Solution deposition of thin film photovoltaic materials leads to large variations in the morphological and chemical compositions of the film. In order to improve device functionality, it is important to understand how morphology and chemical composition affects charge generation, separation, and collection. This PhD work will first study bulk methods in order to characterize materials in solution and films. The results are then correlated with microscopy studies examining morphology. Other methods used in this PhD work will directly couple spectra and microscopy. Microscopic regions of such films and devices can be illuminated using scanning confocal microscopy or near-field scanning optical microscopy (NSOM), which allows for one to directly probe regions of the film at or below the optical diffraction limit. By scanning the sample over a fixed laser spot we can simultaneously create image maps of the topographical, electrical and optical properties. This technique, known as laser beam induced current (LBIC) allows one to directly probe a local area of a device with 100-300nm resolution. Along with bulk device efficiency studies, near field and confocal data of inorganic and organic materials are investigated. These include devices fabricated with a blend of P3HT (poly[3-hexylthiophene]) and perylene diimide derivatives, and Cu(InxGa1-x)Se2 [CIGS] nanoparticle devices. Finally, we use a new device architecture, a lateral organic photovoltaic (LOPV) in order to spatially resolve transport in functional organic devices. / text

Colloidal nanocrystals with optical properties in the near-infrared (NIR) are of interest for many applications such as photovoltaic (PV) energy conversion, bioimaging, and therapeutics. For PVs and other electronic devices, challenges in using colloidal nanomaterials often deal with the surfaces. Because of the high surface-to-volume ratio of small nanocrystals, surfaces and interfaces play an enhanced role in the properties of nanocrystal films and devices. Organic ligand-capped CuInSe2 (CIS) and Cu(InXGa1-X)Se2 (CIGS) nanocrystals were synthesized and used as the absorber layer in prototype solar cells. By fabricating devices from spray-coated CuInSe nanocrystals under ambient conditions, solar-to-electric power conversion efficiencies as high as 3.1% were achieved. Many treatments of the nanocrystal films were explored. Although some treatments increased the conductivity of the nanocrystal films, the best devices were from untreated CIS films. By modifying the reaction chemistry, quantum-confined CuInSeXS2-X (CISS) nanocrystals were produced. The potential of the CISS nanocrystals for targeted bioimaging was demonstrated via oral delivery to mice and imaging of nanocrystal fluorescence. The size-dependent photoluminescence of Si nanocrystals was measured. Si nanocrystals supported on graphene were characterized by conventional transmission electron microscopy and spherical aberration (Cs)-corrected scanning transmission electron microscopy (STEM). Enhanced imaging contrast and resolution was achieved by using Cs-corrected STEM with a graphene support. In addition, clear imaging of defects and the organic-inorganic interface was enabled by utilizing this technique. / text

Conjugated polymers hold tremendous potential as low-cost, solution processable materials for electronic applications such organic light-emitting diodes and photovoltaics. While the concerted efforts of many research groups have improved the performance of organic electronic devices to near-relevant levels for commercial exploitation over the last decade, the overall performance of organic light-emitting diode and organic photovoltaic devices still lags behind that of their traditional, inorganic counterparts. Realizing the full potential of organic electronics will require a comprehensive, molecular-level understanding of conjugated polymer photophysics. Studying pure, well-defined, and reproducible conjugated polymer materials should enable these efforts; unfortunately, conjugated polymers are typically synthesized by metal-catalyzed step-growth polycondensation reactions that do not allow for rigorous control over polymer molecular weight or molecular weight distribution (i.e., dispersity). Chain-growth syntheses of conjugated polymers would not only allow for precise control over the aforementioned polymer metrics such as molecular weight and dispersity, but could also potentially create new applications by enabling the preparation of more advanced macromolecular structures such as block copolymers and surface grafted polymers. Our efforts toward realizing these goals as well as toward exploiting chain-growth methodologies to better understand fundamental conjugated polymer photophysics and self-assembly will be presented. / text

Semiconductor nanocrystal-based photovoltaics are an interesting new technology with the potential to achieve high efficiencies at low cost. CuInSe2 nanocrystals have been synthesized in solution using arrested precipitation and dispersed in solvent to form a “solar ink”. The inks have been deposited under ambient conditions to fabricate photovoltaic devices with efficiency up to 3%. Despite the low cost spray coating deposition technique, device efficiencies remain too low for commercialization. Higher efficiencies up to 7% have been achieved using a high temperature selenization process, but this process is too expensive. New nanocrystal film treatment processes are necessary which can improve the device efficiency at low cost. To this end, CuInSe2 nanocrystals were synthesized using a diphenyl phosphine:Se precursor which allows for precise control over the nanocrystal size. The size is controlled by changing the temperature of the reaction. The smallest size nanocrystals demonstrated extremely high device open circuit voltage. Ligand exchange procedures were used to replace the insulating oleylamine capping ligand used during synthesis with more conductive halide ions or inorganic chalcogenidometallate cluster (ChaM) ligands. These ligands led to improved charge transport in the nanocrystal films. A high-intensity pulsed light processing technique known as photonic curing was used which allows for high temperature sintering of nanocrystal films on temperature-sensitive substrates. High energy pulses cause the nanocrystals to sinter into large grains, primarily through melting and resolidification. The choice of metal back contact has a dramatic effect on the final film morphology, with Au and MoSe2 back contacts providing much better adhesion with the CuInSe2 than Mo back contacts. Nanocrystal sintering without melting can be achieved by replacing the oleylamine ligands with ChaM ligands prior to photonic curing. Low energy photonic curing pulses vaporize the oleylamine ligands without inducing sintering or grain growth. This greatly improved nanocrystal coupling and interparticle charge transport. Multiexcitons were successfully extracted from these nanocrystal films and external quantum efficiencies over 100% were observed. Transient absorption spectroscopy was used to study the multiexciton generation process in CuInSe2 nanocrystal films and colloidal suspensions. The multiexciton generation efficiency, threshold, and Auger lifetimes for CuInSe2 compare well with other nanocrystal materials. / text

