Formation and annealing of dislocation loops induced by nitrogen implantation of ZnO

Although zinc oxide is a promising material for the fabrication of short wavelength optoelectronic devices, p-type doping is a step that remains challenging for the realization of diodes. Out of equilibrium methods such as ion implantation are expected to dope ZnO successfully provided that the non-radiative defects introduced by implantation can be annealed out. In this study, ZnO substrates are implanted with nitrogen ions, and the extended defects induced by implantation are studied by transmission electron microscopy and X-ray diffraction (XRD), before and after annealing at 900^{\circ}C. Before annealing, these defects are identified to be dislocation loops lying either in basal planes in high N concentration regions, or in prismatic planes in low N concentration regions, together with linear dislocations. An uniaxial deformation of 0.4% along the c axis, caused by the predominant basal loops, is measured by XRD in the implanted layer. After annealing, prismatic loops disappear while the density of basal loops decreases and their diameter increases. Moreover, dislocation loops disappear completely from the sub-surface region. XRD measurements show a residual deformation of only 0.05% in the implanted and annealed layer. The fact that basal loops are favoured against prismatic ones at high N concentration or high temperature is attributed to a lower stacking fault energy in these conditions. The coalescence of loops and their disappearance in the sub-surface region are ascribed to point defect diffusion. Finally, the electrical and optical properties of nitrogen-implanted ZnO are correlated with the observed structural features.Comment: 8 page

Defect-induced room temperature ferromagnetism in B-doped ZnO

ZnO microrods were grown on glass substrates by the spray pyrolysis method and boron was doped into the ZnO microrods by diffusion. X-ray diffraction results confirmed that the incorporation of B leads to a slight reduction in the deposit texture. Scanning electron microscopy measurements showed that the morphology of the ZnO samples changed from a microrod to nanocrystalline structure with B-doping. Photoluminescence data indicate that B-doping leads to a relative increase of the unstructured green band intensity. Magnetic measurements revealed that B-doped ZnO samples exhibited room temperature ferromagnetism related to defects, in agreement with first principles theoretical calculations

Wide Band Gap Single Wurtzite Ternary Alloy MgZnO Thin Film Grown by MBE

Ternary alloy MgZnO thin film on c-plane sapphire was obtained by radio-frequency (RF) plasma-assisted molecular beam epitaxy (MBE). The films were characterized by photoluminescence (PL), UV-visible absorption and X-ray diffraction (XRD). The band gap of ZnO based MgZnO ternary alloy thin film were be tuned from 3.71eV to 4.2eV at room temperature remaining single wurtzite structure. The band gap can be determined by Tauc plot of the absorption spectrum. High magnesium content ZnO based MgZnO ternary alloy thin films were achieved by controlling substrate temperature, cell temperature and buffer layer conditions. In this thesis we mainly investigated single wurtzite MgZnO ternary alloy as wide band gap ZnO based semiconductor material for fabricating optoelectronic devices

Vapor Phase Growth of ZnO Single Crystals/Thin Films and Attempts for p-type Doping

