Design strategies for ultra-high efficiency photovoltaics

While concentrator photovoltaic cells have shown significant improvements in efficiency in the past ten years, once these cells are integrated into concentrating optics, connected to a power conditioning system and deployed in the field, the overall module efficiency drops to only 34 to 36%. This efficiency is impressive compared to conventional flat plate modules, but it is far short of the theoretical limits for solar energy conversion. Designing a system capable of achieving ultra high efficiency of 50% or greater cannot be achieved by refinement and iteration of current design approaches.

This thesis takes a systems approach to designing a photovoltaic system capable of 50% efficient performance using conventional diode-based solar cells. The effort began with an exploration of the limiting efficiency of spectrum splitting ensembles with 2 to 20 sub cells in different electrical configurations. Incorporating realistic non-ideal performance with the computationally simple detailed balance approach resulted in practical limits that are useful to identify specific cell performance requirements. This effort quantified the relative benefit of additional cells and concentration for system efficiency, which will help in designing practical optical systems.

Efforts to improve the quality of the solar cells themselves focused on the development of tunable lattice constant epitaxial templates. Initially intended to enable lattice matched multijunction solar cells, these templates would enable increased flexibility in band gap selection for spectrum splitting ensembles and enhanced radiative quality relative to metamorphic growth. The III-V material family is commonly used for multijunction solar cells both for its high radiative quality and for the ease of integrating multiple band gaps into one monolithic growth. The band gap flexibility is limited by the lattice constant of available growth templates. The virtual substrate consists of a thin III-V film with the desired lattice constant. The film is grown strained on an available wafer substrate, but the thickness is below the dislocation nucleation threshold. By removing the film from the growth substrate, allowing the strain to relax elastically, and bonding it to a supportive handle, a template with the desired lattice constant is formed. Experimental efforts towards this structure and initial proof of concept are presented.

Cells with high radiative quality present the opportunity to recover a large amount of their radiative losses if they are incorporated in an ensemble that couples emission from one cell to another. This effect is well known, but has been explored previously in the context of sub cells that independently operate at their maximum power point. This analysis explicitly accounts for the system interaction and identifies ways to enhance overall performance by operating some cells in an ensemble at voltages that reduce the power converted in the individual cell. Series connected multijunctions, which by their nature facilitate strong optical coupling between sub-cells, are reoptimized with substantial performance benefit.

Photovoltaic efficiency is usually measured relative to a standard incident spectrum to allow comparison between systems. Deployed in the field systems may differ in energy production due to sensitivity to changes in the spectrum. The series connection constraint in particular causes system efficiency to decrease as the incident spectrum deviates from the standard spectral composition. This thesis performs a case study comparing performance of systems over a year at a particular location to identify the energy production penalty caused by series connection relative to independent electrical connection.

Investigations of the conductor-semiconductor interface

I. Schottky barriers produced by polymeric sulfur nitride, (SN)_x, on nine common III-V and II-VI compound semiconductors are compared to barriers formed by Au. The conductor (SN)_x produces significantly higher barriers to n-type semiconductors and lower barriers to p-type semiconductors than Au, the most electronegative elemental metal. The barrier height improvement, defined as ɸ(SN)_x - ɸ(Au), is smaller on covalent semiconductors than on ionic semiconductors; (SN)x barriers follow the ionic-covalent transition. Details of (SN)_x film deposition, samples preparation, and barrier height measurements are described.

II. The rate of dissolution of amorphous Si into solid Al is measured. The rate of movement of the amorphous Si/Al interface is found to be much faster than predicted by a simple model of the transport of Si through Al. This result is related to defects in the growth of epitaxial Si using the solid phase epitaxy process.

Scalable Methods for Deterministic Integration of Quantum Emitters in Photonic Crystal Cavities

We investigated four unique methods for achieving scalable, deterministic integration of quantum emitters into ultra-high Q{V photonic crystal cavities, including selective area heteroepitaxy, engineered photoemission from silicon nanostructures, wafer bonding and dimensional reduction of III-V quantum wells, and cavity-enhanced optical trapping. In these areas, we were able to demonstrate site-selective heteroepitaxy, size-tunable photoluminescence from silicon nanostructures, Purcell modification of QW emission spectra, and limits of cavity-enhanced optical trapping designs which exceed any reports in the literature and suggest the feasibility of capturing- and detecting nanostructures with dimensions below 10 nm. In addition to process scalability and the requirement for achieving accurate spectral- and spatial overlap between the emitter and cavity, these techniques paid specific attention to the ability to separate the cavity and emitter material systems in order to allow optimal selection of these independently, and eventually enable monolithic integration with other photonic and electronic circuitry.