Donor-acceptor and thiophene based π-conjugated molecules and polymers, along with fullerene derivatives, are extensively used active components in the photoactive layer of organic photovoltaic devices. In this dissertation, we make use of several computational methodologies to investigate structure-property relationships of these organic systems in their molecular forms. We begin with an overview of the field of organic photovoltaics and some of the important problems in organic solar cells that are currently being investigated. This is then followed by a brief review of the electronic-structure methods (e.g. Hartree-Fock theory, Density Functional Theory, and Time-dependent Density Functional Theory) that are employed. We then present the main results of the dissertation. Chapter 3 provides a broad overview on how changes to the donor-acceptor copolymer chemical structure impacts its intrinsic geometric, electronic, and optical properties. Chapter 4 focuses on the characterization of the lowest excited-states and optical absorption spectra in donor-acceptor copolymers. In Chapter 5, we investigate the effects of alkyl side-chain placements in the π-conjugated backbone of oligothiophenes and how that impacts their intramolecular properties as well as the oligomer:fullerene interfacial interactions. Chapter 6 presents our investigation on the role of oligomer:fullerene configuration and reorganization energy on exciton-dissociation and charge-recombination processes. Finally, a synopsis of the work and further considerations are presented in Chapter 7.

The photovoltaic industry provides a pathway to allow renewable energy to meet world wide consumer energy needs. Past and present research and development on silicon based solar cells have helped make them the dominant player in the photovoltaic industry accounting for over 75% in 2005 as accounted by the US Department of Energy. One of the current technological problems is to identify and eliminate sources of mechanical defects such as thermo-elastic stress and cracks leading to the loss of wafer integrity and ultimately breakage of as-grown and processed Si wafers and cells.The RUV method, developed at the University of South Florida, enables fast and accurate crack detection with simple criteria for wafer rejection from solar cell production lines. The RUV system relies on variation of modal vibration characteristics due to physical variations in the wafers caused by cracks. Ultrasonic vibrations are introduced into the wafer using a vacuum coupled transducer and received by an acoustic probe mounted along the periphery of the wafer. Cracks are detected by monitoring shifts in the resonance peak's frequency, bandwidth, and amplitude. In Cz-Si wafers it has been shown that increased crack length leads to a decrease in peak frequency and an increase in peak bandwidth and decreasing peak amplitude. Minimum crack length sensitivity is related to the uniformity of the RUV parameters from wafer to wafer within a batch as well as system characteristics. Typically the RUV system is capable of detecting sub-millimeter length cracks. The use of auto loading and unloading allows the RUV system to achieve mass production level speeds of approximately two seconds per wafer. The RUV system has been successful in detecting cracks in single crystalline and multi-crystalline silicon wafers. Further development of the RUV system would solidify its place in manufacturing plants for non-destructive crack detection in PV cells.The contributing work of the author toward the further development of the RUV crack detection method will be examined in this thesis.

To sustain future civilization, the development of alternative clean-energy technologies to replace fossil fuels has become one of the most crucial and challenging problems of the last few decades. The thin film solar cell is one of the major photovoltaic technologies that is promising for renewable energy. The current commercial thin film PV technologies are based on \(Cu(In,Ga)Se_2\) and CdTe. Despite their success in reducing the module cost below $1/Wp, these absorber materials face limitations due to their use of scarce (In and Te) and toxic (Cd) elements. One promising candidate for an alternative absorber material is tin monosulfide (SnS). Composed of cheap, non-toxic and earth-abundant elemental constituents, SnS can potentially provide inexpensive PV modules to reach the global energy demand in TW levels. Because of the high volatility of sulfur and various oxidation states of tin, non- stoichiometric chemical composition, traces of other phases \((i.e. Sn, Sn_2S_3, and SnS_2)\), and elemental impurities (e.g. oxygen) are usually observed in SnS films obtained from various reported deposition techniques. First, we present a process to prepare pure, stoichiometric, single-phase SnS films from atomic layer deposition (ALD). The as-deposited SnS films exhibit several attractive properties, including suitable energy band gaps \((E_{g,}~ 1.1 – 1.3 eV)\), a large absorption coefficient \((\alpha > 10^4 cm^{˗1})\), and a proper carrier concentration \(([p] ~ 10^{15} – 10^{16} cm^{˗3})\). Then, heterojunction solar cells were fabricated from p-type SnS and n-type zinc oxysulfide (Zn(O,S)). A record high active-area efficiency of 2.46 % was achieved via conduction band offset engineering by varying the oxygen-to-sulfur ratio in Zn(O,S). Finally, we address two approaches potentially used for improving a device efficiency of the SnS solar cell. First, via doping to create an n-type SnS, a p-n homojunction device could be made. We present the processes and the results of doping SnS films with antimony and chlorine, potential n-type dopants. Second, by post-deposition heat treatment, an improvement in the transport properties of SnS film can be achieved. We discuss the effect of temperature and an annealing ambient \((N_2, H_2S\), and sulfur) on grain growth and the electrical properties of annealed SnS films. / Chemistry and Chemical Biology

