The present study aims at studying the surface morphology, crystallinity and optical emission property of Mg added ZnO grown by molecular beam epitaxy. Zn1-xMgxO epitaxial films were first grown at a fixed Zn flux of 1¡Ñ10-7 mbar and Mg flux of 4¡Ñ10-10 to 6.2¡Ñ10-9 mbar on sapphire substrates at 400 oC. The corresponding Mg content (x) is in a range of <0.01 to 0.17. Scanning electron microscopy observations indicated that the surface of the films are flat. The orientation relationship between the film and the substrate is: (0001)Zn1-xMgxO¡ü(0001)Al2O3©M[101 ¡Â0] Zn1-xMgxO¡ü[112 ¡Â0] Al2O3. The full width at half maximum (FWHM) of the (0002) reflection in rocking curve measurement is in a range of 3.83 o to 4.81 o. Photoluminescence results showed that the intensities of both the near band-gap emission and the deep level emission increases with increasing Mg content. The former has FWHM values of 0.16-0.21 eV. While the epitaxial films were grown at a high Zn flux of 5¡Ñ10-7 mbar and Mg flux of 2¡Ñ10-9 to 9.6¡Ñ10-9 mbar on sapphire and LiAlO2 substrates at 400 oC, the film surface are at high roughness. The FWHM of (0002) rocking curve is 4.43 o to 5.71 o for films grown on sapphire and is relatively larger of 6.88 o to 8.18 o for films grown on LiAlO2, respectively. These films possess a stronger near band-gap emission and a lower deep level emission as compared to the films grown at a low Zn flux. After annealed at 600 oC in oxygen or nitrogen, the FWHMs of the (0002) rocking curve for most of the epilayers decreased slightly. The photoluminescence results were rather distinct. For samples having low Mg content (x<0.05), the intensity of the near band-gap emission increases 50-200 ¢H after annealed in oxygen. The intensity of the near band-gap emission did not change but that of the deep level emission decreases ~50 ¢H for the film having x=0.16 after annealing in oxygen. The emission characteristics basically do not change after annealed in nitrogen.

Im Rahmen der Dissertation wurden molekularstrahlepitaktische Verfahren zur Züchtung von Hetero-und Quantenstrukturen auf der Basis der Gruppe II-Oxide entwickelt. Insbesondere wurde ein Wachstumsregime weit entfernt vom thermischen Gleichgewicht etabliert, welches die Mischung von CdO und MgO mit ZnO in phasenreiner Wurtzitstruktur ermöglicht, wobei die Gleichgewichtslöslichkeitsgrenzen dramatisch überschritten werden. In den Mischkristallen kann die Bandlücke kontinuierlich von 2.2 bis 4.4 eV eingestellt werden. Das Wachstum verläuft in einem zweidimensionalen Modus und resultiert in atomar glatten Ober- und Grenzflächen. Ausgeprägte RHEED- Intensitätsoszillationen erlauben die atomlagengenaue Kontrolle der Schichtdicken und somit die Realisierung wohl-defi- nierter Einzel- und Mehrfachquantengrabenstrukturen. Diese zeichnen sich durch eine hohe Photolumineszenzquantenausbeute im gesamten sichtbaren Spektralbereich aus. Laseraktivität kann vom UV bis zum grünen Wellenlängenbereich bei Zimmertemperatur erzielt werden. Das Potenzial dieser Quantenstrukturen in Hinblick auf ihre Anwendung in opto-elektronischen Bauelementen wird diskutiert. / This work focuses on the development of the novel growth approaches for the fabrication of Group II-oxide materials in the form of epitaxial films and heterostructures. It is shown that molecular-beam epitaxial growth far from thermal equilibrium allows one to overcome the standard solubility limit and to alloy ZnO with MgO or CdO in strict wurtzite phase up to mole fractions of several 10 %. In this way, a band-gap range from 2.2 to 4.4 eV can be covered. A clear layerby- layer growth mode controlled by oscillations in reflection high-energy electron diffraction makes it possible to fabricate atomically smooth heterointerfaces and well-defined quantum well structures exhibiting prominent band-gap related light emission in the whole composition range. On appropriately designed structures, laser action from the ultraviolet down to green wavelengths and up to room temperature is achieved. The properties and potential of the "state-of-the-art" materials are discussed in relation to the advantages for their applications in various optoelectronic devices.

