Publications

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A GeNi alloy diffusion barrier for contacts on bismuth antimony telluride is proposed. Multiple gold contact diffusion barriers were tested at different thermal aging conditions in air and reducing atmospheres. Among all diffusion barriers, the GeNi alloy barrier shows the best performance for bulk samples with no substantial degradation of the contact resistance, no contact color change, and no change of thermoelectric properties. We observed DAu-GeNi = (9.8 ± 2.7) × 10-20 m2/s within the GeNi alloy barrier, which is 4 times smaller than DAu-BiSbTe. The presence of the initial Ge layer also proves to be effective in reducing nickel diffusion yielding DNi-BiSbTe = (8.57 ± 0.49) × 10-19 m2/s. During GeNi alloy formation, Ge diffusion into BiSbTe produces GeTe, which apparently blocks the van der Waals gaps eliminating Au and Ni fast diffusion pathways. Thermal aging of BiSbTe nanowires shows that Au and Ni diffusion degrades the thermoelectric power factor, whereas the GeNi alloy barrier sample is mostly preserved. The GeNi alloy barrier is a reliable solution to long-term thermal applications of BiTe-based materials.

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Decoupling the electronic thermal and electrical conductivities is one of the limitations hindering a breakthrough in thermoelectric efficiency. After a conformal surface coating of bismuth telluride nanowires (Bi2Te3 NWs) by porphyrins, the thermal conductivity increases from 0.8 to 1.0 Wm-1K-1 at 300 K without any obvious change in electrical conductivity. Density Functional Theory (DFT) calculations assisted by Boltzmann Transport Equation (BTE) simulations of electronic transport properties indicate that the electronic thermal transport is enhanced by the depletion of surface charge carriers, which results in transition from metallic to semiconducting behavior. Thus, the adsorption of porphyrin onto the Bi2Te3 NWs layer suppresses the surface electronic conduction, resulting in thermal electronic conduction dictated by the bulk of the NW. The results mean that electronic thermal transport can be decoupled from the electrical conductivity by changing the density of surface states on Bi2Te3 NWs.

As a first step to porting scanning tunneling microscopy methods of atomic-precision fabrication to a strained-Si/SiGe platform, we demonstrate post-growth P atomic-layer doping of SiGe heterostructures. To preserve the substrate structure and elastic state, we use a T≤800 ° C process to prepare clean Si0.86Ge0.14 surfaces suitable for atomic-precision fabrication. P-saturated atomic-layer doping is incorporated and capped with epitaxial Si under a thermal budget compatible with atomic-precision fabrication. Hall measurements at T=0.3 K show that the doped heterostructure has R□=570±30Ω, yielding an electron density ne=2.1±0.1×1014cm-2 and mobility μe=52±3cm2V-1s-1, similar to saturated atomic-layer doping in pure Si and Ge. The magnitude of μe and the complete absence of Shubnikov-de Haas oscillations in magnetotransport measurements indicate that electrons are overwhelmingly localized in the donor layer, and not within a nearby buried Si well. This conclusion is supported by self-consistent Schrödinger-Poisson calculations that predict electron occupation primarily in the donor layer.

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Under the direction of the James W. Todd, Assistant Manager for Engineering within the National Nuclear Security Administration Sandia Field Office, the team listed above has performed the attached study to evaluate the vibration sensitivity of the Center for Integrated Nanotechnolog ies and propose possible mitigation strategies .

Nickel-doped α-MnO2 nanowires (Ni-α-MnO2) were prepared with 3.4% or 4.9% Ni using a hydrothermal method. A comparison of the electrocatalytic data for the oxygen reduction reaction (ORR) in alkaline electrolyte versus that obtained with α-MnO2 or Cu-α-MnO2 is provided. In general, Ni-α-MnO2 (e.g., Ni-4.9%) had higher n values (n = 3.6), faster kinetics (k = 0.015 cm s-1), and lower charge transfer resistance (RCT = 2264 Ω at half-wave) values than MnO2 (n = 3.0, k = 0.006 cm s-1, RCT = 6104 Ω at half-wave) or Cu-α-MnO2 (Cu-2.9%, n = 3.5, k = 0.015 cm s-1, RCT = 3412 Ω at half-wave), and the overall activity for Ni-α-MnO2 trended with increasing Ni content, i.e., Ni-4.9% > Ni-3.4%. As observed for Cu-α-MnO2, the increase in ORR activity correlates with the amount of Mn3+ at the surface of the Ni-α-MnO2 nanowire. Examining the activity for both Ni-α-MnO2 and Cu-α-MnO2 materials indicates that the Mn3+ at the surface of the electrocatalysts dictates the activity trends within the overall series. Single nanowire resistance measurements conducted on 47 nanowire devices (15 of α-MnO2, 16 of Cu-α-MnO2-2.9%, and 16 of Ni-α-MnO2-4.9%) demonstrated that Cu-doping leads to a slightly lower resistance value than Ni-doping, although both were considerably improved relative to the undoped α-MnO2. The data also suggest that the ORR charge transfer resistance value, as determined by electrochemical impedance spectroscopy, is a better indicator of the cation-doping effect on ORR catalysis than the electrical resistance of the nanowire. (Figure Presented).

