Thomas J. Kempa

Coaxial silicon nanowires as solar cells and nanoelectronic power sources

Solar cells are attractive candidates for clean and renewable power; with miniaturization, they might also serve as integrated power sources for nanoelectronic systems. The use of nanostructures or nanostructured materials represents a general approach to reduce both cost and size and to improve efficiency in photovoltaics. Nanoparticles, nanorods and nanowires have been used to improve charge collection efficiency in polymer-blend and dye-sensitized solar cells, to demonstrate carrier multiplication, and to enable low-temperature processing of photovoltaic devices. Moreover, recent theoretical studies have indicated that coaxial nanowire structures could improve carrier collection and overall efficiency with respect to single-crystal bulk semiconductors of the same materials. However, solar cells based on hybrid nanoarchitectures suffer from relatively low efficiencies and poor stabilities. In addition, previous studies have not yet addressed their use as photovoltaic power elements in nanoelectronics. Here we report the realization of p-type/intrinsic/n-type (p-i-n) coaxial silicon nanowire solar cells. Under one solar equivalent (1-sun) illumination, the p-i-n silicon nanowire elements yield a maximum power output of up to 200 pW per nanowire device and an apparent energy conversion efficiency of up to 3.4 per cent, with stable and improved efficiencies achievable at high-flux illuminations. Furthermore, we show that individual and interconnected silicon nanowire photovoltaic elements can serve as robust power sources to drive functional nanoelectronic sensors and logic gates. These coaxial silicon nanowire photovoltaic elements provide a new nanoscale test bed for studies of photoinduced energy/charge transport and artificial photosynthesis, and might find general usage as elements for powering ultralow-power electronics and diverse nanosystems.

Single and Tandem Axial p-i-n Nanowire Photovoltaic Devices

Nanowires represent a promising class of materials for exploring new concepts in solar energy conversion. Here we report the first experimental realization of axial modulation-doped p-i-n and tandem p-i-n(+) -p(+)-i-n silicon nanowire (SiNW) photovoltaic elements. Scanning electron microscopy images of selectively etched nanowires demonstrate excellent synthetic control over doping and lengths of distinct regions in the diode structures. Current-voltage (I-V) characteristics reveal clear and reproducible diode characteristics for the p-i-n and p-n SiNW devices. Under simulated one-sun solar conditions (AM 1.5G), optimized p-i-n SiNW devices exhibited an open circuit voltage (Voc) of 0.29 V, a maximum short-circuit current density of 3.5 mA/cm(2), and a maximum efficiency of 0.5%. The response of the short-circuit current versus Voc under varying illumination intensities shows that the diode quality factor is improved from n=1.78 to n=1.28 by insertion of the i-type SiNW segment. The temperature dependence of Voc scales as -2.97 mV/K and extrapolates to the crystalline Si band gap at 0 K, which is in excellent agreement with bulk properties. Finally, a novel single SiNW tandem solar cell consisting of synthetic integration of two photovoltaic elements with an overall p-i-n(+) -p(+)-i-n structure was prepared and shown to exhibit a Voc that is on average 57% larger than that of the single p-i-n device. Fundamental studies of such well-defined nanowire photovoltaics will enable their intrinsic performance limits to be defined.

Coaxial Group III−Nitride Nanowire Photovoltaics

Coaxial core/shell nanowires represent an important class of nanoscale building blocks with substantial potential for exploring new concepts and materials for solar energy conversion. Here, we report the first experimental realization of coaxial group III-nitride nanowire photovoltaic (PV) devices, n-GaN/i-In(x)Ga(1-x)N/p-GaN, where variation of indium mole fraction is used to control the active layer band gap and hence light absorption. Current-voltage data reveal clear diode characteristics with ideality factors from 3.9 to 5.6. Electroluminescence measurements demonstrate tunable emission from 556 to 371 nm and thus confirm band gap variations in the In(x)Ga(1-x)N active layer from 2.25 to 3.34 eV as In composition is varied. Simulated one-sun AM 1.5G illumination yielded open-circuit voltages (V(oc)) from 1.0 to 2.0 V and short-circuit current densities (J(sc)) from 0.39 to 0.059 mA/cm(2) as In composition is decreased from 0.27 to 0 and a maximum efficiency of approximately 0.19%. The n-GaN/i-In(x)Ga(1-x)N/p-GaN nanowire devices are highly robust and exhibit enhanced efficiencies for concentrated solar light illuminations as well as single nanowire J(sc) values as high as 390 mA/cm(2) under intense short-wavelength illumination. The ability to rationally tune the structure and composition of these core/shell III-nitride nanowires will make them a powerful platform for exploring nanoenabled PVs in the future.

