Gaute Otnes

Strategies to obtain pattern fidelity in nanowire growth from large-area surfaces patterned using nanoimprint lithography

Position controlled nanowire growth is important for nanowire-based optoelectronic components which rely on light emission or light absorption. For solar energy harvesting applications, dense arrays of nanowires are needed; however, a major obstacle to obtaining dense nanowire arrays is seed particle displacement and coalescing during the annealing stage prior to nanowire growth. Here, we explore three different strategies to improve pattern preservation of large-area catalyst particle arrays defined by nanoimprint lithography for nanowire growth. First, we see that heat treating the growth substrate prior to nanoimprint lithography improves pattern preservation. Second, we explore the possibility of improving pattern preservation by fixing the seed particles in place prior to annealing by modifying the growth procedure. And third, we show that a SiNx growth mask can fully prevent seed particle displacement. We show how these strategies allow us to greatly improve the pattern fidelity of grown InP nanowire arrays with dimensions suitable for solar cell applications, ultimately achieving 100% pattern preservation over the sampled area. The generic nature of these strategies is supported through the synthesis of GaAs and GaP nanowires.

Doping evaluation of InP nanowires for tandem junction solar cells

In order to push the development of nanowire-based solar cells further using optimized nanowire diameter and pitch, a doping evaluation of the nanowire geometry is necessary. We report on a doping evaluation of n-type InP nanowires with diameters optimized for light absorption, grown by the use of metal-organic vapor phase epitaxy in particle-assisted growth mode using tetraethyltin (TESn) as the dopant precursor. The charge carrier concentration was evaluated using four-probe resistivity measurements and spatially resolved Hall measurements. In order to reach the highest possible nanowire doping level, we set the TESn molar fraction at a high constant value throughout growth and varied the trimethylindium (TMIn) molar fraction for different runs. Analysis shows that the charge carrier concentration in nanowires grown with the highest TMIn molar fraction (not leading to kinking nanowires) results in a low carrier concentration of approximately 10(16) cm(-3). By decreasing the molar fraction of TMIn, effectively increasing the IV/III ratio, the carrier concentration increases up to a level of about 10(19) cm(-3), where it seems to saturate. Axial carrier concentration gradients along the nanowires are found, which can be correlated to a combination of changes in the nanowire growth rate, measured in situ by optical reflectometry, and polytypism of the nanowires observed in transmission electron microscopy.

Comparing Hall Effect and Field Effect Measurements on the Same Single Nanowire

We compare and discuss the two most commonly used electrical characterization techniques for nanowires (NWs). In a novel single-NW device, we combine Hall effect and back-gated and top-gated field effect measurements and quantify the carrier concentrations in a series of sulfur-doped InP NWs. The carrier concentrations from Hall effect and field effect measurements are found to correlate well when using the analysis methods described in this work. This shows that NWs can be accurately characterized with available electrical methods, an important result toward better understanding of semiconductor NW doping.

Absorption and transmission of light in III–V nanowire arrays for tandem solar cell applications

III-V semiconductor nanowires are a platform for next-generation photovoltaics. An interesting research direction is to embed a nanowire array in a transparent polymer, either to act as a stand-alone flexible solar cell, or to be stacked on top of a conventional Si bottom cell to create a tandem structure. To optimize the tandem cell performance, high energy photons should be absorbed in the nanowires whereas low energy photons should be transmitted to and absorbed in the Si cell. Here, through optical measurements on 1.95 eV bandgap GaInP nanowire arrays embedded in a polymer membrane, we identify two mechanisms that could be detrimental for the performance of the tandem cell. First, the Au particles used in the nanowire synthesis can absorb >50% of the low-energy photons, leading to a <40% transmittance, even though the Au particles cover <15% of the surface area. The removal of the Au particles can recover the transmission of low energy photons to >80%. Second, after the removal of the Au particles, a 40% reflectance peak shows up due to resonant back-scattering of light from in-plane waveguide modes. To avoid the excitation of these optical modes in the nanowire array, we propose to limit the pitch of the nanowire array.

InxGa1–xP Nanowire Growth Dynamics Strongly Affected by Doping Using Diethylzinc

Semiconductor nanowires are versatile building blocks for optoelectronic devices, in part because nanowires offer an increased freedom in material design due to relaxed constraints on lattice matching during the epitaxial growth. This enables the growth of ternary alloy nanowires in which the bandgap is tunable over a large energy range, desirable for optoelectronic devices. However, little is known about the effects of doping in the ternary nanowire materials, a prerequisite for applications. Here we present a study of p-doping of InxGa1-xP nanowires and show that the growth dynamics are strongly affected when diethylzinc is used as a dopant precursor. Specifically, using in situ optical reflectometry and high-resolution transmission electron microscopy we show that the doping results in a smaller nanowire diameter, a more predominant zincblende crystal structure, a more Ga-rich composition, and an increased axial growth rate. We attribute these effects to changes in seed particle wetting angle and increased TMGa pyrolysis efficiency upon introducing diethylzinc. Lastly, we demonstrate degenerate p-doping levels in InxGa1-xP nanowires by the realization of an Esaki tunnel diode. Our findings provide insights into the growth dynamics of ternary alloy nanowires during doping, thus potentially enabling the realization of such nanowires with high compositional homogeneity and controlled doping for high-performance optoelectronics devices.

