Exploiting Collective Effects to Direct Light Absorption in Natural and Artificial Light-harvesters

Photosynthesis –the conversion of sunlight to chemical energy –is fundamental for supporting life on our planet. Despite its importance, the physical principles that underpin the primary steps of photosynthesis, from photon absorption to electronic charge separation, remain to be understood in full. Electronic coherence within tightly-packed light-harvesting (LH) units or within individual reaction centers (RCs) has been recognized as an important ingredient for a complete understanding of the excitation energy transfer (EET) dynamics. However, the electronic coherence across units –RC and LH or LH and LH –has been consistently neglected as it does not play a significant role during these relatively slow transfer processes. Here, we turn our attention to the absorption process, which, as we will show, has a much shorter built-in timescale. We demonstrate that the- often overlooked- spatially extended but short-lived excitonic delocalization plays a relevant role in general photosynthetic systems. Most strikingly, we find that absorption intensity is, quite generally, redistributed from LH units to the RC, increasing the number of excitations which can effect charge separation without further transfer steps. A biomemetic nano-system is proposed which is predicted to funnel excitation to the RC-analogue, and hence is the first step towards exploiting these new design principles for efficient artificial light-harvesting.

MICROSCALE DIELECTRIC ANTI-REFLECTION COATINGS FOR PHOTOVOLTAICS

In order to power our planet for the next century, clean energy technologies need to be developed and deployed. Photovoltaic solar cells, which convert sunlight into electricity, are a clear option; however, they currently supply 0.1% of the US electricity due to the relatively high cost per Watt of generation. Thus, our goal is to create more power from a photovoltaic device, while simultaneously reducing its price. To accomplish this goal, we are creating new high efficiency anti-reflection coatings that allow more of the incident sunlight to be converted to electricity, using simple and inexpensive coating techniques that enable reduced manufacturing costs. Traditional anti-reflection coatings (consisting of thin layers of non-absorbing materials) rely on the destructive interference of the reflected light, causing more light to enter the device and subsequently get absorbed. While these coatings are used on nearly all commercial cells, they are wavelength dependent and are deposited using expensive processes that require elevated temperatures, which increase production cost and can be detrimental to some temperature sensitive solar cell materials. We are developing two new classes of anti-reflection coatings (ARCs) based on textured dielectric materials: (i) a transparent, flexible paper technology that relies on optical scattering and reduced refractive index contrast between the air and semiconductor and (ii) silicon dioxide (SiO2) nanosphere arrays that rely on collective optical resonances. Both techniques improve solar cell absorption and ultimately yield high efficiency, low cost devices. For the transparent paper-based ARCs, we have recently shown that they improve solar cell efficiencies for all angles of incident illumination reducing the need for costly tracking of the sun’s position. For a GaAs solar cell, we achieved a 24% improvement in the power conversion efficiency using this simple coating. Because the transparent paper is made from an earth abundant material (wood pulp) using an easy, inexpensive and scalable process, this type of ARC is an excellent candidate for future solar technologies. The coatings based on arrays of dielectric nanospheres also show excellent potential for inexpensive, high efficiency solar cells. The fabrication process is based on a Meyer rod rolling technique, which can be performed at room-temperature and applied to mass production, yielding a scalable and inexpensive manufacturing process. The deposited monolayer of SiO2 nanospheres, having a diameter of 500 nm on a bare Si wafer, leads to a significant increase in light absorption and a higher expected current density based on initial simulations, on the order of 15-20%. With application on a Si solar cell containing a traditional anti-reflection coating (Si3N4 thin-film), an additional increase in the spectral current density is observed, 5% beyond what a typical commercial device would achieve. Due to the coupling between the spheres originated from Whispering Gallery Modes (WGMs) inside each nanosphere, the incident light is strongly coupled into the high-index absorbing material, leading to increased light absorption. Furthermore, the SiO2 nanospheres scatter and diffract light in such a way that both the optical and electrical properties of the device have little dependence on incident angle, eliminating the need for solar tracking. Because the layer can be made with an easy, inexpensive, and scalable process, this anti-reflection coating is also an excellent candidate for replacing conventional technologies relying on complicated and expensive processes.