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Lead halide perovskites are increasingly considered for applications beyond photovoltaics, for example, light emission and detection, where an ability to pattern and prototype microscale geometries can facilitate the incorporation of this class of materials into devices. Here we demonstrate laser direct write of lead halide perovskites, a remarkably simple procedure that takes advantage of the inverse dependence between perovskite solubility and temperature by using a laser to induce localized heating of an absorbing substrate. We demonstrate arbitrary pattern formation of crystalline CH3NH3PbBr3 on a range of substrates and fabricate and characterize a microscale photodetector using this approach. This direct write methodology provides a path forward for the prototyping and production of perovskite-based devices.

We describe a high-resolution patterning approach that combines the spatial control inherent to laser direct writing with the versatility of benchtop chemical synthesis. By taking advantage of the steep thermal gradient that occurs while laser heating a metal edge in contact with solution, diverse materials comprising transition metals are patterned with feature size resolution nearing 1 μm. We demonstrate fabrication of reduced metallic nickel in one step and examine electrical properties and air stability through direct-write integration onto a device platform. This strategy expands the chemistries and materials that can be used in combination with laser direct writing.

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Semiconducting nanowires have been explored for a number of applications in optoelectronics such as photodetectors and solar cells. Currently, there is ample interest in identifying the mechanisms that lead to photoresponse in nanowires in order to improve and optimize performance. However, distinguishing among the different mechanisms, including photovoltaic, photothermoelectric, photoemission, bolometric, and photoconductive, is often difficult using purely optoelectronic measurements. In this work, we present an approach for performing combined and simultaneous thermoelectric and optoelectronic measurements on the same individual nanowire. We apply the approach to GaN/AlGaN core/shell and GaN/AlGaN/GaN core/shell/shell nanowires and demonstrate the photothermoelectric nature of the photocurrent observed at the electrical contacts at zero bias, for above- and below-bandgap illumination. Furthermore, the approach allows for the experimental determination of the temperature rise due to laser illumination, which is often obtained indirectly through modeling. We also show that under bias, both above- and below-bandgap illumination leads to a photoresponse in the channel with signatures of persistent photoconductivity due to photogating. Finally, we reveal the concomitant presence of photothermoelectric and photogating phenomena at the contacts in scanning photocurrent microscopy under bias by using their different temporal response. Our approach is applicable to a broad range of nanomaterials to elucidate their fundamental optoelectronic and thermoelectric properties.

The thermoelectric properties of unintentionally n-doped core GaN/AlGaN core/shell N-face nanowires are reported. We found that the temperature dependence of the electrical conductivity is consistent with thermally activated carriers with two distinctive donor energies. The Seebeck coefficient of GaN/AlGaN nanowires is more than twice as large as that for the GaN nanowires alone. However, an outer layer of GaN deposited onto the GaN/AlGaN core/shell nanowires decreases the Seebeck coefficient at room temperature, while the temperature dependence of the electrical conductivity remains the same. We attribute these observations to the formation of an electron gas channel within the heavily-doped GaN core of the GaN/AlGaN nanowires. The room-temperature thermoelectric power factor for the GaN/AlGaN nanowires can be four times higher than the GaN nanowires. Selective doping in bandgap engineered core/shell nanowires is proposed for enhancing the thermoelectric power.

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Nanowire transistors are generally formed by metal contacts to a uniformly doped nanowire. The transistor can be modeled as a series combination of resistances from both the channel and the contacts. In this study, a simple model is proposed consisting of a resistive channel in series with two Schottky metal-semiconductor contacts modeled using the WKB approximation. This model captures several phenomena commonly observed in nanowire transistor measurements, including the mobility as a function of gate potential, mobility reduction with respect to bulk mobility, and non-linearities in output characteristics. For example, the maximum measured mobility as a function of gate voltage in a nanowire transistor can be predicted based on the semiconductor bulk mobility in addition to barrier height and other properties of the contact. The model is then extended to nanowires with axial p-n junctions having an inde- pendent gate over each wire segment by splitting the channel resistance into a series component for each doping segment. Finally, the contact-channel model is applied to low-frequency noise analysis in nanowire devices, where the noise can be generated in both the channel and the contacts. Because contacts play a major, yet often neglected, role in nanowire transistor operation, they must be accounted for in order to extract meaningful parameters from I-V and noise measurements.

