James F. Cahoon

Tuning Light Absorption in Core/Shell Silicon Nanowire Photovoltaic Devices through Morphological Design

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 °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.

Preparation and Characterization of Polyimide/Organoclay Nanocomposites

Abstract Organically modified montmorrillonite clay, containing a long chain aliphatic quarternary ammonium cation, was used to prepare polyimide/organoclay hybrids. Several approaches were examined in an attempt to achieve fully exfoliated nanocomposites. These included simple mixing of the clay in a pre-made high molecular weight poly(amide acid) solution; simple mixing followed by sonication of the organoclay/poly(amide acid) solutions; and the preparation of high molecular weight poly(amide acid)s in the presence of the organoclay dispersed in N-methyl-2-pyrrolidinone (NMP). The best results were obtained using the in-situ polymerization approach. The resulting nanocomposite films (both amide acid and imide), containing 3–8% by weight of organoclay, were characterized by differential scanning calorimetry (DSC), dynamic thermogravimetric analysis (TGA), transmission electron microscopy (TEM), X-ray diffraction (XRD) and thin film tensile properties. A significant degree of dispersion was observed in the nanocomposite films of the amide acid and the imide. After thermal treatment of amide acid films to effect imidization, in both air and nitrogen, the films were visually darker than control films without clay and the level of clay dispersion appeared to have decreased. In the latter case, the separation between the layers of the clay decreased to a spacing less than that present in the original organoclay. These observations suggest that thermal degradation of the aliphatic quarternary ammonium cation occurred likely during thermal treatment to effect imidization and solvent removal. These thermal degradation effects were less pronounced when thermal treatment was performed under nitrogen. The polyimide/organoclay hybrid films exhibited higher room temperature tensile moduli and lower strength and elongation to break than the control films.

Coaxial multishell nanowires with high-quality electronic interfaces and tunable optical cavities for ultrathin photovoltaics

Silicon nanowires (NWs) could enable low-cost and efficient photovoltaics, though their performance has been limited by nonideal electrical characteristics and an inability to tune absorption properties. We overcome these limitations through controlled synthesis of a series of polymorphic core/multishell NWs with highly crystalline, hexagonally-faceted shells, and well-defined coaxial (p/n) and p/intrinsic/n (p/i/n) diode junctions. Designed 200–300 nm diameter p/i/n NW diodes exhibit ultralow leakage currents of approximately 1 fA, and open-circuit voltages and fill-factors up to 0.5 V and 73%, respectively, under one-sun illumination. Single-NW wavelength-dependent photocurrent measurements reveal size-tunable optical resonances, external quantum efficiencies greater than unity, and current densities double those for silicon films of comparable thickness. In addition, finite-difference-time-domain simulations for the measured NW structures agree quantitatively with the photocurrent measurements, and demonstrate that the optical resonances are due to Fabry-Perot and whispering-gallery cavity modes supported in the high-quality faceted nanostructures. Synthetically optimized NW devices achieve current densities of 17 mA/cm2 and power-conversion efficiencies of 6%. Horizontal integration of multiple NWs demonstrates linear scaling of the absolute photocurrent with number of NWs, as well as retention of the high open-circuit voltages and short-circuit current densities measured for single NW devices. Notably, assembly of 2 NW elements into vertical stacks yields short-circuit current densities of 25 mA/cm2 with a backside reflector, and simulations further show that such stacking represents an attractive approach for further enhancing performance with projected efficiencies of > 15% for 1.2 μm thick 5 NW stacks.

Determining Transition State Geometries in Liquids Using 2D-IR

Many properties of chemical reactions are determined by the transition state connecting reactant and product, yet it is difficult to directly obtain any information about these short-lived structures in liquids. We show that two-dimensional infrared (2D-IR) spectroscopy can provide direct information about transition states by tracking the transformation of vibrational modes as a molecule crossed a transition state. We successfully monitored a simple chemical reaction, the fluxional rearrangement of Fe(CO)5, in which the exchange of axial and equatorial CO ligands causes an exchange of vibrational energy between the normal modes of the molecule. This energy transfer provides direct evidence regarding the time scale, transition state, and mechanism of the reaction.

Design Principles for Photovoltaic Devices Based on Si Nanowires with Axial or Radial p–n Junctions

Semiconductor nanowires (NWs) are a developing platform for electronic and photonic technologies, and many demonstrated devices utilize a p-type/n-type (p-n) junction encoded along either the axial or radial directions of the wires. These miniaturized junctions enable a diverse range of functions, from sensors to solar cells, yet the physics of the devices has not been thoroughly evaluated. Here, we present finite-element modeling of axial and radial Si NW p-n junctions with total diameters of ~240 nm and donor/acceptor doping levels ranging from 10(16) to 10(20) cm(-3). We evaluate the photovoltaic performance of horizontally oriented NWs under 1 sun illumination and compare simulated current-voltage data to experimental measurements, permitting detailed analysis of NW performance, limitations, and prospect as a technology for solar energy conversion. Although high surface-to-volume ratios are cited as detrimental to NW performance, radial p-n junctions are surprisingly insensitive to surface recombination, with devices supporting open-circuit voltages (V(OC)) of ~0.54 V and internal quantum efficiencies of 95% even with high surface recombination velocities (SRVs) of 10(5) cm/s. Axial devices, in which the depletion region is exposed to the surface, are far more sensitive to SRV, requiring substantially lower values of 10(3)-10(4) cm/s to produce the same level of performance. For low values of the SRV (<100 cm/s), both axial and radial NWs can support V(OC) values of >0.70 V if the bulk minority carrier lifetime is 1 μs or greater. Experimental measurements on NWs grown by a vapor-liquid-solid mechanism yield V(OC) of 0.23 and 0.44 V for axial and radial NWs, respectively, and show that axial devices are limited by a SRV of ~7 × 10(3) cm/s while radial devices are limited by a bulk lifetime of ~3 ns. The simulations show that with further development the electrical characteristics of 200-300 nm Si NWs are sufficient to support power-conversion efficiencies of 15-25%. The analysis presented here can be generalized to other semiconductor homo- and heterojunctions, and we expect that insights from finite element modeling will serve as a powerful method to guide the design of advanced nanoscale structures.

