Achieving high efficiency solar cells and concurrently driving down the cell cost has been among the key objectives for photovoltaic researchers to attain a lower levelized cost of energy (LCOE). While the performance of silicon (Si) based solar cells have almost saturated at an efficiency of ~25%, III-V compound semiconductor based solar cells have steadily shown performance improvement at approximately 1% (absolute) increase per year, with a recent record efficiency of 46%. However, the expensive cost has made it challenging for the high efficiency III-V solar cells to compete with the mainstream Si technology. Novel approaches to lower down the cost per watt for III-V solar cells will position them to be among the key contenders in the renewable energy sector. Integration of such high-efficiency III-V multijunction solar cells on significantly cheaper and large area Si substrate has the potential to address the future LCOE roadmaps by unifying the high-efficiency merits of III-V materials with low-cost and abundance of Si. However, the 4% lattice mismatch, thermal mismatch polar-on-nonpolar epitaxy makes the direct growth of GaAs on Si challenging, rendering the metamorphic cell sensitive to dislocations. The focus of this dissertation is to systematically investigate heterogeneously integrated III-V multijunction solar cells on Si substrate. Utilizing a combination of comprehensive solar cell modeling and experimental techniques, we seek to better understand the material properties and correlate them to improve the device performance, with simulation providing a very valuable feedback loop. Key technical design considerations and optimal performance projections are discussed for integrating metamorphic III-V multijunction solar cells on Si substrates for 1-sun and concentrated photovoltaics. Key factors limiting the “GaAs-on-Si” cell performance are identified, and novel approaches focused on minimizing threading dislocation density are discussed. Finally, we discuss a novel epitaxial growth path utilizing high-quality and thin epitaxial Ge layers directly grown on Si substrate to create virtual “Ge-on-Si” substrate for III-V-on-Si multijunction photovoltaics. With the plummeting price of Si solar cells accompanied with the tremendous headroom available for improving the III-V solar cell efficiencies, the future prospects for successful integration of III-V solar cell technology with Si substrate looks very promising to unlock an era of next generation of high-efficiency and low-cost photovoltaics. / Ph. D.

La production durable d’énergie et la recherche d’alternatives aux sources non renouvelables font l’objet d’un grand intérêt à l’heure actuelle. Le principal objectif de cette thèse était de synthétiser et étudier de nouveaux complexes organométalliques à base de Ru-acétylure, puis évaluer leurs propriétés photovoltaïques dans des cellules solaires hybrides à colorant et organique à hétérojonction volumique. Des complexes bimétalliques dissymétriques ont été développés afin d’obtenir des chromophores à absorption panchromatique, en bénéficiant d’une structure « push-pull » et du motif [Ru(dppe)2] comme excellent relai d’électron. En parallèle des complexes symétriques à un ou deux centres métalliques ont été développés, ceux-ci ont ensuite été intégrés à des cellules solaires organiques à hétérojonction volumique. Lors de cette étude, chaque dispositif a fait l’objet de différentes étapes d’optimisations dans le but d’améliorer les transferts de charges en améliorant la morphologie de la couche active. Les principales méthodes d’optimisations appliquées ont consisté à réaliser des traitements par « solvent vapor annealing », ajouter des additifs structurants et utiliser le colorant dans une matrice polymère dans un dispositif à mélange ternaire. / Today the sustainable energy production and research for alternatives to non-renewable sources attract a lot of interest. The aim of this PhD research was to synthetize and study new organometallic complexes Ru-diacetylide based, then to characterize their photovoltaic properties in hybrid dye-sensitized and organic bulk-heterojunction solar cells. To obtain panchromatic chromophores, asymmetric bimetallic complexes have been designed using [Ru(dppe)2] unit as excellent electron relay in a “push-pull” structure. In parallel, symmetric complexes have been developed with one or two metallic centres, and then they have been integrated to organic bulk-heterojunction solar cells. For this study, each device has been optimized through different steps, in order to improve charges transfers by improving morphology of the active layer. The main methods of optimization applied consisted of application of “solvent vapor annealing” treatment, addition of structure additives and addition of the dye in polymer matrix, in ternary molecules blend device.