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An integrated hybrid photovoltaic-thermoelectric system has been developed using multiple layers of organic photosensitizers on inorganic semiconductors in order to efficiently convert UV-visible and IR energy into electricity. The hot anode of n-type ZnO nanowires was fabricated using a thermal process on pre-seeded layer and results to be crystalline with a transmittance up to 92 % and a bandgap of 3.32 eV. The visible-UV light-active organic layer was deposited between the anode and cathode at room temperature using a layer-by-layer deposition onto ITO and ZnO and Bi2Te3 nanowires from aqueous solution. The organic layer, a cooperative binary ionic (CBI) solid is composed of oppositely charged porphyrin metal (Zn(II) and Sn(IV)(OH–)2) derivatives that are separately water soluble, but when combined form a virtually insoluble solid. The electron donor/acceptor properties (energy levels, band gaps) of the solid can be controlled by the choice of metals and the nature of the peripheral substituent groups of the porphyrin ring. The highly thermoelectric structure, which acts as a cold cathode, is composed of p-type Bi2Te3 nanowires with a thermoelectric efficiency (ZT) between ~0.7 to 1, values that are twice that expected for bulk Bi2Te3. Lastly, efficiency of the integrated device, was found to be 35 at 0.2 suns illumination and thermoelectric properties are enhanced by the charge transfer between the CBI and the Bi2Te3 is presented in terms of photo- and thermogenerated current and advantages of the low cost fabrication process is discussed.

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We have demonstrated single-mode lasing in a single gallium nitride nanowire using distributed feedback by external coupling to a dielectric grating. By adjusting the nanowire grating alignment we achieved a mode suppression ratio of 17dB.

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Measurements of the electrical and thermal transport properties of one-dimensional nanostructures (e.g.nanotubes and nanowires) are typically obtained without detailed knowledge of the specimen's atomic-scale structure or defects. To address this deficiency, we have developed a microfabricated, chip-based characterization platform that enables both transmission electron microscopy (TEM) of the atomic structure and defects as well as measurement of the thermal transport properties of individual nanostructures. The platform features a suspended heater line that physically contacts the center of a suspended nanostructure/nanowire that was placed using insitu scanning electron microscope nanomanipulators. Suspension of the nanostructure across a through-hole enables TEM characterization of the atomic and defect structure (dislocations, stacking faults, etc) of the test sample. This paper explains, in detail, the processing steps involved in creating this thermal property measurement platform. As a model study, we report the use of this platform to measure the thermal conductivity and defect structure of a GaN nanowire. © 2011 IOP Publishing Ltd.

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Measurements of the electrical and thermal transport properties of one-dimensional nanostructures (e.g., nanotubes and nanowires) typically are obtained without detailed knowledge of the specimen's atomic-scale structure or defects. To address this deficiency we have developed a microfabricated, chip-based characterization platform that enables both transmission electron microscopy (TEM) of atomic structure and defects as well as measurement of the thermal transport properties of individual nanostructures. The platform features a suspended heater line that contacts the center of a suspended nanostructure/nanowire that was placed using in-situ scanning electron microscope nanomanipulators. One key advantage of this platform is that it is possible to measure the thermal conductivity of both halves of the nanostructure (on each side of the central heater), and this feature permits identification of possible changes in thermal conductance along the wire and measurement of the thermal contact resistance. Suspension of the nanostructure across a through-hole enables TEM characterization of the atomic and defect structure (dislocations, stacking faults, etc.) of the test sample. As a model study, we report the use of this platform to measure the thermal conductivity and defect structure of GaN nanowires. The utilization of this platform for the measurements of other nanostructures will also be discussed.

The use of nanowires for thermoelectric energy generation has gained momentum in recent years as an approach to improve the figure of merit (ZT) due in part to larger phonon scattering at the boundary resulting in reduced thermal conductivity while electrical conductivity is not significantly affected. Silicon-germanium (SiGe) alloy nanowires are promising candidates to further reduce thermal conductivity by phonon scattering because bulk SiGe alloys already have thermal conductivity comparable to reported Si nanowires. In this work, we show that thermal and electrical conductivity can be measured for the same single nanowire eliminating the uncertainties in ZT estimation due to measuring the thermal conduction on one set of wires and the electrical conduction on another set. In order to do so, we use nanomanipulation to place vapor-liquid-solid boron-doped SiGe alloy nanowires on predefined surface structures. Furthermore, we developed a contact-annealing technique to achieve negligible electrical contact resistance for the placed nanowires that allows us, for the first time, to measure electrical and thermal properties on the same device. We observe that thermal conductivity for SiGe nanowires is dominated by alloy scattering for nanowires down to 100 nm in diameter between the temperature range 40-300 K. The estimated electronic contribution of the thermal conductivity as given by the Wiedemann-Franz relationship is about 1 order of magnitude smaller than the measured thermal conductivity which indicates that phonons carry a large portion of the heat even at such small dimensions.