The growth of ZnO single crystals and ZnO thin films on Si substrates by an open-system vapor phase method was studied in this thesis. The as-grown ZnO single crystals were investigated by means of photoluminescence (PL). Two unique emissions were observed in virgin and hydrogenated crystals. The up-to-now attempts for the p-type doping of ZnO were summarized and our doping studies were performed using nitrogen and antimony. The seed-free and open-system vapor phase method is a simple and low cost approach to grow good quality ZnO single crystals. The growth parameters, including flow rates of N2, H2, O2, and growth temperatures, have various influences on the crystal growth, and also on the optical properties of the as grown crystals. The as-grown crystals are c-axis oriented needle crystals, and the crystals typically have a maximum length of 40 mm and a maximum diameter of 1 mm. The needle-shaped crystals are n-type with main donors due to Al, Ga, and In impurities, as determined from the PL spectra. Two unidentified PL emission lines (P1 at 3.3643 eV and P2 at 3.3462 eV) are observed in our vapor phase grown ZnO single crystals. P1 is attributed to the recombination of an exciton bound to a shallow donor，which has a binding energy of 42.2 meV. Hydrogenation of the as-grown ZnO single crystal leads to the appearance of the P2 line and a great reduction of the P1 line. Subsequent isochronal annealing in the ambient atmosphere leads to gradual reduction of P2 and the reappearance of P1. The PL measurements indicate that hydrogen is involved in the defect origins of the P2 line. ZnO thin films were deposited on Si substrates by the vapor phase method. Three different types of configurations with alternative source materials and oxidizers were employed and compared. It is demonstrated that, methods with lower growth temperatures are easier to deposit homogenous ZnO films on Si substrate. Donor-acceptor-pair (DAP) transition at 3.245 eV and its phonon replicas were observed in the PL spectra of the thin films, which are grown by the hydrogen-free vapor phase method. The appearance of DAP transition indicates the presence of acceptor in the films. The long-standing challenge of p-type doping in ZnO is mainly attributed to the low valence band maximum (VBM) at the absolute energy scale, the spontaneous formation of compensating defects and the lack of appropriate acceptors with small ionization energy. Two attempts for the p-type doping of ZnO were performed by nitrogen diffusion into ZnO single crystals from plasma after the growth or by in-situ doping antimony during the growth of ZnO films. No hole conductivity could however be achieved in our doped samples.In dieser Arbeit wurde das Wachstum von ZnO-Einkristallen und Dünnfilmschichten auf Si durch chemische Gasphasenabscheidung in einem offenen System untersucht. Die hergestellten ZnO-Einkristalle wurden mit Photolumineszenzmessungen (PL) untersucht. Es konnten sowohl in unbehandelten als auch in mit Wasserstoff behandelten Proben zwei charakteristische Linien beobachtet werden. Sowohl die bisherigen Versuche zur p-Typ Dotierung von ZnO als auch die in dieser Arbeit durchgeführten Versuche mit Stickstoff und Antimon werden zusammengefasst und präsentiert. Die Keimkristall-freie Gasphasenabscheidung (CVD) in offenen Systemen ist eine einfache und kostengünstige Methode zur Herstellung von qualitativ hochwertigen ZnO-Einkristallen. Die Wachstumsparameter, einschließlich der Flussraten von N2, H2 und O2 sowie der Wachstumstemperatur beeinflussen das Kristallwachstum sowie die optischen Eigenschaften der hergestellten Kristalle. Die hergestellten Kristalle wachsen typischerweise als entlang der c-Achse orientierte Nadeln mit Längen von bis zu 40 mm und Durchmessern von bis zu 1 mm. Die nadelförmigen Kristalle besitzen eine n-Typ Dotierung, welche hauptsächlich durch Verunreinigung mit Al, Ga und In verursacht wird. Zwei bisher nicht identifizierte PL-Linien (P1 bei 3,3643 eV und P2 bei 3,3462 eV) wurden in den hergestellten Kristallen beobachtet. P1 wird der Rekombination von Exzitonen an flachen Donatoren mit einer Bindungsenergie von 42,2 meV zugeordnet. Eine Wasserstoffbehandlung der hergestellten Kristalle führt zum Erscheinen der P2-Linie und einer starken Unterdrückung der P1-Linie. Anschließende isochronische Temperung in Luft führt zu einer schrittweisen Reduzierung der Intensität der P2-Linie und zu einer Verstärkung der P1-Linie. Photolumineszenzmessungen weisen auf eine Korrelation von P2 mit Wasserstoff hin. Zusätzlich wurden mit der CVD-Methode dünne ZnO-Schichten auf Si-Substraten abgeschieden. Drei unterschiedliche Konfigurationen mit verschiedenen Ausgangsmaterialien (ZnO-Pulver bw. Zn-Pulver) und verschiedenen Oxidationsmitteln (O2 bzw. Wasser) wurden untersucht und verglichen. Es wird gezeigt, dass mit den Konfigurationen mit geringerer Wachstumstemperatur am einfachsten homogene ZnO-Schichten auf Si abgeschieden werden können. Ein Donator-Akzeptor-Paar-Übergang (DAP) bei 3,245 eV und die dazugehörigen Phononenrepliken wurden in den Schichten beobachtet, welche in einer Wasserstoff-freien Konfiguration abgeschieden wurden. Diese DAP-Übergänge sind ein Hinweis auf die Anwesenheit von Akzeptoren. Die seit langem bestehende Herausforderung der p-Typ-Dotierung von ZnO hat ihre Wurzeln hauptsächlich in dem niedrig liegenden Valenzbandmaximum (VBM) auf der absoluten Energieskala, der spontanen Bildung von kompensierenden Defekten sowie dem Mangel an geeigneten Akzeptoren mit geringer Ionisierungsenergie. Zwei Versuche zur p-Typ-Dotierung von ZnO durch Behandlung der Kristalle mit N-Plasma bzw. durch in-situ Dotierung mit Sb während des Kristallwachstums wurden durchgeführt. Allerdings konnte damit keine nachweisbare Löcherleitung in den behandelten Proben erreicht werden