Tin(II) sulfide (SnS) is an earth-abundant, inexpensive, and non-toxic absorber material for thin film solar cells. SnS films are deposited by atomic layer deposition (ALD) through the reaction of a tin precursor, bis(N,N'-diisopropylacetamidinato)tin(II), and hydrogen sulfide. The SnS films demonstrate excellent surface morphology, crystal structure, phase purity, stoichiometry, elemental purity, and optical and electrical properties. / Engineering and Applied Sciences

The widespread adoption of hybrid organic-inorganic solar cells has been delayed by low performance. Improving performance requires a firm understanding of how to optimize both material composition and processing parameters. In this thesis, we examine processing parameters that include solution composition, annealing temperature, and the rates of spin casting and evaporative coating. We also find that the optimal weight ratio for the active layer of a ZnO:P3HT solar cell is 40 wt. % ZnO. / text

Energetics, charge selectivity and interfacial charge transfer kinetics affect the efficiency of solar electric energy conversion and solar photochemical formation of fuels. The research described herein focuses on understanding and controlling the energetics, charge selectivity, and interfacial charge transfer processes in organic photovoltaics, as well as new generation semiconductor-semiconductor and metal-semiconductor heterostructured nanorods (NRs) as photocatalysts. Waveguide and transmission based spectroelectrochemistries, photoemission spectroscopies, and impedance spectroscopy were used to characterize the frontier orbital energies, charge selectivity and interfacial charge transfer kinetics in heterostructured NRs and organic photovoltaics. CdSe NRs tipped with Au nanoparticles and CdSe seeded CdS NRs tipped with Pt nanoparticles were used to study the effect of compositional asymmetry and catalytic sites on band edge energies of NRs. We used UV photoemission spectroscopy (UPS) and waveguide and transmission-based spectroelectrochemistry of NR monolayers/multilayers on conductive substrates to estimate valence/conduction band energies. Potential-modulated attenuated total reflectance (PM-ATR) spectroscopy was utilized to measure the apparent heterogeneous rate constants of reversible electron injection into NR films on indium tin oxide (ITO). We conclude from these measurements that metal tipping, which is designed to enhance the photocatalytic activity of semiconductor NRs, altered band edge energies and enhanced electronic coupling to conductive substrates, in ways that are predicted to influence their efficiency as photoelectrocatalysts. Monolayers of functionalized phosphonic acid ruthenium phthalocyanines (RuPcPA) tethered to ITO as a model organic photovoltaic donor/electrode interface were studied to understand the aggregation and orientation dependent charge transfer kinetics and energetics of these systems. The effect of surface roughness on the orientation of RuPcPA was theoretically modeled and compared to the experimental results. Electrochemical and spectroelectrochemical studies revealed the presence of only monomeric species on ITO. Impedance spectroscopy (IS) and PM-ATR were used to measure charge transfer rate constants. Further, frontier orbital energies of RuPcPA modified ITO were measured using UPS, and the results indicated favorable energetics for hole collection at the RuPcPA/ITO interface for OPV applications. The effect of "UV-light soaking" on the performance of organic photovoltaic devices employing metal oxide (MO) electron selective interlayers (ESL) was addressed using sputtered zinc oxide (ZnO) ESL films. This study provides a coherent methodology for differentiating between the proposed origins of the s-shaped current-voltage (J-V) responses in the literature for organic photovoltaics using MO ESLs. We use IS and UPS to demonstrate that the energetic barrier for charge extraction at the ZnO/active layer interface leads to the observed s-shape response in OPVs using ZnO ESLs. Furthermore, this study provides clear guidelines for minimizing the s-shaped J-V response and the effect of UV light on the performances of OPV devices using ZnO ESLs. We have developed solution electrochemical protocols to characterize nanometer-scale porosity and electronic properties of both solution-deposited and sputtered ZnO thin films used as interlayers for electron-harvesting contacts in inverted organic solar cells on ITO substrates. These electrochemical experiments were performed in order to evaluate the hole-blocking abilities of these ZnO ESLs as well as their effective "pinhole density," thus demonstrating a strong correlation to their OPV performances. These electrochemical experiments can be used to characterize and optimize ESLs rapidly, before OPV device fabrication.