Aaron M. Katzenmeyer

Patterned radial GaAs nanopillar solar cells.

Photovoltaic devices using GaAs nanopillar radial p-n junctions are demonstrated by means of catalyst-free selective-area metal-organic chemical vapor deposition. Dense, large-area, lithographically defined vertical arrays of nanowires with uniform spacing and dimensions allow for power conversion efficiencies for this material system of 2.54% (AM 1.5 G) and high rectification ratio of 213 (at ±1 V). The absence of metal catalyst contamination results in leakage currents of ∼236 nA at -1 V. High-resolution scanning photocurrent microscopy measurements reveal the independent functioning of each nanowire in the array with an individual peak photocurrent of ∼1 nA at 544 nm. External quantum efficiency shows that the photocarrier extraction highly depends on the degenerately doped transparent contact oxide. Two different top electrode schemes are adopted and characterized in terms of Hall, sheet resistance, and optical transmittance measurements.

A Perspective on Nanowire Photodetectors: Current Status, Future Challenges, and Opportunities

One-dimensional semiconductor nanostructures (nanowires (NWs), nanotubes, nanopillars, nanorods, etc.) based photodetectors (PDs) have been gaining traction in the research community due to their ease of synthesis and unique optical, mechanical, electrical, and thermal properties. Specifically, the physics and technology of NW PDs offer numerous insights and opportunities for nanoscale optoelectronics, photovoltaics, plasmonics, and emerging negative index metamaterials devices. The successful integration of these NW PDs on CMOS-compatible substrates and various low-cost substrates via direct growth and transfer-printing techniques would further enhance and facilitate the adaptation of this technology module in the semiconductor foundries. In this paper, we review the unique advantages of NW-based PDs, current device integration schemes and practical strategies, recent device demonstrations in lateral and vertical process integration with methods to incorporate NWs in PDs via direct growth (nanoepitaxy) methods and transfer-printing methods, and discuss the numerous technical design challenges. In particular, we present an ultrafast surface-illuminated PD with 11.4-ps full-width at half-maximum (FWHM), edge-illuminated novel waveguide PDs, and some novel concepts of light trapping to provide a full-length discussion on the topics of: 1) low-resistance contact and interfaces for NW integration; 2) high-speed design and impedance matching; and 3) CMOS-compatible mass-manufacturable device fabrication. Finally, we offer a brief outlook into the future opportunities of NW PDs for consumer and military application.

Kinetics and mechanism of metal-organic framework thin film growth: Systematic investigation of HKUST-1 deposition on QCM electrodes.

We describe a systematic investigation of the factors controlling step-by-step growth of the metal–organic framework (MOF) [Cu3(btc)2(H2O)3]·xH2O (also known as HKUST-1), using quartz crystal microbalance (QCM) electrodes as an in situ probe of the reaction kinetics and mechanism. Electrodes coated with silica, alumina and gold functionalized with OH– and COOH–terminated self-assembled monolayers (SAMs) were employed to determine the effects of surface properties on nucleation. Deposition rates were measured using the high sensitivity available from QCM-D (D = dissipation) techniques to determine rate constants in the early stage of the process. Films were characterized using grazing incidence XRD, SEM, AFM, profilometry and reflection–absorption IR spectroscopy. The effects of reaction time, concentration, temperature and substrate on the deposition rates, film crystallinity and surface morphology were evaluated. The initial growth step, in which the surface is exposed to copper ions (in the form of an ethanolic solution of copper(II) acetate) is fast and independent of temperature, after which all subsequent steps are thermally activated over the temperature range 22–62 °C. Using these data, we propose a kinetic model for the Cu3(btc)2 growth on surfaces that includes rate constants for the individual steps. The magnitude of the activation energies, in particular the large entropy decrease, suggests an associative reaction with a tight transition state. The measured activation energies for the step-by-step MOF growth are an order of magnitude lower than the value previously reported for bulk Cu3(btc)2 crystals. Finally, the results of this investigation demonstrate that the QCM method is a powerful tool for quantitative, in situ monitoring of MOF growth in real time.

Efficient Terahertz Emission from InAs Nanowires

Abstract : We observe intense pulses of far-infrared electromagnetic radiation emitted from arrays of InAs nanowires. The terahertz radiation power efficiency of these structures is 15 times higher than a planar InAs substrate. This is explained by the preferential orientation of coherent plasma motion to the wire surface, which overcomes radiation trapping by total-internal reflection.We present evidence that this radiation originates from a low-energy acoustic surface plasmon mode of the nanowire. This is supported by independent measurements of electronic transport on individual nanowires, ultrafast terahertz spectroscopy, and theoretical analysis. Our combined experiments and analysis further indicate that these plasmon modes are specific to high aspect ratio geometries.

