Strain-Engineered Multilayer Epitaxial Lift-Off for Cost-Efficient III-V Photovoltaics and Optoelectronics.

The efficient removal of epitaxially grown materials from their host substrate has a pivotal role in reducing the cost and material consumption of III-V solar cells and in making flexible thin-film devices. A multilayer epitaxial lift-off process is demonstrated that is scalable in both film size and in the number of released films. The process utilizes in-built, individually engineered epitaxial strain in each film to tailor the bending without the need for external layers to induce strain. Even without external support layers, the films retain good integrity after the lift-off, as evidenced by photoluminescence measurements. The films can be further processed into devices, demonstrated here with the fabrication of cm-scale solar cells using a three-layer lift-off process. Based on the included cost analysis, the solar cells are fabricated with a facile two-step process from the as-released films. The scalable multilayer lift-off process is highly cost-efficient and enables a 4-to-6-fold reduction in the cost with respect to the single-layer epitaxial lift-off process. The results are therefore significant for III-V photovoltaics and any other technologies that rely on thin-film III-V semiconductors.

CuI as a Hole-Selective Contact for GaAs Solar Cells.

Carrier-selective contacts have emerged as a promising architecture for solar cell fabrication. In this report, the first hole-selective III-V semiconductor solar cell is demonstrated using copper iodide (CuI) on i-GaAs. Surface passivation quality of GaAs is found to be essential for open-circuit voltage (VOC), with good correlation between photoluminescence properties of the GaAs layer and the VOC. Passivation with <10 nm thick In0.49Ga0.51P layers is shown to provide an over 300 mV improvement. Oxygen-rich CuI is formed by natural oxidation in the atmosphere, and the increased oxygen content of ∼10% is validated by energy-dispersive X-ray measurements. The oxygen incorporation is shown to improve hole selectivity and thus solar conversion efficiency. Ultraviolet photoelectron spectroscopy indicates a high work function of ∼6 eV for the oxygen-rich CuI. With optimized GaAs surface passivation and oxygen-rich CuI, a VOC of nearly 1 V and a solar conversion efficiency of 13.4% are achieved. The solar cell structure includes only undoped GaAs, a surface passivation layer, and non-epitaxial CuI contact and is therefore very promising to various low-cost crystal growth methods. The results have a significant impact on III-V solar cell fabrication and costs as it (i) enables fully carrier-selective architectures, (ii) reduces cell fabrication complexity, and (iii) is suitable for layers grown by low-cost crystal growth techniques.

Enhanced terahertz emission from mushroom-shaped InAs nanowire network induced by linear and nonlinear optical effects.

The development of powerful terahertz (THz) emitters is the cornerstone for future THz applications, such as communication, medical biology, non-destructive inspection, and scientific research. Here, we report the THz emission properties and mechanisms of mushroom-shaped InAs nanowire (NW) network using linearly polarized laser excitation. By investigating the dependence of THz signal to the incidence pump light properties (e.g. incident angle, direction, fluence, and polarization angle), we conclude that the THz wave emission from the InAs NW network is induced by the combination of linear and nonlinear optical effects. The former is a transient photocurrent accelerated by the photo-Dember field, while the latter is related to the resonant optical rectification effect. Moreover, thep-polarized THz wave emission component is governed by the linear optical effect with a proportion of ∼85% and the nonlinear optical effect of ∼15%. In comparison, thes-polarized THz wave emission component is mainly decided by the nonlinear optical effect. The THz emission is speculated to be enhanced by the localized surface plasmon resonance absorption of the In droplets on top of the NWs. This work verifies the nonlinear optical mechanism in the THz generation of semiconductor NWs and provides an enlightening reference for the structural design of powerful and flexible THz surface and interface emitters in transmission geometry.

Effect of crystal structure on the Young's modulus of GaP nanowires.

Young's modulus of tapered mixed composition (zinc-blende with a high density of twins and wurtzite with a high density of stacking faults) gallium phosphide (GaP) nanowires (NWs) was investigated by atomic force microscopy. Experimental measurements were performed by obtaining bending profiles of as-grown inclined GaP NWs deformed by applying a constant force to a series of NW surface locations at various distances from the NW/substrate interface. Numerical modeling of experimental data on bending profiles was done by applying Euler-Bernoulli beam theory. Measurements of the nano-local stiffness at different distances from the NW/substrate interface revealed NWs with a non-ideal mechanical fixation at the NW/substrate interface. Analysis of the NWs with ideally fixed base resulted in experimentally measured Young's modulus of 155 ± 20 GPa for ZB NWs, and 157 ± 20 GPa for WZ NWs, respectively, which are in consistence with a theoretically predicted bulk value of 167 GPa. Thus, impacts of the crystal structure (WZ/ZB) and crystal defects on Young's modulus of GaP NWs were found to be negligible.