We also developed an analytic photonic crystal design process yielding optimized cavity tapers with minimal computational effort, and reported on a general cavity modification which exhibits improved fabrication tolerance by relying exclusively on positional- rather than dimensional tapering. We compared several experimental coupling techniques for device characterization. Significant efforts were devoted to optimizing cavity fabrication, including the use of atomic layer deposition to improve surface quality, exploration into factors affecting the design fracturing, and automated analysis of SEM images. Using optimized fabrication procedures, we experimentally demonstrated 1D photonic crystal nanobeam cavities exhibiting the highest Q/V reported on substrate. Finally, we analyzed the bistable behavior of the devices to quantify the nonlinear optical response of our cavities.

Paths Towards High Efficiency Silicon Photovoltaics

While photovoltaics hold much promise as a sustainable electricity source, continued cost reduction is necessary to continue the current growth in deployment. A promising path to continuing to reduce total system cost is by increasing device efficiency. This thesis explores several silicon-based photovoltaic technologies with the potential to reach high power conversion efficiencies. Silicon microwire arrays, formed by joining millions of micron diameter wires together, were developed as a low cost, low efficiency solar technology. The feasibility of transitioning this to a high efficiency technology was explored. In order to achieve high efficiency, high quality silicon material must be used. Lifetimes and diffusion lengths in these wires were measured and the action of various surface passivation treatments studied. While long lifetimes were not achieved, strong inversion at the silicon / hydrofluoric acid interface was measured, which is important for understanding a common measurement used in solar materials characterization.

Cryogenic deep reactive ion etching was then explored as a method for fabricating high quality wires and improved lifetimes were measured. As another way to reach high efficiency, growth of silicon-germanium alloy wires was explored as a substrate for a III-V on Si tandem device. Patterned arrays of wires with up to 12% germanium incorporation were grown. This alloy is more closely lattice matched to GaP than silicon and allows for improvements in III-V integration on silicon.

Heterojunctions of silicon are another promising path towards achieving high efficiency devices. The GaP/Si heterointerface and properties of GaP grown on silicon were studied. Additionally, a substrate removal process was developed which allows the formation of high quality free standing GaP films and has wide applications in the field of optics.

Finally, the effect of defects at the interface of the amorphous silicon heterojuction cell was studied. Excellent voltages, and thus efficiencies, are achievable with this system, but the voltage is very sensitive to growth conditions. We directly measured lateral transport lengths at the heterointerface on the order of tens to hundreds of microns, which allows carriers to travel towards any defects that are present and recombine. This measurement adds to the understanding of these types of high efficiency devices and may aid in future device design.

Structural change of laser-irradiated Ge2Sb2Te5 films studied by electrical property measurement

Sheet resistance of laser-irradiated Ge2Sb2Te5 thin films prepared by magnetron sputtering was measured by the four-point probe method. With increasing laser power the sheet resistance undergoes an abrupt drop from 10(7) to 10(3) Omega/square at about 580 mW. The abrupt drop in resistance is due to the structural change from amorphous to crystalline state as revealed by X-ray diffraction (XRD) study of the samples around the abrupt change point. Crystallized dots were also formed in the amorphous Ge2Sb2Te5 films by focused short pulse laser-irradiated, the resistivities at the crystallized dots and the non-crystallized area are 3.375 x 10(-3) and 2.725 Omega m, sheet resistance is 3.37 x 10(4) and 2.725 x 10(7) Omega/square respectively, deduced from the I-V Curves that is obtained by conductive atomic force microscope (C-AFM). (C) 2008 Elsevier B.V. All rights reserved.

Strong plasmonic enhancement of photovoltage in graphene.