Single crystalline kinked semiconductor nanowire superstructures

The ability to control and modulate the composition1–4, doping1,3–5, crystal structure6–8 and morphology9,10 of semiconductor nanowires during the synthesis process has allowed researchers to explore various applications of nanowires11–15. However, despite advances in nanowire synthesis, progress towards the ab initio design and growth of hierarchical nanostructures has been limited. Here we demonstrate a ‘nanotectonic’ approach that provides iterative control over the nucleation and growth of nanowires and use it to grow kinked or zigzag nanowires in which the straight sections are separated by triangular joints. Moreover, the lengths of the straight sections can be controlled and the growth direction remains coherent along the nanowire. We also grow dopant-modulated structures in which specific device functions, including p-n diodes and field-effect transistors, can be precisely localized at the kinked junctions in the nanowires.

Receiving and transmitting light-like radio waves: Antenna effect in arrays of aligned carbon nanotubes

We present optical measurements of random arrays of aligned carbon nanotubes, and show that the response is consistent with conventional radio antenna theory. We first demonstrate the polarization effect, the suppression of the reflected signal when the electric field of the incoming radiation is polarized perpendicular to the nanotube axis. Next, we observe the interference colors of the reflected light from an array, and show that they result from the length matching antenna effect. This antenna effect could be used in a variety of optoelectronic devices, including THz and IR detectors.

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.

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.

Semiconductor nanowires: a platform for exploring limits and concepts for nano-enabled solar cells

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.

Design of Nanowire Optical Cavities as Efficient Photon Absorbers

Recent investigations of semiconductor nanowires have provided strong evidence for enhanced light absorption, which has been attributed to nanowire structures functioning as optical cavities. Precise synthetic control of nanowire parameters including chemical composition and morphology has also led to dramatic modulation of absorption properties. Here we report finite-difference time-domain (FDTD) simulations for silicon (Si) nanowire cavities to elucidate the key factors that determine enhanced light absorption. The FDTD simulations revealed that a crystalline Si nanowire with an embedded 20-nm-thick amorphous Si shell yields 40% enhancement of absorption as compared to a homogeneous crystalline Si nanowire, under air-mass 1.5 global solar spectrum for wavelengths between 280 and 1000 nm. Such a large enhancement in absorption results from localization of several resonant modes within the amorphous Si shell. A nanowire with a rectangular cross section exhibited enhanced absorption at specific wavelengths with respect to a hexagonal nanowire. The pronounced absorption peaks were assigned to resonant modes with a high symmetry that red-shifted with increasing size of the rectangular nanowire. We extended our studies to investigate the optical properties of single- and multilayer arrays of these horizontally oriented nanowire building blocks. The absorption efficiency of a nanowire stack increases with the number of nanowire layers and was found to be greater than that of a bulk structure or even a single nanowire of equivalent thickness. Lastly, we found that a single-layer nanowire array preserves the structured absorption spectrum of a single nanowire and ascribed this result to a diffraction effect of the periodic nanowire array. The results from these provide insight into the design of nanowire optical cavities with tunable and enhanced light absorption and thus, could help enable the development of ultrathin solar cells and other nanoscale optoelectronic devices.

Influence of iron doping on tetravalent nickel content in catalytic oxygen evolving films

Significance Iron-doped nickel oxide films are the most active nonnoble metal oxygen evolution reaction (OER) catalysts in alkaline electrolyte. Since Corrigan’s original discovery of enhanced activity with Fe doping in nickel oxides, the chemical basis for this synergy remains unclear. Recent studies suggest iron to assume a high valent oxidation state, thus promoting OER. We provide evidence for an alternative role of Fe3+ as a Lewis acid in the host nickel oxide. We observe that Fe3+ promotes the formation of Ni4+, which leads to enhanced catalytic activity. This result is consistent with Fe3+ to be one of the strongest Lewis acidic metals by any measure of Lewis acidity, including hard–soft acid base theory, metal ion pKas, and chemical inertness. Iron doping of nickel oxide films results in enhanced activity for promoting the oxygen evolution reaction (OER). Whereas this enhanced activity has been ascribed to a unique iron site within the nickel oxide matrix, we show here that Fe doping influences the Ni valency. The percent of Fe3+ doping promotes the formation of formal Ni4+, which in turn directly correlates with an enhanced activity of the catalyst in promoting OER. The role of Fe3+ is consistent with its behavior as a superior Lewis acid.