A single-molecule approach to ZnO defect studies: single photons and single defects

Investigations that probe defects one at a time offer a unique opportunity to observe properties and dynamics that are washed out of ensemble measurements. Here we present confocal fluorescence measurements of individual defects in Al-doped ZnO nanoparticles and undoped ZnO sputtered films that are excited with sub-bandgap energy light. Photon correlation measurements yield both antibunching and bunching, indicative of single-photon emission from isolated defects that possess a metastable shelving state. The single-photon emission is in the range 560 - 720 nm and typically exhibits two broad spectral peaks separated by approximately 150 meV. The excited state lifetimes range from 1 - 13 ns, consistent with the finite-size and surface effects of nanoparticles and small grains. We also observe discrete jumps in the fluorescence intensity between a bright state and a dark state. The dwell times in each state are exponentially distributed and the average dwell time in the bright (dark) state does (may) depend on the power of the exciting laser. Taken together, our measurements demonstrate the utility of a single-molecule approach to semiconductor defect studies and highlight ZnO as a potential host material for single-defect based applications.Comment: 33 pages, 7 figure

Polarity in GaN and ZnO: Theory, measurement, growth, and devices

This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. This article appeared in Appl. Phys. Rev. 3, 041303 (2016) and may be found at https://doi.org/10.1063/1.4963919.The polar nature of the wurtzite crystalline structure of GaN and ZnO results in the existence of a spontaneous electric polarization within these materials and their associated alloys (Ga,Al,In)N and (Zn,Mg,Cd)O. The polarity has also important consequences on the stability of the different crystallographic surfaces, and this becomes especially important when considering epitaxial growth. Furthermore, the internal polarization fields may adversely affect the properties of optoelectronic devices but is also used as a potential advantage for advanced electronic devices. In this article, polarity-related issues in GaN and ZnO are reviewed, going from theoretical considerations to electronic and optoelectronic devices, through thin film, and nanostructure growth. The necessary theoretical background is first introduced and the stability of the cation and anion polarity surfaces is discussed. For assessing the polarity, one has to make use of specific characterization methods, which are described in detail. Subsequently, the nucleation and growth mechanisms of thin films and nanostructures, including nanowires, are presented, reviewing the specific growth conditions that allow controlling the polarity of such objects. Eventually, the demonstrated and/or expected effects of polarity on the properties and performances of optoelectronic and electronic devices are reported. The present review is intended to yield an in-depth view of some of the hot topics related to polarity in GaN and ZnO, a fast growing subject over the last decade

Microscopic Dynamics and Transport of Hydrogen in Proton Conducting Oxides

The microscopic motion of hydrogen in solid oxides plays an important role in defect migration and reaction processes. Understanding the vibrational dynamics associated with both hydrogen-oxygen (O-H) bonds and the surrounding ionic environment allows one to better characterize these fundamental interactions. This thesis presents a comprehensive investigation into the vibrational decay dynamics of O-H and O-D stretch modes in crystalline oxides using time-resolved infrared pump-probe spectroscopy.;Measurements of the vibrational lifetimes of hydrogen related local modes in potassium tantalate (KTaO3) and titanium dioxide (TiO2 ) show that the localized O-H vibration is very closely tied to proton transport. In KTaO3 we find the lifetimes to be on the order of a few hundred picoseconds and determine that the vibrational decay is due to a lattice-assisted tunneling process. Furthermore, we identify the assisting phonon and extract the excited-state tunneling rate. In TiO2 we measure the lifetimes at only a few picoseconds. Here, the decay can be described by a classical hopping process. In both cases the absorption-stimulated transfer rate is found to be dramatically larger than spontaneous or thermally activated proton transfer.;These studies provide valuable information regarding the details and fundamentals of hydrogen-lattice interactions in solid oxides. Such insight is valuable for better understanding the role of hydrogen in materials important for a variety of applications ranging from optoelectronics to alternative energy technologies