Direct imaging of free carrier and trap carrier motion in silicon nanowires by spatially-separated femtosecond pump-probe microscopy.

We have developed a pump-probe microscope capable of exciting a single semiconductor nanostructure in one location and probing it in another with both high spatial and temporal resolution. Experiments performed on Si nanowires enable a direct visualization of the charge cloud produced by photoexcitation at a localized spot as it spreads along the nanowire axis. The time-resolved images show clear evidence of rapid diffusional spreading and recombination of the free carriers, which is consistent with ambipolar diffusion and a surface recombination velocity of ∼10(4) cm/s. The free carrier dynamics are followed by trap carrier migration on slower time scales.

Doubling absorption in nanowire solar cells with dielectric shell optical antennas.

Semiconductor nanowires (NWs) often exhibit efficient, broadband light absorption despite their relatively small size. This characteristic originates from the subwavelength dimensions and high refractive indices of the NWs, which cause a light-trapping optical antenna effect. As a result, NWs could enable high-efficiency but low-cost solar cells using small volumes of expensive semiconductor material. Nevertheless, the extent to which the antenna effect can be leveraged in devices will largely determine the economic viability of NW-based solar cells. Here, we demonstrate a simple, low-cost, and scalable route to dramatically enhance the optical antenna effect in NW photovoltaic devices by coating the wires with conformal dielectric shells. Scattering and absorption measurements on Si NWs coated with shells of SiN(x) or SiO(x) exhibit a broadband enhancement of light absorption by ∼ 50-200% and light scattering by ∼ 200-1000%. The increased light-matter interaction leads to a ∼ 80% increase in short-circuit current density in Si photovoltaic devices under 1 sun illumination. Optical simulations reproduce the experimental results and indicate the dielectric-shell effect to be a general phenomenon for groups IV, II-VI, and III-V semiconductor NWs in both lateral and vertical orientations, providing a simple route to approximately double the efficiency of NW-based solar cells.

Horizontal Silicon Nanowires with Radial p–n Junctions: A Platform for Unconventional Solar Cells

The silicon p-n junction is the most successful solar energy technology to date, yet it accounts for a marginal percentage of worldwide energy production. To change the status quo, a disruptive technological breakthrough is needed. In this Perspective, we discuss the potential for complex silicon nanowires to serve as a platform for next-generation photovoltaic devices. We review the synthesis, electrical characteristics, and optical properties of core/shell silicon nanowires that are subwavelength in diameter and contain radial p-n junctions. We highlight the unique features of these nanowires, such as optical antenna effects that concentrate light and intense built-in electric fields that enable ultrafast charge-carrier separation. We advocate a paradigm in which nanowires are arranged in periodic horizontal arrays to form ultrathin devices. Unlike conventional planar silicon, nanowire structures provide the flexibility to incorporate multiple semiconductor, dielectric, and metallic materials in a single system, providing the foundation for a disruptive, unconventional solar energy technology.

Site-Selective Passivation of Defects in NiO Solar Photocathodes by Targeted Atomic Deposition

For nanomaterials, surface chemistry can dictate fundamental material properties, including charge-carrier lifetimes, doping levels, and electrical mobilities. In devices, surface defects are usually the key limiting factor for performance, particularly in solar-energy applications. Here, we develop a strategy to uniformly and selectively passivate defect sites in semiconductor nanomaterials using a vapor-phase process termed targeted atomic deposition (TAD). Because defects often consist of atomic vacancies and dangling bonds with heightened reactivity, we observe-for the widely used p-type cathode nickel oxide-that a volatile precursor such as trimethylaluminum can undergo a kinetically limited selective reaction with these sites. The TAD process eliminates all measurable defects in NiO, leading to a nearly 3-fold improvement in the performance of dye-sensitized solar cells. Our results suggest that TAD could be implemented with a range of vapor-phase precursors and be developed into a general strategy to passivate defects in zero-, one-, and two-dimensional nanomaterials.

Imaging Charge Separation and Carrier Recombination in Nanowire p-i-n Junctions Using Ultrafast Microscopy

Silicon nanowires incorporating p-type/n-type (p-n) junctions have been introduced as basic building blocks for future nanoscale electronic components. Controlling charge flow through these doped nanostructures is central to their function, yet our understanding of this process is inferred from measurements that average over entire structures or integrate over long times. Here, we have used femtosecond pump-probe microscopy to directly image the dynamics of photogenerated charge carriers in silicon nanowires encoded with p-n junctions along the growth axis. Initially, motion is dictated by carrier-carrier interactions, resulting in diffusive spreading of the neutral electron-hole cloud. Charge separation occurs at longer times as the carrier distribution reaches the edges of the depletion region, leading to a persistent electron population in the n-type region. Time-resolved visualization of the carrier dynamics yields clear, direct information on fundamental drift, diffusion, and recombination processes in these systems, providing a powerful tool for understanding and improving materials for nanotechnology.