperature over the entire range studied, consistent with improving crystalline quality. The Seebeck coefficient also improves with crystalline quality to 350 °C, above which void coalescence and reduced Sb content from the BST matrix correlate with a decrease in the Seebeck coefficient. Nevertheless, a plateau exists for an optimal power factor between 350 and 450 °C, implying thermal stability to higher temperatures than previously reported.
Neutron sensing is critical in civilian and military applications. Conventional neutron sensors are limited by size, weight, cost, portability and helium supply. Here the microfabrication of gadolinium (Gd) conversion material-based heterojunction diodes for detecting thermal neutrons using electrical signals produced by internal conversion electrons (ICEs) is described. Films with negligible stress were produced at the tensile-compressive crossover point, enabling Gd coatings of any desired thickness by controlling the radiofrequency sputtering power and using the zero-point near p(Ar) of 50 mTorr at 100 W. Post-deposition Gd oxidation-induced spallation was eliminated by growing a residual stress-free 50 nm neodymium-doped aluminum cap layer atop Gd. The resultant coatings were stable for at least 6 years, demonstrating excellent stability and product shelf-life. Depositing Gd directly on the diode surface eliminated the air gap, leading to a 200-fold increase in electron capture efficiency and facilitating monolithic microfabrication. The conversion electron spectrum was dominated by ICEs with energies of 72, 132 and 174 keV. Results are reported for neutron reflection and moderation by polyethylene for enhanced sensitivity, and γ- and X-ray elimination for improved specificity. The optimal Gd thickness was 10.4 μm for a 300 μm-thick partially depleted diode of 300 mm 2 active surface area. Fast detection (within 10 min) at a neutron source-to-diode distance of 11.7 cm was achieved with this configuration. All ICE energies along with γ-ray and K α,β X-rays were modeled to emphasize correlations between experiment and theory. Semi-conductor thermal neutron detectors offer advantages for field-sensing of radioactive neutron sources.
The room temperature electronic transport properties of 100 nm-thick thermoelectric Bi0.8Sb0.2 films, sputter-deposited onto quartz substrates and post-annealed in an ex-situ furnace, systematically correlate with the overall microstructural quality, improving with increasing annealing temperature until close to the melting point for the alloy composition. Furthermore, the optimized films have high crystalline quality with ~99% of the grains oriented with the trigonal axis perpendicular to the substrate surface. Film resistivities and Seebeck coefficients are accurately measured by preventing deleterious surface oxide formation via a SiN capping layer and using Nd-doped Al for contacts. Our resulting values are similar to single crystals and significantly better than previous reports from films and polycrystalline bulk alloys.
Neutron sensing is critical in civilian, military, industrial, biological, medical, basic research, and environmental applications. Conventional neutron sensors are limited by size, weight, cost, portability, and helium supply. Here the microfabrication of Gd conversion material-based heterojunction diodes is described for detecting thermal neutrons using electrical signals produced by internal conversion electrons (ICE). Films with negligible stress were produced at the tensile-compressive crossover point, enabling Gd coatings of any desired thickness by controlling the radiofrequency sputtering power and using the zero-point near p(Ar) of 50 mTorr at 100 W. Post-deposition Gd oxidation-induced spallation was eliminated by growing a residual stress-free 50 nm neodymium-doped aluminum cap layer atop Gd. Resultant coatings were stable for at least six years demonstrating excellent product shelf life. Depositing Gd on the diode surface eliminated air gap, leading to improved efficiency and facilitating monolithic microfabrication. The conversion electron spectrum was dominated by ICE with energies of 72, 132, and 174 keV. Results are reported on neutron reflection and moderation by polyethylene for enhanced sensitivity and g- and X-ray elimination for improved specificity. Optimal Gd thickness was 10.4 um with 300 um thick partially depleted diode of 300 mm2 active surface area. Fast detection within 10 minutes at a neutron source-to-diode distance of 11.7 cm was achieved using this configuration. All ICE energies along with g-ray and Ka X-ray were modeled to emphasize correlations between experiment and theory and to calculate efficiencies. Semiconductor thermal neutron detectors offer advantages for field-sensing of radioactive neutron sources. ACKNOWLEDGEMENTS Sandia National Laboratories is a multi-program laboratory operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Company, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000. We thank Edward Cole, David Wheeler, Robert Koudelka, and Lyle Brunke for productive interactions and materials support.