Managing Resonant and Nonresonant Lasing Modes in GaAs Nanowire Random Lasers.

Random lasers are promising, easy-to-fabricate light sources that rely on scattering instead of well-defined optical cavities. We demonstrate random lasing in GaAs nanowires using both randomly oriented and vertically aligned arrays. These configurations are shown to lase in both resonant and nonresonant modes, where aligned nanowires support predominantly resonant lasing and randomly oriented favors nonresonant lasing. On the basis of numerical simulations, aligning the nanowires increases the system's scattering efficiency leading to higher quality factor modes and thus favoring the resonant modes. We further demonstrate two methods to optically suppress resonant mode lasing by increasing the number of excited modes. The light output-light input curves show a pronounced kink for the resonant lasing mode while the nonresonant mode is kink-free. The resonant lasing modes may be used as tunable lasers, and the nonresonant modes exhibit near-thresholdless amplification. Switching between lasing modes opens up new opportunities to use lasers in broader applications.

Management of light and scattering in InP NWs by dielectric polymer shell.

Understanding and management of light is of great importance for nanoscale devices. This report demonstrates enhanced absorption, photoluminescence and scattering in InP nanowires when coated with dielectric polymer shell. The shells increase absorption and emission by a factor of ∼2 and photoluminescence by a factor of ∼4. A thorough optical characterization is provided, including reflectance, transmission, luminescence and scattering to incident and transmitted directions. From this characterization, we derive the distribution of absorbed light within the structure (InP nanowires, Au seed particles and the substrate). Additionally, reflectance, transmission and emission are shown to become increasingly diffuse with the dielectric shells. The results are thought to provide better understanding in light-matter interaction in nanostructures, as well as to provide valuable tools for light and scattering management in nanoscale optoelectronics.

Direct Growth of Light-Emitting III-V Nanowires on Flexible Plastic Substrates.

Semiconductor nanowires are routinely grown on high-priced crystalline substrates as it is extremely challenging to grow directly on plastics and flexible substrates due to high-temperature requirements and substrate preparation. At the same time, plastic substrates can offer many advantages such as extremely low price, light weight, mechanical flexibility, shock and thermal resistance, and biocompatibility. We explore the direct growth of high-quality III-V nanowires on flexible plastic substrates by metal-organic vapor phase epitaxy (MOVPE). We synthesize InAs and InP nanowires on polyimide and show that the fabricated NWs are optically active with strong light emission in the mid-infrared range. We create a monolithic flexible nanowire-based p-n junction device on plastic in just two fabrication steps. Overall, we demonstrate that III-V nanowires can be synthesized directly on flexible plastic substrates inside a MOVPE reactor, and we believe that our results will further advance the development of the nanowire-based flexible electronic devices.

Thermal conductivity suppression in GaAs-AlAs core-shell nanowire arrays.

Semiconductor nanowire heterostructures have been shown to provide appealing properties for optoelectronics and solid-state energy harvesting by thermoelectrics. Among these nanoarchitectures, coaxial core-shell nanowires have been of primary interest due to their electrical functionality, as well as intriguing phonon localization effects in the surface-dominated regime predicted via atomic simulations. However, experimental studies on the thermophysical properties of III-V semiconductor core-shell nanowires remain scarce regardless of the ubiquitous nature of these compounds in solid-state applications. Here, we present thermal conductivity measurements of the arrays of GaAs nanowires coated with AlAs shells. We unveil a strong suppression in thermal transport facilitated by the AlAs shells, up to ∼60%, producing a non-monotonous dependence of thermal conductivity on the shell thickness. Such translation of the novel heat transport phenomena to macroscopic nanowire arrays paves the way for rational thermal design in nanoscale applications.

InAs-Nanowire-Based Broadband Ultrafast Optical Switch.

Due to their tunable optical properties with various shapes, sizes, and compositions, nanowires (NWs) have been regarded as a class of semiconductor nanostructures with great potential for photodetectors, light-emitting diodes, gas sensors, microcavity lasers, optical modulators, and converters. Indium arsenide (InAs), an attractive III-V semiconductor NW with the advantages of narrow bandgap and large electron mobility, has attracted considerable interest in infrared optoelectronic and photonic devices. Here, we studied the ultrafast carrier dynamics and nonlinear optical responses of InAs NWs ranging from 1.0 to 2.8 µm and demonstrated the InAs-NW-based ultrafast broadband optical switch for passively Q-switching in all-solid-state laser systems. Furthermore, we achieved ultrafast optical modulation for laser mode-locking at 1.0 µm, paving the way for their applications in the field of ultrafast optics. These exotic optical properties indicate that InAs NWs have significant potential for various optoelectronic and photonic devices, especially in the mid-infrared wavelength range.

