Jesper Wallentin

InP Nanowire Array Solar Cells Achieving 13.8% Efficiency by Exceeding the Ray Optics Limit

Improving Nanowire Photovoltaics In principle, solar cells based on arrays of nanowires made from compound inorganic semiconductors, such as indium phosphide (InP), should decrease materials and fabrication costs compared with planar junctions. In practice, device efficiencies tend to be low because of poor light absorption and increased rates of unproductive charge recombination in the surface region. Wallentin et al. (p. 1057, published online 17 January) now report that arrays of p-i-n InP nanowires (that switch from positive to negative doping), grown to millimeter lengths, can be optimized by varying the nanowire diameter and length of the n-doped segment. Efficiencies as high as 13.8% were achieved, which are comparable to the best planar InP photovoltaics. Nanowire solar cells were fabricated that exhibit high photocurrents and low surface recombination. Photovoltaics based on nanowire arrays could reduce cost and materials consumption compared with planar devices but have exhibited low efficiency of light absorption and carrier collection. We fabricated a variety of millimeter-sized arrays of p-type/intrinsic/n-type (p-i-n) doped InP nanowires and found that the nanowire diameter and the length of the top n-segment were critical for cell performance. Efficiencies up to 13.8% (comparable to the record planar InP cell) were achieved by using resonant light trapping in 180-nanometer-diameter nanowires that only covered 12% of the surface. The share of sunlight converted into photocurrent (71%) was six times the limit in a simple ray optics description. Furthermore, the highest open-circuit voltage of 0.906 volt exceeds that of its planar counterpart, despite about 30 times higher surface-to-volume ratio of the nanowire cell.

Nanowires With Promise for Photovoltaics

Solar energy harvesting for electricity production is regarded as a fully credible future energy source: plentiful and without serious environmental concerns. The breakthrough for solar energy technology implementation has, however, been hampered by two issues: the conversion efficiency of light into electricity and the solar panel production cost. The use of III-V nanowires (NWs) in photovoltaics allows to respond to both these demands. They offer efficient light absorption and significant cost reduction. These low-dimensional structures can be grown epitaxially in dense NW arrays directly on silicon wafers, which are abundant and cheaper than the germanium substrates used for triple-junction solar cells today. For planar structures, lattice matching poses a strong restriction on growth. III-V NWs offer to create highly efficient multijunction devices, since multiple materials can be combined to match the solar spectrum without the need of tightly controlled lattice matching. At the same time, less material is required for NW-based solar cells than for planar-based architecture. This approach has potential to reach more than 50% in efficiency. Here, we describe our work on NW tandem solar cells, aiming toward two junctions absorbing different parts of the solar spectrum, connected in series via a tunnel diode.

A general approach for sharp crystal phase switching in InAs, GaAs, InP, and GaP nanowires using only group V flow.

III-V-based nanowires usually exhibit random mixtures of wurtzite (WZ) and zinc blende (ZB) crystal structure, and pure crystal phase wires represent the exception rather than the rule. In this work, the effective group V hydride flow was the only growth parameter which was changed during MOVPE growth to promote transitions from WZ to ZB and from ZB to WZ. Our technique works in the same way for all investigated III-Vs (GaP, GaAs, InP, and InAs), with low group V flow for WZ and high group V flow for ZB conditions. This strongly suggests a common underlying mechanism. It displays to our best knowledge the simplest changes of the growth condition to control the nanowire crystal structure. The inherent reduction of growth variables is a crucial requirement for the interpretation in the frame of existing understanding of polytypism in III-V nanowires. We show that the change in surface energetics of the vapor-liquid-solid system at the vapor-liquid and liquid-solid interface is likely to control the crystal structure in our nanowires.

Electron trapping in InP nanowire FETs with stacking faults.

Semiconductor III-V nanowires are promising components of future electronic and optoelectronic devices, but they typically show a mixed wurtzite-zinc blende crystal structure. Here we show, theoretically and experimentally, that the crystal structure dominates the conductivity in such InP nanowires. Undoped devices show very low conductivities and mobilities. The zincblende segments are quantum wells orthogonal to the current path and our calculations indicate that an electron concentration of up to 4.6 × 10(18) cm(-3) can be trapped in these. The calculations also show that the room temperature conductivity is controlled by the longest zincblende segment, and that stochastic variations in this length lead to an order of magnitude variation in conductivity. The mobility shows an unexpected decrease for low doping levels, as well as an unusual temperature dependence that bear resemblance with polycrystalline semiconductors.