Les cellules solaires nanostructurées ont été développées pour réduire le coût du photovoltaïque et le rendre compétitif aux autres sources d’énergies. Dans ce but deux cellules solaires ont été étudié durant la thèse: la cellule « eta » (Extremely Thin Absorber) et la cellule hybride à polymères. Dans un premier temps, des couches 2D et nanofils de ZnO ont été réalisés par voie électrochimique sur des substrats verre/TCO (oxyde transparent et conducteur). Il est montré que la température du bain, la densité de charge et la concentration de l’électrolyte support (KCl) infleuncent la morphologie, composition, cristallisation et propriétés optiques des couches. Les films déposés à 0,1 M KCl et à T ≥ 50°C, présente de bonnes propriétés physico-chimiques. La couche 2D est ensuite utilisée pour la croissance des nanofils de ZnO et leurs dimensions sont ajustées avec la moprhologie et l’épaisseur de cette couche. L’électrolyte support et la densité de charge permettent également de contrôler les dimensions des nanofils. Dans un deuxième temps, les nanofils de ZnO ont été photo-sensibilisés par deux types d’absorbeurs : CuInS2 (CIS) et Cu2ZnSnS4 (CZTS). Ils ont été réalisés par différentes méthodes : SILAR (Successive Ion Layer Adsorption and Reaction), électrodépôt et dépôt de nanoparticules pré-synthétisées (pour CIS). Les films préparés par voie SILAR sont très uniformes autour des nanofils. Tandis que ceux réalisés par électrodépôt sont moins homogènes mais de très bonnes qualités cristallines. Grâce à la fonctionnalisation des nanofils, une couche de nanoparticules de CuInS2 très uniforme est déposée. Les cellules « eta » réalisées avec ces structures cœur/coquille montrent un effet photovoltaïque. Les films de ZnO électrodéposés ont été intégrés dans des cellules solaires hybrides à polymères sur substrats verres et plastiques. Ces cellules ont montré de bons rendements et une haute stabilité. / Nanostructured solar cells have been proposed as a solution for photovoltaic cost reduction and to rival the cost of grid-powered electricity. Regarding this challenge, two kinds of solar cells have been studied within the PhD thesis: the Extremely Thin Absorber Solar cells (eta) and the polymer hybrid solar cell. First, we are reporting on the electrochemical deposition of ZnO 2D layers and nanowires on glass substrates covered with TCO (Transparent Conducting Oxide). It is shown that the bath temperature and the supporting electrolyte concentration (KCl) play an important role on the ZnO layer morphology, composition, crystallization and optical properties. The film deposited from 0.1 M KCl and T ≥ 50°C exhibit very good optical and structural properties. These 2D layers are used for consequent ZnO nanowires electrodeposition and their dimensions could be tailored by the seed layer morphology and thickness. The supporting electrolyte concentration and the passed charge density could be additionally used to control their dimensions. Then, the ZnO nanowires have been photosensitized with two absorbers: CuInS2 (CIS) and Cu2ZnSnS4 (CZTS). These materials are prepared by: Successive Ion Layer Adsorption and Reaction (SILAR), electrodeposition and nanoparticules deposition (for CIS). The SILAR films are very uniform around the nanowires. The layers prepared by electrodeposition are less uniform but exhibit very good structural properties. Uniform thin film of CuInS2 nanoparticules are deposited onto functionalized ZnO nanowires. The eta solar cells fabricated with these core/shell nanostructures have shown a photovoltaic effect. The ZnO thin films have been integrated in hybrid solar cells on flexible and rigid substrates. These cells show good power conversion efficiency and a high stability.

The subject of this diploma thesis is to analyse solar cells, demonstrate linearized model of PN junction and show basic techniques of measurement of this model. Solar cells measurement and acquired results are also presented.

