Person:

Day, Robert

Over the past decade extensive studies of single semiconductor nanowire and nanowire array photovoltaic devices have explored the potential of these materials as platforms for a new generation of efficient and cost-effective solar cells. This feature review discusses strategies for implementation of semiconductor nanowires in solar energy applications, including advances in complex nanowire synthesis and characterization, fundamental insights from characterization of devices, utilization and control of the unique optical properties of nanowires, and new strategies for assembly and scaling of nanowires into diverse arrays that serve as a new paradigm for advanced solar cells.

Enhanced synthetic control of the morphology, crystal structure, and composition of nanostructures can drive advances in nanoscale devices. Axial and radial semiconductor nanowires are examples of nanostructures with one and two structural degrees of freedom, respectively, and their synthetically tuned and modulated properties have led to advances in nanotransistor, nanophotonic, and thermoelectric devices. Similarly, developing methods that allow for synthetic control of greater than two degrees of freedom could enable new opportunities for functional nanostructures. Here we demonstrate the first regioselective nanowire shell synthesis in studies of Ge and Si growth on faceted Si nanowire surfaces. The selectively deposited Ge is crystalline, and its facet position can be synthetically controlled in situ. We use this synthesis to prepare electrically addressable nanocavities into which solution soluble species such as Au nanoparticles can be incorporated. The method furnishes multicomponent nanostructures with unique photonic properties and presents a more sophisticated nanodevice platform for future applications in catalysis and photodetection.

Subwavelength diameter semiconductor nanowires can support optical resonances with anomalously large absorption cross sections, and thus tailoring these resonances to specific frequencies could enable a number of nanophotonic applications. Here, we report the design and synthesis of core/shell p-type/intrinsic/n-type (p/i/n) Si nanowires (NWs) with different sizes and cross-sectional morphologies as well as measurement and simulation of photocurrent spectra from single-NW devices fabricated from these NW building blocks. Approximately hexagonal cross-section p/i/n coaxial NWs of various diameters (170–380 nm) were controllably synthesized by changing the Au catalyst diameter, which determines core diameter, as well as shell deposition time, which determines shell thickness. Measured polarization-resolved photocurrent spectra exhibit well-defined diameter-dependent peaks. The corresponding external quantum efficiency (EQE) spectra calculated from these data show good quantitative agreement with finite-difference time-domain (FDTD) simulations and allow assignment of the observed peaks to Fabry–Perot, whispering-gallery, and complex high-order resonant absorption modes. This comparison revealed a systematic red-shift of equivalent modes as a function of increasing NW diameter and a progressive increase in the number of resonances. In addition, tuning shell synthetic conditions to enable enhanced growth on select facets yielded NWs with approximately rectangular cross sections; analysis of transmission electron microscopy and scanning electron microscopy images demonstrate that growth of the n-type shell at (860^{\circ}C) in the presence of phosphine leads to enhanced relative Si growth rates on the four {113} facets. Notably, polarization-resolved photocurrent spectra demonstrate that at longer wavelengths the rectangular cross-section NWs have narrow and significantly larger amplitude peaks with respect to similar size hexagonal NWs. A rectangular NW with a diameter of 260 nm yields a dominant mode centered at 570 nm with near-unity EQE in the transverse-electric polarized spectrum. Quantitative comparisons with FDTD simulations demonstrate that these new peaks arise from cavity modes with high symmetry that conform to the cross-sectional morphology of the rectangular NW, resulting in low optical loss of the mode. The ability to modulate absorption with changes in nanoscale morphology by controlled synthesis represents a promising route for developing new photovoltaic and optoelectronic devices.