PLD GROWTH OF HIGH QUALITY ZINC OXIDE THIN FILMS ON SI SUBSTRATES AND DEVICE DEVELOPMENT

Growth of high quality zinc oxide thin films on silicon substrates is particularly important because it combines the unique features of zinc oxide (ZnO) with mature CMOS technology and paves the way for device developments. However, this is a challenging task due to several technical and material-related fundamental issues which exist with the growth of this highly sought after compound semiconductor. In general, metal-oxide semiconductors suffer from non-stoichiometric growth which leads to unipolar doping properties, such as ZnO grows nominally n-type while NiO grows p-type. Thus, these materials can be doped easily either n or p-type while the other polarity is hard to achieve, if not impossible. Although methods for the growth of p-type films, using extrinsic doping or exotic precursors with post growth treatments have been reported on different substrates, the problem of controlled and stable extrinsic p-type doping of ZnO films remains an open subject for research. In the present work, we have achieved the growth of undoped p-type ZnO films on Si (100) substrates by pulsed laser deposition through the optimization of growth conditions and adjustments of growth dynamics. Currently no other reports of undoped p-type ZnO on Si substrates by PLD growth exist, showing stable p-type conductivity in a repeatable process. The structural, optical, and electrical properties of the grown films were examined using techniques such as X-ray photoelectron spectroscopy (XPS), X-ray diffraction spectroscopy (XRD), Photoluminescence spectroscopy (PL), Hall Effect four-point probe Van Der Pauw measurements, and Current-Voltage (I-V) measurements for the p-n heterojunctions. Electrical behavior of ZnO is generally attributed to intrinsic defects which include vacancies, interstitials, and anti-sites of Zn and O in addition to external contamination related defects such as hydrogen complexes. The effects of growth conditions and intrinsic defects including hydrogen contamination on the properties of the grown layers are studied. Moreover, the growth dynamics of ZnO polar planes, i.e. the stacking of O-2 and Zn+2 planes, on n and p-type Si substrates are discussed. Once material studies and growth optimizations are completed, high quality ZnO films are used in device fabrication. Two types of optoelectronic devices, a photoresistor and a Schottky diode are fabricated on Si substrates, and the electrical behavior of the devices are investigated. The high quality ZnO films also contributed to the development of a surface acoustic wave (SAW) biosensor

Electrical transport mechanisms of Neodymium-doped rare-earth semiconductors

This study reports the electrical properties of Nd-doped cerium oxide (CeO2) films synthesized by microwave assisted hydrothermal using a two-point probe technique. Positron annihilation lifetime spectroscopy studies evidenced that, as the Nd content rises, a structural disorder occurs. This is caused by an increase in oxygen vacancies surrounded with Nd (defective clusters), with the mean lifetime components ranging between 290 and 300 ps. Particle size estimation showed values from 8.6 to 28.9 nm. Along with the increase of neodymium impurities, also the conductivity increases, due to the hopping conduction mechanism between defective species. This gives rise to a response time of only 6 s, turning these materials candidates to realize gas sensor devices. Ab initio investigations showed that the improved electric conduction is boosted mostly by the reduced Nd2+ than the Ce3+, where the oxygen vacancies play a fundamental role.Fil: Vaz, Isabela C. F.. Federal University of Itajubá; BrasilFil: Macchi, Carlos Eugenio. Universidad Nacional del Centro de la Provincia de Buenos Aires; Argentina. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Somoza, Alberto Horacio. Universidad Nacional del Centro de la Provincia de Buenos Aires; Argentina. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Rocha, Leandro S. R.. Universidade Federal do São Carlos; BrasilFil: Longo, Elson. Universidade Federal do São Carlos; BrasilFil: Cabral, Luis. Universidade Estadual de Campinas; BrasilFil: da Silva, Edison Z.. Universidade Estadual de Campinas; BrasilFil: Simões, Alexandre Zirpoli. Universidade Estadual Paulista Julio de Mesquita Filho; BrasilFil: Zonta, Giulia. Università di Ferrara; ItaliaFil: Malagu, Cesare. Università di Ferrara; ItaliaFil: Desimone, Paula Mariela. Universidad Nacional de Mar del Plata; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Ponce, Miguel Adolfo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; Argentina. Universidad Nacional de Mar del Plata; ArgentinaFil: Moura, Francisco. Federal University of Itajubá; Brasi