In Situ Characterization of Optical Absorption by Carbonaceous Aerosols: Calibration and Measurement

Light absorption by aerosols has a great impact on climate change. A Photoacoustic spectrometer (PA) coupled with aerosol-based classification techniques represents an in situ method that can quantify the light absorption by aerosols in a real time, yet significant differences have been reported using this method versus filter based methods or the so-called difference method based upon light extinction and light scattering measurements. This dissertation focuses on developing calibration techniques for instruments used in measuring the light absorption cross section, including both particle diameter measurements by the differential mobility analyzer (DMA) and light absorption measurements by PA. Appropriate reference materials were explored for the calibration/validation of both measurements. The light absorption of carbonaceous aerosols was also investigated to provide fundamental understanding to the absorption mechanism. The first topic of interest in this dissertation is the development of calibration nanoparticles. In this study, bionanoparticles were confirmed to be a promising reference material for particle diameter as well as ion-mobility. Experimentally, bionanoparticles demonstrated outstanding homogeneity in mobility compared to currently used calibration particles. A numerical method was developed to calculate the true distribution and to explain the broadening of measured distribution. The high stability of bionanoparticles was also confirmed. For PA measurement, three aerosol with spherical or near spherical shapes were investigated as possible candidates for a reference standard: C60, copper and silver. Comparisons were made between experimental photoacoustic absorption data with Mie theory calculations. This resulted in the identification of C60 particles with a mobility diameter of 150 nm to 400 nm as an absorbing standard at wavelengths of 405 nm and 660 nm. Copper particles with a mobility diameter of 80 nm to 300 nm are also shown to be a promising reference candidate at wavelength of 405 nm. The second topic of this dissertation focuses on the investigation of light absorption by carbonaceous particles using PA. Optical absorption spectra of size and mass selected laboratory generated aerosols consisting of black carbon (BC), BC with non-absorbing coating (ammonium sulfate and sodium chloride) and BC with a weakly absorbing coating (brown carbon derived from humic acid) were measured across the visible to near-IR (500 nm to 840 nm). The manner in which BC mixed with each coating material was investigated. The absorption enhancement of BC was determined to be wavelength dependent. Optical absorption spectra were also taken for size and mass selected smoldering smoke produced from six types of commonly seen wood in a laboratory scale apparatus.

Large-Scale Controlled-Condition Experiment to Evaluate Light Weight Deflectometers for Modulus Determination and Compaction Quality Assurance of Unbound Pavement Materials

Compaction control using lightweight deflectometers (LWD) is currently being evaluated in several states and countries and fully implemented for pavement construction quality assurance (QA) by a few. Broader implementation has been hampered by the lack of a widely recognized standard for interpreting the load and deflection data obtained during construction QA testing. More specifically, reliable and practical procedures are required for relating these measurements to the fundamental material property—modulus—used in pavement design. This study presents a unique set of data and analyses for three different LWDs on a large-scale controlled-condition experiment. Three 4.5x4.5 m2 test pits were designed and constructed at target moisture and density conditions simulating acceptable and unacceptable construction quality. LWD testing was performed on the constructed layers along with static plate loading testing, conventional nuclear gauge moisture-density testing, and non-nuclear gravimetric and volumetric water content measurements. Additional material was collected for routine and exploratory tests in the laboratory. These included grain size distributions, soil classification, moisture-density relations, resilient modulus testing at optimum and field conditions, and an advanced experiment of LWD testing on top of the Proctor compaction mold. This unique large-scale controlled-condition experiment provides an excellent high quality resource of data that can be used by future researchers to find a rigorous, theoretically sound, and straightforward technique for standardizing LWD determination of modulus and construction QA for unbound pavement materials.

Nonlinear Optics and Carrier Dynamics in Nanostructured and Two-Dimensional Materials

