A phenomenon of wurtzite (w), zincblende (zb), and rock-salt (rs) phase separation was investigated in ZnCdO films having Cd contents in the range of 0%-60% settling a discussion on the phase stability issues in ZnCdO. First, low-Cd-content (17%) ZnCdO was realized preferentially in a w matrix determining optimal Zn-lean conditions by tuning the precursor decomposition rates during synthesis. However, more detailed analysis of x-ray diffraction and photoluminescence (PL) data revealed that the w single-phase stability range is likely to be as narrow as 0%-2% Cd, while samples containing 7%-17% of Cd exhibit a mixture of w and zb phases. Second, high-Cd-content (32%-60%) ZnCdO samples were realized, supplying more of the Cd precursor utilizing Zn-lean growth conditions, however, resulting in a mixture of w, zb, and rs phases. Characteristic PL signatures at 2.54 and 2.31 eV were attributed to zb-ZnCdO and rs-CdO, respectively, while the band gap variation in w-Zn 1−x Cd x O is given by (3.36-0.063x) as determined at 10 K. The phase separation is interpreted in terms of corresponding changes in the charge distribution and reduced stacking fault energy.

Zinc oxide (ZnO) has been used in a wide range of products for many years, including, among others, varistors, surface acoustic wave devices and cosmetics. Besides these established applications, ZnO and its ternary alloys are now also being considered as potential materials for optoelectronic applications, such as light emitting diodes, photovoltaics, sensors, displays, etc. Unlike other materials, which could be used alternatively, ZnO has the advantage of being inexpensive, chemically stable and relatively plentiful. In spite of the long research history, fabrication of defect free ternary alloys and stable p-type ZnO is still challenging. The aim of this work was therefore to provide a better understanding of ZnO ternary alloys, so that -based on the gained knowledge -their optical properties can be further improved and, in a second step, optoelectronic applications based on these materials can soon be commercialized. The work carried out in this thesis was two-fold: the first part aimed at identifying the origin of defect related luminescence phenomena in ZnMgO, and the second part was dedicated to the exploration of a novel ZnCdO-based heterostructure photovoltaic applications.In the case of ZnMgO, luminescence properties of deep level defects were studied by photoluminescence (PL) spectroscopy and a model was proposed to explain the changes in the deep band emission with increasing Mg content. In this model, the observed trends can be understood by considering interaction of native zinc and oxygen defects of the ZnO sublattice with Mg interstitials (Mg i ). In summary, the deep level bands at 3.0 and 2.8 eV, which show a blueshift with increasing Mg content, were assigned to free-to-bound type transitions between zinc interstitials (Zn i ) with the valence band edge and between the conduction band edge with zinc vacancies (V Zn ), respectively. A red band at 2.0 eV, which does not show an apparent shift of the peak energy for increasing Mg content, is associated with the oxygen vacancies (V O ). Two luminescence bands at 2.3 and 2.5 eV, which are redshifted for higher Mg concentrations, were assigned to transitions between zinc and oxygen interstitials and between zinc interstitials and zinc vacancies, respectively. The redshift is interpreted in terms of a competing supply of electrons from slightly deeper Mg i donor states. The ZnMgO band gap diagram, which the model is based on, has contributed to gain valuable information about the nature of the deep defects both in ZnO and ZnMgO and is therefore of fundamental interest.In the second part of this work, focused on ZnCdO, a stacked heterostructure was designed for iii iv Abstract application in a photoelectrochemical cell, which is used for hydrogen production by photoelectrolysis using the semiconductor as an absorber. Optical and photoelectrochemical measurements led to the conclusion that the optical emission band for the ZnCdO heterostructures is broadened compared to a ZnO single layer. The broadened emission could be explained by combined ...

Surface plasmon (SP) mediated near band-edge emission in Ag/ZnO nanorods has been systematically studied by using a temperature-dependent photoluminescence spectra technique. It was found that the mediation mainly concerns SP couplings with two emissions, one from neutral donor-bound exciton D 0 X recombination and another from the radiative transition of free electron to neutral acceptor (e, A 0). The first coupling process is demonstrated to prevail in the temperature range from 300 to 150 K, while the second is dominant below 150 K. The competition mechanism and the role of exciton and carrier delocalizations in the coupling processes have been explored in the unique Ag/ZnO nanostructures.

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