From the wide spectrum of potential applications of graphene, ranging from transistors and chemical sensors to nanoelectromechanical devices and composites, the field of photonics and optoelectronics is believed to be one of the most promising. Indeed, graphene's suitability for high-speed photodetection was demonstrated in an optical communication link operating at 10 Gbit s(-1). However, the low responsivity of graphene-based photodetectors compared with traditional III-V-based ones is a potential drawback. Here we show that, by combining graphene with plasmonic nanostructures, the efficiency of graphene-based photodetectors can be increased by up to 20 times, because of efficient field concentration in the area of a p-n junction. Additionally, wavelength and polarization selectivity can be achieved by employing nanostructures of different geometries.

Strong plasmonic enhancement of photovoltage in graphene

From the wide spectrum of potential applications of graphene, ranging from transistors and chemical sensors to nanoelectromechanical devices and composites, the field of photonics and optoelectronics is believed to be one of the most promising. Indeed, graphene's suitability for high-speed photodetection was demonstrated in an optical communication link operating at 10 Gbit s 1. However, the low responsivity of graphene-based photodetectors compared with traditional III-V-based ones is a potential drawback. Here we show that, by combining graphene with plasmonic nanostructures, the efficiency of graphene-based photodetectors can be increased by up to 20 times, because of efficient field concentration in the area of a p-n junction. Additionally, wavelength and polarization selectivity can be achieved by employing nanostructures of different geometries. © 2011 Macmillan Publishers Limited. All rights reserved.

Electronic properties of GaAs, InAs and InP nanowires studied by terahertz spectroscopy.

We have performed a comparative study of ultrafast charge carrier dynamics in a range of III-V nanowires using optical pump-terahertz probe spectroscopy. This versatile technique allows measurement of important parameters for device applications, including carrier lifetimes, surface recombination velocities, carrier mobilities and donor doping levels. GaAs, InAs and InP nanowires of varying diameters were measured. For all samples, the electronic response was dominated by a pronounced surface plasmon mode. Of the three nanowire materials, InAs nanowires exhibited the highest electron mobilities of 6000 cm² V⁻¹ s⁻¹, which highlights their potential for high mobility applications, such as field effect transistors. InP nanowires exhibited the longest carrier lifetimes and the lowest surface recombination velocity of 170 cm s⁻¹. This very low surface recombination velocity makes InP nanowires suitable for applications where carrier lifetime is crucial, such as in photovoltaics. In contrast, the carrier lifetimes in GaAs nanowires were extremely short, of the order of picoseconds, due to the high surface recombination velocity, which was measured as 5.4 × 10⁵ cm s⁻¹. These findings will assist in the choice of nanowires for different applications, and identify the challenges in producing nanowires suitable for future electronic and optoelectronic devices.

Noncontact measurement of charge carrier lifetime and mobility in GaN nanowires

The first noncontact photoconductivity measurements of gallium nitride nanowires (NWs) are presented, revealing a high crystallographic and optoelectronic quality achieved by use of catalyst-free molecular beam epitaxy. In comparison with bulk material, the NWs exhibit a long conductivity lifetime (>2 ns) and a high mobility (820 ± 120 cm 2/(V s)). This is due to the weak influence of surface traps with respect to other III-V semiconducting NWs and to the favorable crystalline structure of the NWs achieved via strain-relieved growth. © 2012 American Chemical Society.

Defect-free GaAs/AlGaAs Core-shell nanowires on Si substrates

We report straight and vertically aligned defect-free GaAs nanowires grown on Si(111) substrates by metal-organic chemical vapor deposition. By deposition of thin GaAs buffer layers on Si substrates, these nanowires could be grown on the buffer layers with much less stringent conditions as otherwise imposed by epitaxy of III-V compounds on Si. Also, crystal-defect-free GaAs nanowires were grown by using either a two-temperature growth mode consisting of a short initial nucleation step under higher temperature followed by subsequent growth under lower temperature or a rapid growth rate mode with high source flow rate. These two growth modes not only eliminated planar crystallographic defects but also significantly reduced tapering. Core-shell GaAs-AlGaAs nanowires grown by the two-temperature growth mode showed improved optical properties with strong photoluminescence and long carrier life times. © 2011 American Chemical Society.

Growth of straight InAs-on-GaAs nanowire heterostructures.