We study nanoporous-carbon (NPC) grown via pulsed laser deposition (PLD) as an electrically conductive anode host material for Mg2+ intercalation. NPC has high surface area, and an open, accessible pore structure tunable via mass density that can improve diffusion. We fabricate 2032 coin cells using NPC coated stainless-steel disk anodes, metallic Mg cathodes, and a Grignardbased electrolyte. NPC mass density is controlled during growth, ranging from 0.06-1.3 g/cm3. The specific surface area of NPC increases linearly from 1,000 to 1,700 m2/g as mass density decreases from 1.3 to 0.26 g/cm3, however, the surface area falls off dramatically at lowermass densities, implying a lack of mechanical integrity in such nanostructures. These structural characterizations correlate directly with coin cell electrochemical measurements. In particular, cyclic voltammetry (CV) scans for NPC with density ∼0.5 g/cm3 and BET surface area ∼1500 m2/g infer the possibility of reversible Mg-ion intercalation. Higher density NPC yields capacitive behavior, most likely resulting from the smaller interplanar spacings between graphene sheet fragments and tighter domain boundaries; lower density NPC results in asymmetrical CV scans, consistent with the likely structural degradation resulting from mass transport through soft, low-density carbon materials.
Compositional-homogeneity and crystalline-orientation are necessary attributes to achieve high thermoelectric performance in Bi1-xSbx thin films. Following deposition in vacuum, and upon air exposure, we find that 50%-95% of the Sb in 100-nm thick films segregates to form a nanocrystalline Sb2O3 surface layer, leaving the film bulk as Bi-metal. However, we demonstrate that a thin SiN capping layer deposited prior to air exposure prevents Sb-segregation, preserving a uniform film composition. Furthermore, the capping layer enables annealing in forming gas to improve crystalline orientations along the preferred trigonal axis, beneficially reducing electrical resistivity.
Vertically aligned, untangled planarized arrays of multiwall carbon nanotubes (MWNTs) with Ohmic back contacts were grown in nanopore templates on arbitrary substrates. The templates were prepared by sputter depositing Nd-doped Al films onto W-coated substrates, followed by anodization to form an aluminum oxide nanopore array. The W underlayer helps eliminate the aluminum oxide barrier that typically occurs at the nanopore bottoms by instead forming a thin WO3 layer. The WO3 can be selectively etched to enable electrodeposition of Co catalysts with control over the Co site density. This led to control of the site density of MWNTs grown by thermal chemical vapor deposition, with W also serving as a back electrical contact. Ohmic contact to MWNTs was confirmed, even following ultrasonic cutting of the entire array to a uniform height.
Using galvanostatic pulse deposition, we studied the factors influencing the quality of electroformed Bi1-xSbxnanowires with respect to composition, crystallinity, and preferred orientation for high thermoelectric performance. Two nonaqueous baths with different Sb salts were investigated. The Sb salts used played a major role in both crystalline quality and preferred orientations. Nanowire arrays electroformed using an SbI3-based chemistry were polycrystalline with no preferred orientation, whereas arrays electroformed from an SbCl3-based chemistry were strongly crystallographically textured with the desired trigonal orientation for optimal thermoelectric performance. From the SbCl3 bath, the electroformed nanowire arrays were optimized to have nanocompositional uniformity, with a nearly constant composition along the nanowire length. Nanowires harvested from the center of the array had an average composition of Bi0.75Sb0.25. However, the nanowire compositions were slightly enriched in Sb in a small region near the edges of the array, with the composition approaching Bi0.700.30.