Transport characterization in nanowires using an electrical nanoprobe

Electrical transport in semiconductor nanowires is commonly measured in a field effect transistor configuration, with lithographically defined source, drain and in some cases, top gate electrodes. This approach is labor intensive, requires high-end fabrication equipment, exposes the nanowires to extensive processing chemistry and places practical limitations on minimum nanowire length. Here we describe an alternative, simple method for characterizing electrical transport in nanowires directly on the growth substrate, without any need for post growth processing. Our technique is based on contacting nanowires using a nano-manipulator probe retrofitted inside of a scanning electron microscope. Using this approach, we characterize electrical transport in GaN nanowires grown by catalyst-free selective epitaxy, as well as InAs and Ge nanowires grown by a Au-catalyzed vapor solid liquid technique. We find that in situations where contacts are not limiting carrier injection (GaN and InAs nanowires), electrical transport transitions from Ohmic conduction at low bias to space-charge-limited conduction at higher bias. Using this transition and a theory of space-charge-limited transport which accounts for the high aspect ratio nanowires, we extract the mobility and the free carrier concentration. For Ge nanowires, we find that the Au catalyst forms a Schottky contact resulting in rectifying current‐voltage characteristics, which are strongly dependent on the nanowire diameter. This dependence arises due to an increase in depletion width at decreased nanowire diameter and carrier recombination at the nanowire surface. (Some figures in this article are in colour only in the electronic version)

Harvesting and Transferring Vertical Pillar Arrays of Single-Crystal Semiconductor Devices to Arbitrary Substrates

Development of devices that can be fabricated on amorphous substrates using multiple single-crystal semiconductors with different physical, electrical, and optical characteristics is important for highly efficient portable and flexible electronics, optoelectronics, and energy conversion devices. Reducing the use of single-crystal substrates can contribute to low-cost and environmentally benign devices covering a large area. We demonstrate a technique to harvest and transfer vertically aligned single-crystal semiconductor micro- and nanopillars from a single-crystal substrate to a low-cost carrier substrate while simultaneously preserving the integrity, order, shape, and fidelity of the transferred pillar arrays. The transfer technique facilitates multilayer process integration by exploiting a vertical embossing and lateral fracturing method using a spin-coated polymer layer on a carrier substrate. Electrical contacts are formed using a bilayer of metal and conducting polymer such as gold (Au) and polyaniline (PAni). In this method, the original single-crystal substrate can be repeatedly used for generating more devices and is minimally consumed, whereas in conventional fabrication methods, the substrate is employed solely as a mechanical support. This heterogeneous integration technique potentially offers devices with low physical fill factor contributing to lower leakage current and noise, reduced parasitic capacitance, and enhanced photon-semiconductor interactions, and enables heterogeneous multimaterial integration such as silicon with compound semiconductors for rapidly expanding large-scale applications, including low-cost and flexible electronics, displays, tactile sensors, and energy conversion systems.

Poole-Frenkel effect and phonon-assisted tunneling in GaAs nanowires.

We present electronic transport measurements of GaAs nanowires grown by catalyst-free metal-organic chemical vapor deposition. Despite the nanowires being doped with a relatively high concentration of substitutional impurities, we find them inordinately resistive. By measuring sufficiently high aspect ratio nanowires individually in situ, we decouple the role of the contacts and show that this semi-insulating electrical behavior is the result of trap-mediated carrier transport. We observe Poole-Frenkel transport that crosses over to phonon-assisted tunneling at higher fields, with a tunneling time found to depend predominantly on fundamental physical constants as predicted by theory. By using in situ electron beam irradiation of individual nanowires, we probe the nanowire electronic transport when free carriers are made available, thus revealing the nature of the contacts.

Synthesis of crystalline ZnO nanostructures on arbitrary substrates at ambient conditions

In this paper, we report on a new method of synthesis for ZnO nanowires on arbitrary substrates and nanowalls on aluminum coated substrates at ambient conditions. Our method is based on sonochemical reaction of Zinc acetate dihydrate (Zn(O2CCH3)2-2H2O) Zinc nitrate hexahydrate (Zn(NO3)2-6H2O) and hexamethylenetetramine (HMT, (CH2).6N4) in aqueous solutions. Repetitive growth cycles resulted in synthesis of ZnO nanowires and nanowalls with controlled dimensions and large aspect ratios. Extensive analysis by transmission electron microscopy (TEM), energy dispersive x-ray spectroscopy (EDS) and UV-Visible spectroscopy revealed the crystalline ZnO composition of the synthesized nanostructures. The proposed method is a rapid, inexpensive, low-temperature, catalyst-free, CMOS compatible and environmentally benign alternative to existing growth techniques.

Purely sonochemical route for oriented zinc oxide nanowire growth on arbitrary substrate

We report a simple sonochemical method for the seeding and synthesis of Zinc Oxide nanowire arrays that can be formed on a number of substrates that are stable in alcohol and aqueous solution. Vertically aligned ZnO NWs were synthesized from a single solution at room-ambient via ultrasonic excitation. Prior to the NW growth, a ZnO seed layer was deposited using the same system with a different solution. The optimal conditions to produce a high density of oriented wires along with their optical characteristics are presented for ZnO NWs with a significantly high growth rate compared with traditional growth techniques such as evaporation, chemical vapor deposition and sputtering. Our method promises a mass-manufacturable process for fast and inexpensive ZnO NW production for practical low cost electronics, photonics and energy conversion applications.

Poly(hydridocarbyne) as Highly Processable Insulating Polymer Precursor to Micro/Nanostructures and Graphite Conductors

Carbon-based electronic materials have received much attention since the discovery and elucidation of the properties of the nanotube, fullerene allotropes, and conducting polymers. Amorphous carbon, graphite, graphene, and diamond have also been the topics of intensive research. In accordance with this interest, we herein provide the details of a novel and facile method for synthesis of poly(hydridocarbyne) (PHC), a preceramic carbon polymer reported to undergo a conversion to diamond-like carbon (DLC) upon pyrolysis and also provide electrical characterization after low-temperature processing and pyrolysis of this material. The results indicate that the strongly insulating polymer becomes notably conductive in bulk form upon heating and contains interspersed micro- and nanostructures, which are the subject of ongoing research.