One of the main motivations for the great interest in semiconductor nanowires is the possibility of easily growing advanced heterostructures that might be difficult or even impossible to achieve in thin films. For III-V semiconductor nanowires, axial heterostructures with an interchange of the group III element typically grow straight in only one interface direction. In the case of InAs-GaAs heterostructures, straight nanowire growth has been demonstrated for growth of GaAs on top of InAs, but so far never in the other direction. In this article, we demonstrate the growth of straight axial heterostructures of InAs on top of GaAs. The heterostructure interface is sharp and we observe a dependence on growth parameters closely related to crystal structure as well as a diameter dependence on straight nanowire growth. The results are discussed by means of accurate first principles calculations of the interfacial energies. In addition, the role of the gold seed particle, the effect of its composition at different stages during growth, and its size are discussed in relation to the results observed.

High purity GaAs nanowires free of planar defects: Growth and characterization

We investigate how to tailor the structural, crystallographic and optical properties of GaAs nanowires. Nanowires were grown by Au nanoparticle-catalyzed metalorganic chemical vapor deposition. A high arsine flow rate, that is, a high ratio of group V to group III precursors, imparts significant advantages. It dramatically reduces planar crystallographic defects and reduces intrinsic carbon dopant incorporation. Increasing V/III ratio further, however, instigates nanowire kinking and increases nanowire tapering. By choosing an intermediate V/III ratio we achieve uniform, vertically aligned GaAs nanowires, free of planar crystallographic defects, with excellent optical properties and high purity. These findings will greatly assist the development of future GaAs nanowire-based electronic and optoelectronic devices, and are expected to be more broadly relevant to the rational synthesis of other III-V nanowires. © 2008 WILEY-VCH Verlag GmbH & Co. KGaA.

Quantum dots and nanowires for photonics applications

We review our results on integrated photonic devices fabricated using InGaAs quantum-dots. Selective-area metal organic chemical vapor deposition (MOCVD) is used to grow the active region with quantum dots emitting at different wavelengths for fabrication of the integrated devices. We will also review the structural and optical properties of III-V nanowires, and axial and radial nanowire heterostructures grown by MOCVD. In addition to binary nanowires, such as GaAs, InAs, and InP, we have demonstrated ternary InGaAs and AlGaAs nanowires. Core-shell nanowires consisting of GaAs cores with AlGaAs shells, and core-multishell nanowires with several alternating shells of AlGaAs and GaAs, exhibit strong photoluminescence. Axial segments of InGaAs have been incorporated within GaAs nanowires to form GaAs/InGaAs nanowire superlattices.

Low-cost high-efficiency GaN LED on large-area si substrate

The use of large size Si substrates for epitaxy of nitride light emitting diode (LED) structures has attracted great interest because Si wafers are readily available in large diameter at low cost. In addition, such wafers are compatible with existing processing lines for the 6-inch and larger wafer sizes commonly used in the electronics industry. With the development of various methods to avoid wafer cracking and reduce the defect density, the performance of GaN-based LED and electronic devices has been greatly improved. In this paper, we review our methods of growing crack-free InGaN-GaN multiple quantum well (MQW) LED structures of high crystalline quality on Si(111) substrates. The performance of processed LED devices and its dependence on the threading dislocation density were studied. Full wafer-level LED processing using a conventional 6-inch III-V processing line is also presented, demonstrating the great advantage of using large-size Si substrates for mass production of GaN LED devices.

Bryodrilus fuscistriatus, a new enchytraeid species (Oligochaeta : Enchytraeidae) from northeastern China

Bryodrilus fuscistriatus, a new enchytraeid species from Mt. Changbaishan, Jilin Province, north-eastern China, is described. It is characterized by brown epidermal glands, 7 pairs of preclitellar nephridia, poorly-developed clitellar glands, spermatheca with 2 sessile globular diverticula, and a long sperm funnel with a very broad collar. It is similar to the Alaskan B. tunicatus Dozsa-Farkas & Christensen, 2002 in possessing two diverticula in the spermathecal ampulla and the origin of the dorsal vessel, and the Chinese B. longifistulatus and B. macrotheca Xie et al., 2000c in body size, long sperm funnel and undeveloped clitellar glands, but it differs from B. tunicatus by the presence of brown-striped epidermal gland cells in III-V, a poorly-elevated clitellum, the absence of copulatory glands in XIII-XIV, the regular outline of coelomocytes, and 7 pairs of preclitellar nephridia; from B. longifistulatus and B. macrotheca by the shape of spermatheca, the color of epidermal gland cells, the position of the first pair nephridia, and the origin of dorsal vessel.