Nanostructured Transparent Conducting Oxides for Device Applications

Research on transparent conducting oxides (TCOs) alternative to indium tin oxide (ITO) has attracted a lot of attention due to the serious concern related to cost and chemical stability of indium tin oxide. The primary aim of this research is to develop low cost alternative transparent conducting oxides with an eye towards (1) increasing the organic solar cell efficiency and (2) fabricating transparent electronic devices utilizing p-type TCOs. To investigate the fundamental properties, the novel TCO films have been grown on sapphire and economical glass substrates using pulsed laser deposition (PLD) technique. The films were also grown under different deposition conditions in order to understand the effect of processing parameters on the film properties. The characteristics of the thin films have been investigated in detail using (X-ray diffraction, TEM, X-ray photoelectron spectroscopy (XPS), UV- photoelectron spectroscopy (UPS), four probe resistivity and UV-Vis transmittance measurements) in order to establish processing-structure-property correlation. ZnO doped with group III elements is a promising candidate because of its superior stability in hydrogen environment, benign nature and relatively inexpensive supply. However, ZnO based TCO films suffer from low work function (4.4 eV, compared to that of 4.8 eV for ITO), which increases the energy barrier and affects the carrier transport across ZnGa0.05O/organic layer interface. To overcome this issue of ZnO based TCOs, the growth of bilayered structure consisting of very thin MoOx (2.0 < x < 2.75), and/or p-Li xNi1-xO (0 ≤ x≤ 0.07) over layer on Zn0.95Ga 0.05O (GZO) film by pulsed laser ablation is proposed. The multiple oxidation states present in the over layers (Mo4+, Mo 5+ and Mo6+ in MoOx and Ni2+ and Ni3+ in NiO1+x), which result in desired TCO characteristics were determined and controlled by growth parameters and optimal target composition. These optimized bilayer films exhibited good optical transmittance (≥ 80%) and low resistivity of ∼ 10-4 O-cm. The optimized NiO1+x / GZO and MoOx / GZO bilayers showed significant increase in work function values (∼5.3 eV). The work function of the bilayer films was tuned by varying the processing conditions and doping of over layers. Preliminary test device results of the organic photovoltaic cells (OPVs) based on these surfaces modified TCO layers have shown an increase in the open circuit voltage (Voc) and/or increase in Fill factor (FF) and the power conversion efficiency of these devices. These results suggest that the surface modified GZO films have a potential to substitute for ITO in transparent electrode applications.;To gain a better understanding of the fundamentals and factors affecting the properties of p-type TCO, NiO thin films have been grown on c-sapphire and glass substrates with controlled properties. Growth of NiO on c-sapphire occurs epitaxially in [111] direction with two types of crystalline grains rotated by 60° with respect to each other. We have also investigated the effects of the deposition parameters and Li doping concentration variations on the electrical and optical properties of NiO thin films. The analysis of the resistivity measurement showed that doped Li+ ions occupy the substitutional sites in the NiO films, enhancing the p-type conductivity. The minimum resistivity of 0.15 O-cm was obtained for Li0.07Ni 0.93O film. The results of this research help to understand the conduction mechanisms in TCOs and are critical to further improvement and optimization of TCO properties. This work has also demonstrated interesting possibilities for fabricating a p-LixNi1-xO/ i-MgZnO /n-ZnO heterojunction diode on c-sapphire. It has been demonstrated that epitaxial LixNi 1-xO can be grown on ZnO integrated with c-sapphire. Heteroeptaxial growth of the p-n junction is technologically important as it minimizes the electron scattering at the interface. The insertion of i-MgZnO between the p and n layer led to improved current-voltage characteristics with reduced leakage current.;An attempt has been made to elucidate the role of point defects, in controlling the carrier concentration and transport characteristics of nanostructured TCO films. This study presents the systematic changes in structural, electrical and optical properties of NiO thin films introduced by nanosecond duration Ultraviolet Excimer laser pulses. NiO films show transformation from p-type semiconducting to n-type conducting behavior with three order of magnitude decrease in resistivity, while maintaining its cubic crystal structure and good epitaxial relationship. This phenomenon is reversible via oxygen annealing. From XPS analysis, a strong correlation has been established between n-type conductivity and non-equilibrium concentrations of laser induced Ni 0-like defect states.