<div>In this paper various applications of axial tensile load, bending load, and rolling loading has been applied to a Copper Indium Gallium Diselenide (CIGS) Solar Cell to lean how it would affect the solar cell parameters of: Open circuit voltage (Voc), Short circuit current, (Isc), Maximum power (Pmax), and Efficiency (EFF), and Fill Factor (FF). These Relationships were found for with three different experiments. The first experiment the applies axial tensile stress is to a CIGS solar cell ranging from 0 to 200 psi with various strain rates: 0.0001, 0.001, 0.01, and 0.1 in/sec as well as various relaxation time: 1min, 5min, and 10 min while the performance of solar cell is measured. The results of this gave several trends couple pertaining the Voc . The first is that open circuit voltage increases slightly with increasing stress. The second is the rate of increase (the slope) increases with longer relaxation times. The second set of trend pertains to the Isc. The first is that short circuit current generally is larger with larger stress. The second is there seems to be a general increase in the Isc up to a given threshold of stress. After that threshold the Isc seems to decrease. The threshold stress varies depending on strain rate and relaxation time. The second set of experiments consisted of holding a CIGS solar cell in a fixed curved position while it was in operational use. The radii of the curved cells were: 0.41, 0.20, 0.16, 0.13, 0.11, 0.094, and 0.082 m. The radii were performed for both concave and convex cell curvature. The trends for this show a slight decrease in all cell parameters with decreasing radii, the exception being Voc which is not effecting, the convex curvature causing a slightly faster decrease than the concave. This set of experiments were also processed to find the trends of the single diode model parameters of series resistance (Rs), shunt resistance (Rsh), dark current (I0), and saturation current (IL), which agreed with the experimental results. The second experiment consisted of rolling a CIGS solar cell in tensile (cells towards dowel.) and compression (cells away from dowel) around a dowel to create internal damage. The diameter of the dowels decreased. The dowel diameters were: 2. 1.75, 1.25, 1, 0.75, 0.5, and 0.25 inches. This experiment showed similar trends as the bending one but also had a critical diameter of 1.75 in where beyond that damage much greater. Finally a parametric study was done in COMSOL Multiphysics® to examine how changes in the CIGS material properties of electron mobility (EM), electron life time, (EL), hole mobility 15 (HM), and Hole life time (HL) effect the cell parameters. The trends are of an exponential manner that converges to a given value as the material properties increase. When EL, EM, HL are very small, on the order of 10-4 times smaller than their accepted values, a transient like responses occurs.<br></div>

This dissertation focuses on the design, synthesis, and characterization of a variety of organic dyes, semiconducting materials, and surface redox-active modifiers of potential interest to organic-based emerging photovoltaics. A discussion of the materials’ optoelectronic properties, their ability to modify and promote electron transfer through an organic/transparent conducting-oxide interface, and finally their effect on the photovoltaic properties of devices utilizing them as light-harvesters is provided where relevant. The first two research chapters discuss mono-chromophoric asymmetric squaraine-based sensitizers and covalently linked, dual-chromophoric, porphyrin-squaraine sensitizers as light absorbers in dye-sensitized solar cells (DSSCs), in an attempt to address two problems often encountered with DSSCs utilizing this class of near infra-red sensitizers; The lack of panchromatic absorption and aggregation on the surface. Also, this dissertation discusses the design and synthesis of asymmetric perylene diimide phosphonic acid (PDI-PA) redox-active surface modifiers, and reports on the electron-transfer rates and efficiencies across the interface of an ITO electrode (widely used in organic-electronic devices) modified with these perylene diimides. Finally two series of hole-transport materials based on oligothiophenes and benzodithiophenes are reported: optoelectronic properties and preliminary performance of organic photovoltaic (OPV) devices fabricated with them is discussed.

Innovative electronic device concepts that use polarization charges to provide improved performance were validated. The strength of the electric fields created by polarization charges (PCs) was suggested to act as an additional design parameter in the creation of devices using III-nitride and other highly polar materials. Results indicated that polarization induced electric fields can replace conventional doping schemes to create the charge separation region of solar cells and would allow for a decoupling of device performance from doping requirements. Additionally, a model for calculating current through polarization induced tunnel diodes was proposed. The model was found to agree well with experimental current values. Several polarization induced tunnel junction (PTJ) designs were analyzed. A novel double-barrier PTJ was conceived that would allow for the creation of a multi-junction solar cell using strained InGaN absorption layers. Future research would include the fabrication of these devices and the inclusion of thermal effects in the model for calculating current through PTJs.