III-V nanowires on black silicon and low-temperature growth of self-catalyzed rectangular InAs NWs.

We report the use of black silicon (bSi) as a growth platform for III-V nanowires (NWs), which enables low reflectance over a broad wavelength range as well as fabrication of optoelectronic devices by metalorganic vapor phase epitaxy. In addition, a new isolated growth regime is reported for self-catalyzed InAs NWs at record-low temperatures of 280 °C-365 °C, where consistently rectangular [-211]-oriented NWs are obtained. The bSi substrate is shown to support the growth of additionally GaAs and InP NWs, as well as heterostructured NWs. As seed particles, both ex-situ deposited Au nanoparticles and in-situ deposited In droplets are shown feasible. Particularly the InAs NWs with low band gap energy are used to extend low-reflectivity wavelength region into infrared, where the bSi alone remains transparent. Finally, a fabricated prototype device confirms the potential of III-V NWs combined with bSi for optoelectronic devices. Our results highlight the promise of III-V NWs on bSi for enhancing optoelectronic device performance on the low-cost Si substrates, and we believe that the new low-temperature NW growth regime advances the understanding and capabilities of NW growth.

Young's Modulus of Wurtzite and Zinc Blende InP Nanowires.

The Young's modulus of thin conical InP nanowires with either wurtzite or mixed "zinc blende/wurtzite" structures was measured. It has been shown that the value of Young's modulus obtained for wurtzite InP nanowires (E[0001] = 130 ± 30 GPa) was similar to the theoretically predicted value for the wurtzite InP material (E[0001] = 120 ± 10 GPa). The Young's modulus of mixed "zinc blende/wurtzite" InP nanowires (E[111] = 65 ± 10 GPa) appeared to be 40% less than the theoretically predicted value for the zinc blende InP material (E[111] = 110 GPa). An advanced method for measuring the Young's modulus of thin and flexible nanostructures is proposed. It consists of measuring the flexibility (the inverse of stiffness) profiles 1/k(x) by the scanning probe microscopy with precise control of loading force in nanonewton range followed by simulations.

Synthesis and properties of ultra-long InP nanowires on glass.

We report on the synthesis of Au-catalyzed InP nanowires (NWs) on low-cost glass substrates. Ultra-dense and ultra-long (up to ∼250 µm) InP NWs, with an exceptionally high growth rate of ∼25 µm min-1, were grown directly on glass using metal organic vapor phase epitaxy (MOVPE). Structural properties of InP NWs grown on glass were similar to the ones grown typically on Si substrates showing many structural twin faults but the NWs on glass always exhibited a stronger photoluminescence (PL) intensity at room temperature. The PL measurements of NWs grown on glass reveal two additional prominent impurity related emission peaks at low temperature (10 K). In particular, the strongest unusual emission peak with an activation energy of 23.8 ± 2 meV was observed at 928 nm. Different possibilities including the role of native defects (phosphorus and/or indium vacancies) are discussed but most likely the origin of this PL peak is related to the impurity incorporation from the glass substrate. Furthermore, despite the presence of suspected impurities, the NWs on glass show outstanding light absorption in a wide spectral range (60%-95% for λ = 300-1600 nm). The optical properties and the NW growth mechanism on glass is discussed qualitatively. We attribute the exceptionally high growth rate mostly to the atmospheric pressure growth conditions of our MOVPE reactor and stronger PL intensity on glass due to the impurity doping. Overall, the III-V NWs grown on glass are similar to the ones grown on semiconductor substrates but offer additional advantages such as low-cost and light transparency.

Lithography-free shell-substrate isolation for core-shell GaAs nanowires.

A facile and scalable lithography-free technique(5) for the rapid construction of GaAs core-shell nanowires incorporating shell isolation from the substrate is reported. The process is based on interrupting NW growth and applying a thin spin-on-glass (SOG) layer to the base of the NWs and resuming core-shell NW growth. NW growth occurred in an atmospheric pressure metalorganic vapour phase epitaxy (MOVPE) system with gold nanoparticles used as catalysts for the vapour-liquid-solid growth. It is shown that NW axial core growth and radial shell growth can be resumed after interruption and even exposure to air. The SOG residues and native oxide layer that forms on the NW surface are shown to prevent or perturb resumption of epitaxial NW growth if not removed. Both HF etching and in situ annealing of the air-exposed NWs in the MOVPE were shown to remove the SOG residues and native oxide layer. While both procedures are shown capable of removing the native oxide and enabling resumption of epitaxial NW growth, in situ annealing produced the best results and allowed construction of pristine core-shell NWs. No growth occurred on SOG and it was observed that axial NW growth was more rapid when a SOG layer covered the substrate. The fabricated p-core/n-shell NWs exhibited diode behaviour upon electrical testing. The isolation of the NW shells from the substrate was confirmed by scanning electron microscopy and electrical measurements. The crystal quality of the regrown core-shell NWs was verified with a high resolution transmission electron microscope. The reported technique potentially provides a pathway using MOVPE for scalable and high-throughput production of shell-substrate isolated core-shell NWs on an industrial scale.

