We demonstrate the merits of an unexplored precursor, tetrasilane (Si₄H₁₀), as compared to disilane (Si₂H₆) for the growth of defect-free, epitaxial hexagonal silicon (Si). We investigate the growth kinetics of hexagonal Si shells epitaxially around defect-free wurtzite gallium phosphide (GaP) nanowires. Two temperature regimes are identified, representing two different surface reaction mechanisms for both types of precursors. Growth in the low temperature regime (415 °C-600 °C) is rate limited by interaction between the Si surface and the adsorbates, and in the high temperature regime (600 °C-735 °C) by chemisorption. The activation energy of the Si shell growth is 2.4 ±0.2 eV for Si₂H₆ and 1.5 ±0.1 eV for Si₄H₁₀ in the low temperature regime. We observe inverse tapering of the Si shells and explain this phenomenon by a basic diffusion model where the substrate acts as a particle sink. Most importantly, we show that, by using Si₄H₁₀ as a precursor instead of Si₂H₆, non-tapered Si shells can be grown with at least 50 times higher growth rate below 460 °C. The lower growth temperature may help to reduce the incorporation of impurities resulting from the growth of GaP.

The diffusion of photovoltaic systems is deterred by the struggle in combining high efficiency and low cost. Nanowire devices have been demonstrated to hold great promise to solve this predicament, but the substrate cost is still an unavoidable obstacle. Repeated nanowire growth on a single substrate is demonstrated by embedding InP nanowires in a polymer layer and removing them from the substrate. Our approach promises cost reduction by using the substrate multiple times. In addition, it provides a pathway to increase the open-circuit voltage by placing a mirror at the backside of the cell.

Charge carrier-selective contacts transform a light-absorbing semiconductor into a photovoltaic device. Current record efficiency solar cells nearly all use advanced heterojunction contacts that simultaneously provide carrier selectivity and contact passivation. One remaining challenge with heterojunction contacts is the tradeoff between better carrier selectivity/contact passivation (thicker layers) and better carrier extraction (thinner layers). Here we demonstrate that the nanowire geometry can remove this tradeoff by utilizing a permanent local gate (molybdenum oxide surface layer) to control the carrier selectivity of an adjacent ohmic metal contact. We show an open-circuit voltage increase for single indium phosphide nanowire solar cells by up to 335 mV, ultimately reaching 835 mV, and a reduction in open-circuit voltage spread from 303 to 105 mV after application of the surface gate. Importantly, reference experiments show that the carriers are not extracted via the molybdenum oxide but the ohmic metal contacts at the wire ends.

Direct band gap III-V semiconductors, emitting efficiently in the amber-green region of the visible spectrum, are still missing, causing loss in efficiency in light emitting diodes operating in this region, a phenomenon known as the "green gap". Novel geometries and crystal symmetries however show strong promise in overcoming this limit. Here we develop a novel material system, consisting of wurtzite Al_xIn_1-xP nanowires, which is predicted to have a direct band gap in the green region. The nanowires are grown with selective area metalorganic vapor phase epitaxy and show wurtzite crystal purity from transmission electron microscopy. We show strong light emission at room temperature between the near-infrared 875 nm (1.42 eV) and the "pure green" 555 nm (2.23 eV). We investigate the band structure of wurtzite Al_xIn_1-xP using time-resolved and temperature-dependent photoluminescence measurements and compare the experimental results with density functional theory simulations, obtaining excellent agreement. Our work paves the way for high-efficiency green light emitting diodes based on wurtzite III-phosphide nanowires.

Semiconductor nanowires are nanoscale structures holding promise in many fields such as optoelectronics, quantum computing, and thermoelectrics. Nanowires are usually grown vertically on (111)-oriented substrates, while (100) is the standard in semiconductor technology. The ability to grow and to control impurity doping of 〈100〉 nanowires is crucial for integration. Here, we discuss doping of single-crystalline 〈100〉 nanowires, and the structural and optoelectronic properties of p-n junctions based on 〈100〉 InP nanowires. We describe a novel approach to achieve low resistance electrical contacts to nanowires via a gradual interface based on p-doped InAsP. As a first demonstration in optoelectronic devices, we realize a single nanowire light emitting diode in a 〈100〉-oriented InP nanowire p-n junction. To obtain high vertical yield, which is necessary for future applications, we investigate the effect of the introduction of dopants on the nanowire growth.