Two identified setbacks for CIGS based devices in order to obtain higher efficiency are parasitic absorption in the window layer structure and losses in open-circuit voltage due to bad interfaces. This study investigated how the performance of the solar cell is affected by depositing intrinsic ZnO (i-ZnO) and ZnMgO with atomic layer deposition (ALD) instead of the conventional sputtering. No significant improvement in fill factor was obtained by the use of ALD compared to sputtering, leading to the conclusion that pinholes in the sputtered film are not a detrimental factor for the cell. As the thickness of the i-layer increased, an increase in FF was observed for the ALD-deposited i-layer, whereas a decrease was observed for the sputtered i-layer. The open-circuit voltage was considered constant between the two series with only small fluctuations, indicating that the defect chemistry of the i-ZnO/CdS interface was not improved with the use of ALD. In this study it is shown that a gain in short-circuit current can be obtained for CIGS solar cells in the high energy region of the spectrum by reducing the thickness of the i-ZnO, as well as alloying the ZnO with Mg. When compared with a baseline layer sample with a sputtered i-layer thickness of around 90 nm, the estimated gain in short-circuit current density without a loss in fill factor was 0.14 and 0.20 mA/cm2 for ALD and sputtering, respectively. For the series with a ZnMgO i-layer, the highest estimated gain was 0.17 mA/cm2. This was observed for the sample with a 4:1 (Zn:Mg) pulse ratio, whereas higher Mg contents yielded a too high band gap that resulted in an electron blocking barrier.

Wide band gap semiconductors such as MgxZn1-xO represent an excellent choice for making optical photodetectors and emitters operating in the UV spectral region. High crystal and optical quality MgxZn1-xO thin films were grown epitaxially on c-plane sapphire substrates by plasma-assisted Molecular Beam Epitaxy. ZnO thin films with high crystalline quality, low defect and dislocation densities, and sub-nanometer surface roughness were achieved by applying a low temperature nucleation layer. The critical growth conditions were discussed to obtain a high quality film: the sequence of Zn and O sources for initial growth of nucleation layer, growth temperatures for both ZnO nucleation and growth layers, and Zn/O ratio. By tuning Mg/Zn flux ratio, wurtzite MgxZn1-xO thin films with Mg composition as high as x=0.46 were obtained without phase segregation. The steep optical absorption edges were shown with a cut-off wavelength as short as 278nm, indicating of suitability of such material for solar blind photo detectors. Consequently, Metal-Semiconductor-Metal photoconductive and Schottky barrier devices with interdigital electrode geometry and active surface area of 1 mm2 were fabricated and characterized. Photoconductor based on showed ~100 A/W peak responsivity at wavelength of ~260nm. ZnO homoepitaxial growth was also demonstrated which has the potential to achieve very low dislocation densities and high efficiency LEDs. Two types of Zn-polar ZnO substrates were chosen in this study: one with 0.5° miscut angle toward the [1-100] direction and the other iv without any miscut angle. We have demonstrated high quality films on both substrates with a low growth temperature (610°C) compared to most of other reported work on homoepitaxial growth. An atomically flat surface with one or two monolayer step height along the [0001] direction was achieved. By detail discussions about several impact factors for the epitaxial films, ZnO films with high crystallinity verified by XRD in different crystal orientations, high PL lifetime (~0.35 ns), and not obvious threading dislocations were achieved. Due to the difficulty of conventional p-type doping with p dopant, we have explored the possibility of p-type doping with the assistance of other novel method, i.e. polarization induced effect. The idea is the sheet layer of two dimensional hole gases (2DHG) caused by the wurtzite structure’s intrinsic polarization effect can be expanded to three dimension hole distribution by growing a MgZnO layer with a Mg concentration gradient. By simulation of LED structure with gradient MgZnO structure, the polarization effect was found not intense as that for III-nitrides because the difference of spontaneous polarization between ZnO and MgO is smaller than that of GaN and AlN, and the piezoelectric polarization effect may even cancel the spontaneous polarization induced effect. We have grown the linear gradient MgZnO structure with Mg composition grading from 0% to 43%, confirmed by SIMS. Hall measurement did not show any p-type conductivity, which further indicates MgZnO’s weak polarization doping effect. However, the gradient MgZnO layer could act as an electron blocking layer without blocking holes injected from p layer, which is useful for high efficiency light emitters.