A technique for large-area position-controlled growth of GaAs nanowire arrays.

We demonstrate a technique for fabricating position-controlled, large-area arrays of vertical semiconductor nanowires (NWs) with adjustable periods and NW diameters. In our approach, a Au-covered GaAs substrate is first coated with a thin film of photoresponsive azopolymer, which is exposed twice to a laser interference pattern forming a 2D surface relief grating. After dry etching, an array of polymer islands is formed, which is used as a mask to fabricate a matrix of gold particles. The Au particles are then used as seeds in vapour-liquid-solid growth to create arrays of vertical GaAs NWs using metalorganic vapour phase epitaxy. The presented technique enables producing NWs of uniform size distribution with high throughput and potentially on large wafer sizes without relying on expensive lithography techniques. The feasibility of the technique is demonstrated by arrays of vertical NWs with periods of 255-1000 nm and diameters of 50-80 nm on a 2 × 2 cm area. The grown NWs exhibit high long range order and good crystalline quality. Although only GaAs NWs were grown in this study, in principle, the presented technique is suitable for any material available for Au seeded NW growth.

Fabrication of dual-type nanowire arrays on a single substrate.

A novel method for fabricating dual-type nanowire (NW) arrays is presented. Two growth steps, selective-area epitaxy (SAE) in the first step and vapor-liquid-solid (VLS) in the second step, are used to grow two types of NWs on the same GaAs substrate. Different precursors can be used for the growth steps, resulting in sophisticated compositional control, as demonstrated for side-by-side grown GaAs and InP NWs. It was found that parasitic growth occurs on the NWs already present on the substrate during the second growth step and that the SAE NWs shadow the growth of the VLS NWs. Optical reflectance measurements revealed the dual-type array having improved light trapping properties compared to single-type arrays. Dual-type NW arrays could be practical for thermoelectric generation, photovoltaics and sensing where composition control of side-by-side NWs and complex configurations are beneficial.

Aluminum-Induced photoluminescence red shifts in core-shell GaAs/Al(x)Ga(1-x)As nanowires.

We report a new phenomenon related to Al-induced carrier confinement at the interface in core-shell GaAs/Al(x)Ga(1-x)As nanowires grown using metal-organic vapor phase epitaxy with Au as catalyst. All Al(x)Ga(1-x)As shells strongly passivated the GaAs nanowires, but surprisingly the peak photoluminescence (PL) position and the intensity from the core were found to be a strong function of Al composition in the shell at low temperatures. Large and systematic red shifts of up to ~66 nm and broadening in the PL emission from the GaAs core were observed when the Al composition in the shell exceeded 3%. On the contrary, the phenomenon was observed to be considerably weaker at the room temperature. Cross-sectional transmission electron microscopy reveals Al segregation in the shell along six Al-rich radial bands displaying a 3-fold symmetry. Time-resolved PL measurements suggest the presence of indirect electron-hole transitions at the interface at higher Al composition. We discuss all possibilities including a simple shell-core-shell model using simulations where the density of interface traps increases with the Al content, thus creating a strong local electron confinement. The carrier confinement at the interface is most likely related to Al inhomogeneity and/or Al-induced traps. Our results suggest that a low Al composition in the shell is desirable in order to achieve ideal passivation in GaAs nanowires.

High quality GaAs nanowires grown on glass substrates.

We report for the first time the growth of GaAs nanowires directly on low-cost glass substrates using atmospheric pressure metal organic vapor phase epitaxy via a vapor-liquid-solid mechanism with gold as catalyst. Substrates used in this work were of float glass type typically seen in household window glasses. Growth of GaAs nanowires on glass were investigated for growth temperatures between 410 and 580 °C. Perfectly cylindrical nontapered nanowires with a growth rate of ~33 nm/s were observed at growth temperatures of 450 and 470 °C, whereas highly tapered pillar-like wires were observed at 580 °C. Nanowires grew horizontally on the glass surface at 410 °C with a tendency to grow in vertically from the substrate as the growth temperature was increased. X-ray diffraction and transmission electron microscopy revealed that the nanowires have a perfect zinc blende structure with no planar structural defects or stacking faults. Strong photoluminescence emission was observed both at low temperature and room temperature indicating a high optical quality of GaAs nanowires. Growth comparison on impurity free fused silica substrate suggests unintentional doping of the nanowires from the glass substrate.