High-performance single nanowire tunnel diodes.

We demonstrate single nanowire tunnel diodes with room temperature peak current densities of up to 329 A/cm(2). Despite the large surface to volume ratio of the type-II InP-GaAs axial heterostructure nanowires, we measure peak to valley current ratios (PVCR) of up to 8.2 at room temperature and 27.6 at liquid helium temperature. These sub-100-nm-diameter structures are promising components for solar cells as well as electronic applications.

Changes in Contact Angle of Seed Particle Correlated with Increased Zincblende Formation in Doped InP Nanowires.

Nanowires grown with the vapor-liquid-solid method commonly exhibit polytypism, showing both zincblende and wurtzite crystal structure. We have grown p-type InP nanowires using DEZn as a dopant precursor and studied the wetting of the seed particle and the nanowire crystal structure. The nanowires grown with high DEZn molar fractions exhibit deformed seed particles after growth. We observe 20% smaller nanowire diameter at the highest DEZn molar fraction, indicating a significant increase in contact angle of the seed particle during growth. The decrease in diameter correlates with an increase in zincblende segment length as measured by TEM. We explain the results with a modified nucleation model.

Probing the Wurtzite Conduction Band Structure Using State Filling in Highly Doped InP Nanowires.

We have grown InP nanowires doped with hydrogen sulfide, which exhibit sulfur concentrations of up to 1.4%. The highest doped nanowires show a pure wurtzite crystal structure, in contrast to bulk InP which has the zinc blende structure. The nanowires display photoluminescence which is strongly blue shifted compared with the band gap, well into the visible range. We find evidence of a second conduction band minimum at the gamma point about 0.23 eV above the band edge, in excellent agreement with recent theoretical predictions. Electrical measurements show high conductivity and breakdown currents of 10(7) A/cm(2).

Tunnel Field-Effect Transistors Based on InP-GaAs Heterostructure Nanowires.

We present tunneling field-effect transistors fabricated from InP-GaAs heterostructure nanowires with an n-i-p doping profile, where the intrinsic InP region is modulated by a top gate. The devices show an inverse subthreshold slope down to 50 mV/dec averaged over two decades with an on/off current ratio of approximately 10(7) for a gate voltage swing (V(GS)) of 1 V and an on-current of 2.2 μA/μm. Low-temperature measurements suggest a mechanism of trap-assisted tunneling, possibly explained by a narrow band gap segment of InGaAsP.

Particle-assisted GaxIn1−xP nanowire growth for designed bandgap structures

Non-tapered vertically straight Ga(x)In(1-x)P nanowires were grown in a compositional range from Ga(0.2)In(0.8)P to pure GaP in particle-assisted mode by controlling the trimethylindium, trimethylgallium and hydrogen chloride flows in metal-organic vapor phase epitaxy. X-ray energy dispersive spectroscopy in transmission electron microscopy revealed homogeneous radial material composition in single nanowires, whereas variations in the material composition were found along the nanowires. High-resolution x-ray diffraction indicates a variation of the material composition on the order of about 19% measuring an entire sample area, i.e., including edge effects during growth. The non-capped nanowires emit room temperature photoluminescence strongly in the energy range of 1.43-2.16 eV, correlated with the bandgap expected from the material composition.

A new route toward semiconductor nanospintronics: highly Mn-doped GaAs nanowires realized by ion-implantation under dynamic annealing conditions.

We report on highly Mn-doped GaAs nanowires (NWs) of high crystalline quality fabricated by ion beam implantation, a technique that allows doping concentrations beyond the equilibrium solubility limit. We studied two approaches for the preparation of Mn-doped GaAs NWs: First, ion implantation at room temperature with subsequent annealing resulted in polycrystalline NWs and phase segregation of MnAs and GaAs. The second approach was ion implantation at elevated temperatures. In this case, the single-crystallinity of the GaAs NWs was maintained, and crystalline, highly Mn-doped GaAs NWs were obtained. The electrical resistance of such NWs dropped with increasing temperature (activation energy about 70 meV). Corresponding magnetoresistance measurements showed a decrease at low temperatures, indicating paramagnetism. Our findings suggest possibilities for future applications where dense arrays of GaMnAs nanowires may be used as a new kind of magnetic material system.