Cu(In,Ga)Se2-based thin-film solar cells are one of the most promising photovoltaic technologies nowadays. Despite significant improvements to the performance of Cu(In,Ga)Se2 (CIGS) in recent decades, the electrical characteristics of CIGS solar cells still have not been completely understood, especially the origins and the properties of metastabilities. This project focuses on the electrical characterization of CIGS based thin film devices with different Cu contents. Different characterization techniques have been used in this project. With varying Cu content, the structural properties, basic parameters, space charge distribution, temperature dependent properties, reverse bias- and white light illumination- induced metastable effects and breakdown behaviors have been investigated.

Polycrystalline thin-film solar cells have reached a levelized cost of energy that is competitive with all other sources of electricity. The technology has significantly improved in recent years, with laboratory cell efficiencies for cadmium telluride (CdTe), perovskites, and copper indium gallium diselenide (CIGS) each exceeding 22 percent. Both CdTe and CIGS solar panels are now produced at the gigawatt scale. However, there are ongoing challenges, including the continued need to improve performance and stability while reducing cost. Advancing polycrystalline solar cell technology demands an in-depth understanding of efficiency, scaling, and degradation mechanisms, which requires sophisticated characterization methods. These methods will enable researchers and manufacturers to improve future solar modules and systems.

The demand for clean and renewable energy sources in recent years has motivated research on the development of low cost, thin film photovoltaic devices. As a consequence, tools for the investigation and characterization of thin film photovoltaic component materials and devices, which can be implemented in real time as well as under in-line and off-line measurement conditions, are becoming increasingly important. Real time spectroscopic ellipsometry (RTSE) and ex-situ mapping spectroscopic ellipsometry (SE) are powerful characterization tools suitable for applications in the optimization of device performance and the evaluation of thin film photovoltaics technology scale-up from dot cell sizes in research laboratories to full module sizes in factories. These non-destructive optical probes implement multichannel spectroscopic detection for achieving high measurement speed, while simultaneously yielding high precision light-matter interaction parameters. The interaction parameters can be analyzed to obtain layer thicknesses as well as their optical properties from which material properties such as composition can be determined. The layer thicknesses and their optical properties in turn provide insights into the fraction of incident light absorbed in the active layer of the solar cell and also provide a basis for short-circuit current optimization through optical simulations. In this dissertation research, Cu(In, Ga)Se2 films with different Ga contents have been prepared by a one stage co-evaporation process. These films have been studied by spectroscopic ellipsometry (RTSE) in real time during their deposition, which has been performed at high temperature (570oC). After cooling the films to room temperature, in-situ SE measurements were undertaken in order to extract the dielectric functions of the thin film materials. An extended parameterization was established through the fitting of these dielectric functions to analytical functions, followed by the development of expressions in the free parameters that describe these analytical functions versus the Ga content. As a result of this parameterization, dielectric function spectra can be predicted for any desired composition. This capability was applied for the structural and compositional mapping of CIGS thin films and solar cells deposited over 10 cm × 10 cm substrate areas. Correlations of the deduced structural and compositional parameters with the corresponding device performance characteristics have yielded important insights with the potential to assist in the optimization of solar cell devices incorporating thin CIGS layers. In addition, a methodology of external quantum efficiency simulation (EQE) has been developed that relies on ex-situ spectroscopic ellipsometry analysis of complete thin film solar cells and so does not require free parameters. The simulations have been applied to CIGS and a-Si:H solar cells, based on the assumption that all photo-generated carriers within the active layers of these cells are collected without any recombination losses. Thus, it should be noted the predicted EQE is the maximum that the solar cell having the given structure can generate, and the difference between the predicted and measured EQE for the same device can provide insights into recombination losses in the device. Because the predicted EQE is based on specular interfaces, it can also be lower than the measured values due to light trapping caused by rough surfaces and interfaces. In another research area of interest for CIGS materials and solar cells, the role of the stage II/III substrate temperature (540oC - 640oC) in the deposition of the films by the three stage process has been studied, as has its effect on device performance, sodium diffusion, and grain size. Since standard soda-lime glass does not tolerate temperatures above 570oC due to glass softening, specially engineered high temperature soda-lime glass produced by Nippon Electric Glass Co., Japan was used as the substrate material in this study. It was found that the average device performance improves up to 620oC as a consequence of reduced shunting and improved diode quality factor which affect the fill factor of the device. At 640oC, however, these parameters have exhibited a wider distribution, and thus have yielded a lower average efficiency for the cells. SEM micrographs of these devices showed that the grain size first increased with increasing temperature up to 620oC, and then showed a bimodal distribution at 640oC. Finally, ex-situ mapping ellipsometry has been applied in the study of silver nanoparticle thin films prepared by the drop casting method. These films are important because of the plasmonic effects they exhibit. Such effects can be exploited by integrating the nanoparticle layers into solar cells in order to promote light trapping, and hence, increase the overall efficiency of the cells. A study of these films with mapping spectroscopic ellipsometry provides a means of determining thickness uniformity over large areas that is critical for scale-up of the deposition processes. The uniformity of other parameters of the films such as the plasmon resonance energy and its broadening are equally important to ensure maximum coupling of light into the solar cell absorber layer.

The distribution of the electrostatic potential in and between the materials in Cu(In,Ga)Se2 thin-film solar cells has a major impact on their superior performance. This thesis reported on the nanoscale imaging of the electrostatic potential on untreated cross sections of operating Cu(In,Ga)Se2 solar cells using Kelvin probe force microscopy.

Chalcopyrites, in particular those with a wide band gap, are fascinating materials in terms of their technological potential in the next generation of thin-film solar cells and in terms of their basic material properties. They exhibit uniquely low defect formation energies, leading to unusual doping and phase behavior and to extremely benign grain boundaries. This book collects articles on a number of those basic material properties of wide-gap chalcopyrites, comparing them to their low-gap cousins. They explore the doping of the materials, the electronic structure and the transport through interfaces and grain boundaries, the formation of the electric field in a solar cell, the mechanisms and suppression of recombination, the role of inhomogeneities, and the technological role of wide-gap chalcopyrites.

Thin-film solar cells are either emerging or about to emerge from the research laboratory to become commercially available devices finding practical various applications. Currently no textbook outlining the basic theoretical background, methods of fabrication and applications currently exist. Thus, this book aims to present for the first time an in-depth overview of this topic covering a broad range of thin-film solar cell technologies including both organic and inorganic materials, presented in a systematic fashion, by the scientific leaders in the respective domains. It covers a broad range of related topics, from physical principles to design, fabrication, characterization, and applications of novel photovoltaic devices.