Understanding and measuring the interaction of light with sub-wavelength structures and atomically thin materials is of critical importance for the development of next generation photonic devices.  One approach to achieve the desired optical properties in a material is to manipulate its mesoscopic structure or its composition in order to affect the properties of the light-matter interaction.  There has been tremendous recent interest in so called two-dimensional materials, consisting of only a single to a few layers of atoms arranged in a planar sheet.  These materials have demonstrated great promise as a platform for studying unique phenomena arising from the low-dimensionality of the material and for developing new types of devices based on these effects.  A thorough investigation of the optical and electronic properties of these new materials is essential to realizing their potential.  In this work we present studies that explore the nonlinear optical properties and carrier dynamics in nanoporous silicon waveguides, two-dimensional graphite (graphene), and atomically thin black phosphorus. We first present an investigation of the nonlinear response of nanoporous silicon optical waveguides using a novel pump-probe method. A two-frequency heterodyne technique is developed in order to measure the pump-induced transient change in phase and intensity in a single measurement. The experimental data reveal a characteristic material response time and temporally resolved intensity and phase behavior matching a physical model dominated by free-carrier effects that are significantly stronger and faster than those observed in traditional silicon-based waveguides.  These results shed light on the large optical nonlinearity observed in nanoporous silicon and demonstrate a new measurement technique for heterodyne pump-probe spectroscopy. Next we explore the optical properties of low-doped graphene in the terahertz spectral regime, where both intraband and interband effects play a significant role. Probing the graphene at intermediate photon energies enables the investigation of the nonlinear optical properties in the graphene as its electron system is heated by the intense pump pulse. By simultaneously measuring the reflected and transmitted terahertz light, a precise determination of the pump-induced change in absorption can be made. We observe that as the intensity of the terahertz radiation is increased, the optical properties of the graphene change from interband, semiconductor-like absorption, to a more metallic behavior with increased intraband processes. This transition reveals itself in our measurements as an increase in the terahertz transmission through the graphene at low fluence, followed by a decrease in transmission and the onset of a large, photo-induced reflection as fluence is increased.  A hybrid optical-thermodynamic model successfully describes our observations and predicts this transition will persist across mid- and far-infrared frequencies.  This study further demonstrates the important role that reflection plays since the absorption saturation intensity (an important figure of merit for graphene-based saturable absorbers) can be underestimated if only the transmitted light is considered. These findings are expected to contribute to the development of new optoelectronic devices designed to operate in the mid- and far-infrared frequency range.  Lastly we discuss recent work with black phosphorus, a two-dimensional material that has recently attracted interest due to its high mobility and direct, configurable band gap (300 meV to 2eV), depending on the number of atomic layers comprising the sample. In this work we examine the pump-induced change in optical transmission of mechanically exfoliated black phosphorus flakes using a two-color optical pump-probe measurement. The time-resolved data reveal a fast pump-induced transparency accompanied by a slower absorption that we attribute to Pauli blocking and free-carrier absorption, respectively. Polarization studies show that these effects are also highly anisotropic - underscoring the importance of crystal orientation in the design of optical devices based on this material. We conclude our discussion of black phosphorus with a study that employs this material as the active element in a photoconductive detector capable of gigahertz class detection at room temperature for mid-infrared frequencies.

EXPERIMENTAL DEMONSTRATION OF LIGHT TRAPPING AND INTERNAL LIGHT SCATTERING IN SOLAR CELLS

Renewable energy technologies have long-term economic and environmental advantages over fossil fuels, and solar power is the most abundant renewable resource, supplying 120 PW over earth’s surface. In recent years the cost of photovoltaic modules has reached grid parity in many areas of the world, including much of the USA. A combination of economic and environmental factors has encouraged the adoption of solar technology and led to an annual growth rate in photovoltaic capacity of 76% in the US between 2010 and 2014. Despite the enormous growth of the solar energy industry, commercial unit efficiencies are still far below their theoretical limits. A push for thinner cells may reduce device cost and could potentially increase device performance. Fabricating thinner cells reduces bulk recombination, but at the cost of absorbing less light. This tradeoff generally benefits thinner devices due to reduced recombination. The effect continues up to a maximum efficiency where the benefit of reduced recombination is overwhelmed by the suppressed absorption. Light trapping allows the solar cell to circumvent this limitation and realize further performance gains (as well as continue cost reduction) from decreasing the device thickness. This thesis presents several advances in experimental characterization, theoretical modeling, and device applications for light trapping in thin-film solar cells. We begin by introducing light trapping strategies and discuss theoretical limits of light trapping in solar cells. This is followed by an overview of the equipment developed for light trapping characterization. Next we discuss our recent work measuring internal light scattering and a new model of scattering to predict the effects of dielectric nanoparticle back scatterers on thin-film device absorption. The new model is extended and generalized to arbitrary stacks of stratified media containing scattering structures. Finally, we investigate an application of these techniques using polymer dispersed liquid crystals to produce switchable solar windows. We show that these devices have the potential for self-powering.