Understanding InP Nanowire Array Solar Cell Performance by Nanoprobe-Enabled Single Nanowire Measurements

III-V solar cells in the nanowire geometry might hold significant synthesis-cost and device-design advantages as compared to thin films and have shown impressive performance improvements in recent years. To continue this development there is a need for characterization techniques giving quick and reliable feedback for growth development. Further, characterization techniques which can improve understanding of the link between nanowire growth conditions, subsequent processing, and solar cell performance are desired. Here, we present the use of a nanoprobe system inside a scanning electron microscope to efficiently contact single nanowires and characterize them in terms of key parameters for solar cell performance. Specifically, we study single as-grown InP nanowires and use electron beam induced current characterization to understand the charge carrier collection properties, and dark current-voltage characteristics to understand the diode recombination characteristics. By correlating the single nanowire measurements to performance of fully processed nanowire array solar cells, we identify how the performance limiting parameters are related to growth and/or processing conditions. We use this understanding to achieve a more than 7-fold improvement in efficiency of our InP nanowire solar cells, grown from a different seed particle pattern than previously reported from our group. The best cell shows a certified efficiency of 15.0%; the highest reported value for a bottom-up synthesized InP nanowire solar cell. We believe the presented approach have significant potential to speed-up the development of nanowire solar cells, as well as other nanowire-based electronic/optoelectronic devices.

InP/GaInP nanowire tunnel diodes

Semiconductor nanowire (NW) solar cells with a single p-n junction have exhibited efficiency comparable to that of their planar counterparts with a substantial reduction in material consumption. Tandem geometry is a path toward the fabrication of devices with even higher efficiencies, for which a key step is the fabrication of tunnel (Esaki) diodes within NWs with the correct diameter, pitch, and material combination for maximized efficiency. InP/GaInP and GaInP/InP NW tunnel diodes with band gap combinations corresponding to high-efficiency solar energy harvesting were fabricated and their electrical characteristics and material properties were compared. Four different configurations, with respect to material composition and doping, were investigated. The NW arrays were grown with metal–organic vapor-phase epitaxy from Au particles by use of nano-imprint lithography, metal evaporation and lift-off. Electrical measurements showed that the NWs behave as tunnel diodes in both InP (bottom)/GaInP (top) and GaInP (bottom)/InP (top) configurations, exhibiting a maximum peak current density of 25 A/cm2, and maximum peak to valley current ratio of 2.5 at room temperature. The realization of NW tunnel diodes in both InP/GaInP and GaInP/InP configurations represent an opportunity for the use of NW tandem solar cells, whose efficiency is independent of the growth order of the different materials, increasing the flexibility regarding dopant incorporation polarity.

Time-resolved photoluminescence characterization of GaAs nanowire arrays on native substrate

Time-resolved photoluminescence (TRPL) measurements of nanowires (NWs) are often carried out on broken-off NWs in order to avoid the ensemble effects as well as substrate contribution. However, the development of NW-array solar cells could benefit from non-destructive optical characterization to allow faster feedback and further device processing. With this work, we show that different NW array and substrate spectral behaviors with delay time and excitation power can be used to determine which part of the sample dominates the detected spectrum. Here, we evaluate TRPL characterization of dense periodic as-grown GaAs NW arrays on a p-type GaAs substrate, including a sample with uncapped GaAs NWs and several samples passivated with AlGaAs radial shell of varied composition and thickness. We observe a strong spectral overlap of substrate and NW signals and find that the NWs can absorb part of the substrate luminescence signal, thus resulting in a modified substrate signal. The level of absorption depends on the NW-array geometry, making a deconvolution of the NW signal very difficult. By studying TRPL of substrate-only and as-grown NWs at 770 and 400 nm excitation wavelengths, we find a difference in spectral behavior with delay time and excitation power that can be used to assess whether the signal is dominated by the NWs. We find that the NW signal dominates with 400 nm excitation wavelength, where we observe two different types of excitation power dependence for the NWs capped with high and low Al composition shells. Finally, from the excitation power dependence of the peak TRPL signal, we extract an estimate of background carrier concentration in the NWs.

Simplifying Nanowire Hall Effect Characterization by Using a Three-Probe Device Design

Electrical characterization of nanowires is a time-consuming and challenging task due to the complexity of single nanowire device fabrication and the difficulty in interpreting the measurements. We present a method to measure Hall effect in nanowires using a three-probe device that is simpler to fabricate than previous four-probe nanowire Hall devices and allows characterization of nanowires with smaller diameter. Extraction of charge carrier concentration from the three-probe measurements using an analytical model is discussed and compared to simulations. The validity of the method is experimentally verified by a comparison between results obtained with the three-probe method and results obtained using four-probe nanowire Hall measurements. In addition, a nanowire with a diameter of only 65 nm is characterized to demonstrate the capabilities of the method. The three-probe Hall effect method offers a relatively fast and simple, yet accurate way to quantify the charge carrier concentration in nanowires and has the potential to become a standard characterization technique for nanowires.

Nanobeam X-ray Fluorescence Dopant Mapping Reveals Dynamics of in Situ Zn-Doping in Nanowires

The properties of semiconductors can be controlled using doping, making it essential for electronic and optoelectronic devices. However, with shrinking device sizes it becomes increasingly difficult to quantify doping with sufficient sensitivity and spatial resolution. Here, we demonstrate how X-ray fluorescence mapping with a nanofocused beam, nano-XRF, can quantify Zn doping within in situ doped III-V nanowires, by using large area detectors and high-efficiency focusing optics. The spatial resolution is defined by the focus size to 50 nm. The detection limit of 7 ppm (2.8 × 1017 cm-3), corresponding to about 150 Zn atoms in the probed volume, is bound by a background signal. In solar cell InP nanowires with a p-i-n doping profile, we use nano-XRF to observe an unintentional Zn doping of 5 × 1017 cm-3 in the middle segment. We investigated the dynamics of in situ Zn doping in a dedicated multisegment nanowire, revealing significantly sharper gradients after turning the Zn source off than after turning the source on. Nano-XRF could be used for quantitative mapping of a wide range of dopants in many types of nanostructures.