This thesis investigates the possibility of enhancing the efficiency of thin film solar cells by including periodic material nonhomogeneities in combination with periodically corrugated back reflectors. Two different types of solar cell are investigated; p-i-n junctions solar cells made from alloys of hydrogenated amorphous silicon (a-Si:H) (containing either carbon or germanium), and Schottky barrier junction solar cells made from alloys of indium gallium nitride (InξGa1-ξN). Material nonhomogeneities are produced by varying the fractions of the constituent elements of the alloys. For example, by varying the content of carbon or germanium in the a-Si:H alloys, semiconductors with bandgaps ranging from 1:3 eV to 1:95 eV can be produced. Changing the bandgap alters both the optical and electrical properties of the material so this necessitates the use of coupled optical and electrical models. To date, the majority of solar cell simulations either prioritise the electrical portion of the simulation or they prioritise the optical portion of the simulation. In this thesis, a coupled optoelectronic model, developed using COMSOL Multiphysics®, was used to simulate solar cells: a two-dimensional finite-element optical model, which solved Maxwell's equations throughout the solar cells, was used to calculate the absorption of incident sunlight; and a finite-element electrical drift-diffusion transport model, either one- or two-dimensional depending on the symmetries of the problem, was used to calculate the steady state current densities throughout the solar cells under external voltage biases. It is shown that a periodically corrugated back reflector made from silver can increase efficiency of an a-Si:H alloy single p-i-n junction solar cell by 9:9% compared to a baseline design, while for a triple junction the improvement is a relatively meagre 1:8%. It is subsequently shown that the efficiency of these single p-i-n junction solar cells with a back reflector can be further increased by the inclusion of material nonhomogeneities, and that increasing the nonhomogeneity progressively increases efficiency, especially in thicker solar cells. In the case of InξGa1-ξN Schottky barrier junction solar cells, the gains are shown to be even greater. An overall increase in efficiency of up to 26:8% over a baseline design is reported.

In bulk-heterojunction solar cells, device performance is influenced by both the intrinsic properties of the individual components - typically conjugated polymers and fullerene derivatives - and how they assemble and interact at their interface. The ability of fullerene to intercalate within the side-chains of a conjugated polymer can significantly affect the microstructure and overall device performance. Here, a series of computational chemistry approaches are applied to investigate the relationships between structure and property in intercalated polymer:fullerene blend. Using a combination of molecular mechanics (MM) calculation and simulations of 2D grazing incidence X-ray diffraction (GIXD) patterns, we have determined the molecular packing configuration of poly (2,5-bis (3-tetradecyl thiophene-2-yl) thieno[3,2-b]thiophene) (PBTTT-C₁₄) and a blend of PBTTT-C₁₄ and [6,6]-phenyl-C₇₁-butyric acid methyl ester (PC₇₁BM). Based on the confirmed packing structures, the electronic properties and morphological disorder were examined using density functional theory (DFT) and molecular dynamics (MD) calculations, respectively; we also investigated the intermolecular interaction energies behind the structure formation. Finally, we examined the vibrational, redox, and optical properties of the pristine polymer and a series of fullerene derivatives to understand the characteristic modes related to the various charged states of the systems.