This document is the final SAND Report for the LDRD Project 102660 - 'Bottomup' meets 'top-down': Self-assembly to direct manipulation of nanostructures on length scales from atoms to microns - funded through the Strategic Partnerships investment area as part of the National Institute for Nano-Engineering (NINE) project.

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We have used scanning tunneling microscopy and low-energy electron microscopy to measure the thermal decay of two-dimensional Cu, Pb-overlayer, and Pb-Cu alloy islands on Pb-Cu(1 1 1) surface alloys. Decay rates covering 6-7 orders of magnitude are accessible by applying the two techniques to the same system. We find that Cu adatom diffusion across the surface alloy is rate-limiting for the decay of both Pb and Pb-Cu islands on the surface alloy and that this rate decreases monotonically with increasing Pb concentration in the alloy. The decrease is attributed to repulsive interactions between Cu adatoms and embedded Pb atoms in the surface alloy. The measured temperature dependences of island decay rates are consistent with first-principles calculations of the Cu binding and diffusion energies related to this 'site-blocking' effect.

We present our research results on membrane pores. The study was divided into two primary sections. The first involved the formation of protein pores in free-standing lipid bilayer membranes. The second involved the fabrication via surface micromachining techniques and subsequent testing of solid-state nanopores using the same characterization apparatus and procedures as that used for the protein pores. We were successful in our ability to form leak-free lipid bilayers, to detect the formation of single protein pores, and to monitor the translocation dynamics of individual homogeneous 100 base strands of DNA. Differences in translocation dynamics were observed when the base was switched from adenine to cytosine. The solid state pores (2-5 nm estimated) were fabricated in thin silicon nitride membranes. Testing of the solid sate pores indicated comparable currents for the same size protein pore with excellent noise and sensitivity. However, there were no conditions under which DNA translocation was observed. After considerable effort, we reached the unproven conclusion that multiple (<1 nm) pores were formed in the nitride membrane, thus explaining both the current sensitivity and the lack of DNA translocation blockages.

Density functional calculations show that the electric field effect on Si ad-dimer diffusion on Si(0 0 1) is largely a reflection of the position dependence of the ad-dimer’s dipole moment. We can use surface diffusion barriers’ dependence on perpendicular electric fields to discriminate between diffusion mechanisms. Since the previously accepted mechanism for ad-dimer diffusion on Si(0 0 1) has the opposite field dependence to what is observed, it cannot be the one that dominates mass-transport. Here, we identify an alternate process, with a similar barrier at zero electric field and field dependence in agreement with measurements. For rotation, calculations to date show linear field dependence, in contrast to experiments.

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Diffusion of Pd in the Pd/Cu(100) surface alloy was studied as a function of temperature using atom tracking scanning tunneling microscopy. It was shown that Pd diffused by a vacany-exchange mechanism, by following the motion of individual Pd atom incorporated in the surface. Activation energy was measured for diffusion of incorporated Pd atom and was found to be in agreement with ab intio calculated energy.

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Atom-tracking scanning tunneling microscopy (AT-STM) was applied to the study of Ge-Si dimer diffusion. It was possible to measure real-time atomic intermixing, determine directly the time and the lattice site at which the intermixing occurs.

The authors carry out a comparative study of the energetic and dynamics of Si-Si, Ge-Ge, and Ge-Si ad-dimers on top of a dimer row in the Si(001) surface, using first-principles calculations. The dynamic appearance of a Ge-Si dimer is distinctively different from that of a Si-Si or Ge-Ge dimer, providing a unique way for its identification by scanning tunneling microscopy (STM). Its rocking motion, observed in STM, actually reflects a 180{degree} rotation of the dimer, involving a piecewise-rotation mechanism. The calculated energy barrier of 0.74 eV is in good agreement with the experimental value of 0.82 eV.

The positions of Ge atoms intermixed in the Si(100) surface at very low concentration are identified using empty-state imaging in scanning tunneling microscopy. A measurable degree of place exchange occurs at temperatures as low as 330 K. Contrary to earlier conclusions, good differentiation between Si atoms and Ge atoms can be achieved by proper imaging conditions.

The authors have used low-energy electron microscopy to investigate the dynamics of the Si(111) 7 x 7 {r_arrow} 1 x 1 phase transition. Because the densities of the two phases differ, the phase transformation is analogous to precipitation in bulk systems: additional material must diffuse to the phase boundaries in order for the transformation to occur. By measuring the size evolution of an ensemble of domains, and comparing the results to simulations, they have identified a new mechanism of precipitate growth. The source of material necessary for the transformation is the random creation of atom/vacancy pairs at the surface. This mechanism contrasts sharply with classical theories of precipitation, in which mass transport kinetics determine the rate of transformation.