Nanowire based solar cells have attracted great attention due to their potential for high efficiency and low device cost. Photovoltaic devices based on InP nanowires now have characteristics comparable to InP bulk solar cells. A detailed and direct correlation of the influence of growth conditions on performance is necessary to improve efficiency further. We explored the effects of the growth temperature, and of the addition of HCl during growth, on the efficiency of nanowire array based solar cell devices. By increasing HCl, the saturation dark current was reduced, and thereby the nanowire solar cell efficiency was enhanced from less than 1% to 7.6% under AM 1.5 illumination at 1 sun. At the same time, we observed that the solar cell efficiency decreased by increasing the tri-methyl-indium content, strongly suggesting that these effects are carbon related.

Photovoltaic cells based on arrays of semiconductor nanowires promise efficiencies comparable or even better than their planar counterparts with much less material. One reason for the high efficiencies is their large absorption cross section, but until recently the photocurrent has been limited to less than 70% of the theoretical maximum. Here we enhance the absorption in indium phosphide (InP) nanowire solar cells by employing broadband forward scattering of self-aligned nanoparticles on top of the transparent top contact layer. This results in a nanowire solar cell with a photovoltaic conversion efficiency of 17.8% and a short-circuit current of 29.3 mA/cm² under 1 sun illumination, which is the highest reported so far for nanowire solar cells and among the highest reported for III-V solar cells. We also measure the angle-dependent photocurrent, using time-reversed Fourier microscopy, and demonstrate a broadband and omnidirectional absorption enhancement for unpolarized light up to 60° with a wavelength average of 12% due to Mie scattering. These results unambiguously demonstrate the potential of semiconductor nanowires as nanostructures for the next generation of photovoltaic devices.

Nanophotonic engineering shows great potential for photovoltaics: the record conversion efficiencies of nanowire solar cells are increasing rapidly and the record open-circuit voltages are becoming comparable to the records for planar equivalents. Furthermore, it has been suggested that certain nanophotonic effects can reduce costs and increase efficiencies with respect to planar solar cells. These effects are particularly pronounced in single-nanowire devices, where two out of the three dimensions are subwavelength. Single-nanowire devices thus provide an ideal platform to study how nanophotonics affects photovoltaics. However, for these devices the standard definition of power conversion efficiency no longer applies, because the nanowire can absorb light from an area much larger than its own size. Additionally, the thermodynamic limit on the photovoltage is unknown a priori and may be very different from that of a planar solar cell. This complicates the characterization and optimization of these devices. Here, we analyse an InP single-nanowire solar cell using intrinsic metrics to place its performance on an absolute thermodynamic scale and pinpoint performance loss mechanisms. To determine these metrics we have developed an integrating sphere microscopy set-up that enables simultaneous and spatially resolved quantitative absorption, internal quantum efficiency (IQE) and photoluminescence quantum yield (PLQY) measurements. For our record single-nanowire solar cell, we measure a photocurrent collection efficiency of >90% and an open-circuit voltage of 850mV, which is 73% of the thermodynamic limit (1.16V).

The emission from nanowires can couple to waveguide modes supported by the nanowire geometry, thus governing the far-field angular pattern. To investigate the geometry-induced coupling of the emission to waveguide modes, we acquire Fourier microscopy images of the photoluminescence of nanowires with diameters ranging from 143 to 208 nm. From the investigated diameter range, we conclude that a few nanometers difference in diameter can abruptly change the coupling of the emission to a specific mode. Moreover, we observe a diameter-dependent width of the Gaussian-shaped angular pattern in the far-field emission. This dependence is understood in terms of interference of the guided modes, which emit at the end facets of the nanowire. Our results are important for the design of quantum emitters, solid state lighting, and photovoltaic devices based on nanowires.