As the efficiency potential for the industrial P-type Al-BSF silicon solar cell reaches its limit, new solar cell technologies are required to continue the pursuit of higher efficiency solar power at lower cost. It has been demonstrated in literature that among possible alternative solar cell structures, cells featuring a local BSF (LBSF) have demonstrated some of the highest efficiencies seen to date. Implementation of this technology in industry, however, has been limited due to the cost involved in implementing the photolithography procedures required. Recent advances in solar cell doping techniques, however, have identified ion implantation as a possible means of performing the patterned doping required without the need for photolithography. In addition, past studies have examined the potential for building solar cells on N-type silicon substrates, as opposed to P-type. Among other advantages, it is possible to create N-type solar cells which do not suffer from the efficiency degradation under light exposure that boron-doped P-type solar cells are subject to. Industry has not been able to capitalize on this potential for improved solar cell efficiency, in part because the fabrication of an N-type solar cell requires additional masking and doping steps compared to the P-type solar cell process. Again, however, recent advances in ion implantation for solar cells have demonstrated the possibility for bypassing these process limitations, fabricating high efficiency N-type cells without any masking steps. It is clear that there is potential for ion implantation to revolutionize solar cell manufacturing, but it is uncertain what absolute efficiency gains may be achieved by moving to such a process. In addition to development of a solar specific ion implant process, a number of new thermal processes must be developed as well. With so many parameters to optimize, it is highly beneficial to have an advanced simulation model which can describe the ion implant, thermal processes, and cell performance accurately. Toward this goal, the current study develops a process and device simulation model in the Sentaurus TCAD framework, and calibrates this model to experimentally measured cells. The study focuses on three main tasks in this regard: Task I - Implant and Anneal Model Development and Validation This study examines the literature in solar and microelectronics research to identify features of ion implant and anneal processes which are pertinent to solar cell processing. It is found that the Monte Carlo ion implant models used in IC fabrication optimization are applicable to solar cell manufacture, with adjustments made to accommodate for the fact that solar cell wafers are often pyramidally textured instead of polished. For modeling the thermal anneal processes required after ion implant, it is found that the boron and phosphorus cases need to be treated separately, with their own diffusion models. In particular, boron anneal simulation requires accurate treatment of boron-interstitial clusters (BICs), transient enhanced diffusion, and dose loss. Phosphorus anneal simulation requires treatment of vacancy and interstitial mediated diffusion, as well as dose loss and segregation. The required models are implemented in the Sentaurus AdvancedModels package, which is used in this study. The simulation is compared to both results presented in literature and physical measurements obtained on wafers implanted at the UCEP. It is found that good experimental agreement may be obtained for sheet resistance simulations of implanted wafers, as well as simulations of boron doping profile shape. The doping profiles of phosphorus as measured by the ECV method, however, contain inconsistencies with measured sheet resistance values which are not explained by the model. Task II - Device Simulation Development and Calibration This study also develops a 3D model for simulation of an N-type LBSF solar cell structure. The 3D structure is parametrized in terms of LBSF dot width and pitch, and an algorithm is used to generate an LBSF structure mesh with this parametrization. Doping profiles generated by simulations in Task I are integrated into the solar cell structure. Boundary conditions and free electrical parameters are calibrated using data from similar solar cells fabricated at the UCEP, as well as data from lifetime test wafers. This simulation uses electrical models recommended in literature for solar cell simulation. It is demonstrated that the 3D solar cell model developed for this study accurately reproduces the performance of an implanted N-type full BSF solar cell, and all parameters fall within ranges expected from theoretical calculations. The model is then used to explore the parameter space for implanted N-type local BSF solar cells, and to determine conditions for optimal solar cell performance. It is found that adding an LBSF to the otherwise unchanged baseline N-type cell structure can produce almost 1% absolute efficiency gain. An optimum LBSF dot pitch of 450um at a dot size of 100um was identified through simulation. The model also reveals that an LBSF structure can reduce the fill factor of the solar cell, but this effect can be offset by a gain in Voc. Further efficiency improvements may be realized by implementing a doping-dependent SRV model and by optimizing the implant dose and thermal anneal. Task III - Development of a Procedure for Ion Implanted N-type LBSF Cell Fabrication Finally, this study explores a method for fabrication of ion-implanted N-type LBSF solar cells which makes use of photolithographically defined nitride masks to perform local phosphorus implantation. The process utilizes implant, anneal, and metallization steps previously developed at the UCEP, as well as new implant masking steps developed in the course of this study. Although an LBSF solar cell has not been completely fabricated, the remaining steps of the process are successfully tested on implanted N-type full BSF solar cells, with efficiencies reaching 20.0%.