Explaining Morphological and Electrical Features of Boron-doped Zinc Oxide to Tailor New Electrodes for Photovoltaics

TCOs are a class of metal oxides that combine transparency to visible light with electrical conductivity. Each TCO is characterized by the trade-off of these two properties which can be tuned for a particular application. This thesis is dedicated to the investigation of one TCO material: boron doped zinc oxide (ZnO:B) deposited by low-pressure chemical vapor deposition (LP-MOCVD). Its main distinction is low absorptance which makes ZnO films deposited by LP-MOCVD ideal as transparent electrodes in thin-film solar cells. Although ZnO:B properties have previously been optimized for this application, the exact processes behind the film formation have not been fully described. This thesis substantially clarifies the processes of the film nucleation and growth evolution, and the mechanisms of incorporation of the B atoms into the ZnO. First, for non-intentionally doped ZnO we establish that the main deposition parameters influencing the film properties are the deposition temperature, the gas precursor ratio and the total gas flow. We experimented with these three parameters across a wide range of parameter values. The films deposited were characterized at different stages of their growth using atomic force microscopy, X-ray diffraction and automated crystallographic orientation mapping. These data reveal the dependence of the film preferential orientation on the deposition conditions. We propose a model based on the adsorbed atom mean free path to explain this dependence. Using deposition parameters learnt from this model, we control the preferential orientation during film growth to increase the grain sizes. Second, we analyze the conductivity to B-doped ZnO films. Boron atoms act as electron donors in ZnO, increasing the electrical conductivity and decreasing the transparency. This work quantifies how the B concentration and spatial distribution affect the film conductivity. Quantification of the B atoms incorporated in the film was performed using nuclear reaction analysis. We found that a high level of O precursor gas favors B incorporation in the film. Combining nano secondary ion mass spectroscopy and Kelvin probe force microscopy we demonstrate that the dopant atoms incorporate in only one of the two sides of each grain. This is a new observation because dopant atoms are commonly assumed to be uniformly distributed in the film. The transparency and electrical conductivity of ZnO depend also on the carrier mobility. The sources of carrier scattering are investigated for intrinsic (i.e. O vacancies and Zn interstitials) and extrinsic (B atoms) impurity concentrations. We observed that for the same B concentration the source of electron scattering depends on the concentration of intrinsic defects: for films with a lower concentration of intrinsic defects, the main source of scattering is the grain boundaries; for films with a higher concentration of intrinsic defects, the main sources are the mechanisms happening in the crystalline region. Finally, LP-MOCVD ZnO:B films were optimized using the previous results and successfully applied in four different types of solar cells: amorphous/microcrystalline silicon, amorphous silicon, copper indium gallium selenide and silicon heterojunction. The advantages of the developed films to these four cells include the simplification of the fabrication process, the reduction of reflectance and parasitic absorption, and a better understanding of carrier transport mechanisms through the device.

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