Sn (II) oxide finds numerous applications in different fields such as thin film transistors1, solar cells2 and sensors.3 In this study we present the fabrication of tin monoxide SnO by using Sn (II) ketoacid oximate complexes as precursors. Tin (II) ketoacidoximates of the type [HON=CRCOO]2Sn where R= Me 1, R= CH2Ph 2, and [(MeON=CMeCOO)3Sn]- NH4 +.2H2O 3 were synthesized by in situ formation of the ketoacid oximate ligand. The crystal structures were determined via single crystal X- ray diffraction of the complexes 1-3 revealed square planar and square pyramidal coordination environments for the Sn atom. Intramolecular hydrogen bonding is observed in all the complexes. Furthermore, the complexes were characterized by Infrared (IR), Nuclear Magnetic Resonance (NMR) and elemental analysis. From thermogravimetric analysis of 1-3, it was found that the complexes decomposed in the range of 160 – 165 oC. Analysis of the gases evolved during decomposition indicated complete loss of the oximato ligand in one step and the formation of SnO. Spin coating of 1 on silicon or glass substrate show uniform coating of SnO. Band gaps of SnO films were measured and found to be in the range of 3.0 – 3.3 eV by UV-Vis spectroscopy. X-ray photoelectron spectroscopy indicated surface oxidation of the SnO film. Heating 1 above 140 oC in air gives SnO of size ranging from 10 – 500 nm and is spherical in shape. The SnO nanomaterial is characterized by powder X-ray diffraction(XRD), Raman spectroscopy, Scanning Electron Microscopy (SEM), and Transmission Electron Microscopy (TEM).

In the pursuit of enhancing the electronic properties of transparent p-type semiconductors, this work uses density functional theory to study the effects of doping tin monoxide with nitrogen, antimony, yttrium and lanthanum. An overview of the theoretical concepts and a detailed description of the methods employed are given, including a discussion about the correction scheme for charged defects proposed by Freysoldt and others [Freysoldt 2009]. Analysis of the formation energies of the defects points out that nitrogen substitutes an oxygen atom and does not provide charge carriers. On the other hand, antimony, yttrium, and lanthanum substitute a tin atom and donate n-type carriers. Study of the band structure and density of states indicates that yttrium and lanthanum improves the hole mobility. Present results are in good agreement with available experimental works and help to improve the understanding on how to engineer transparent p-type materials with higher hole mobilities.

Transparent oxide electronics have emerged as promising materials to shape the future of electronics. While several n-type oxides have been already studied and demonstrated feasibility to be used as active materials in thin film transistors, high performance p-type oxides have remained elusive. This dissertation is devoted to the study of transparent p-type oxide semiconductor tin monoxide and its use in the fabrication of field effect devices. A complete study on the deposition of tin monoxide thin films by direct current reactive magnetron sputtering is performed. Carrier density, carrier mobility and conductivity are studied over a set of deposition conditions where p-type conduction is observed. Density functional theory simulations are performed in order to elucidate the effect of native defects on carrier mobility. The findings on the electrical properties of SnO thin films are then translated to the fabrication of thin films transistors. The low processing temperature of tin monoxide thin films below 200 oC is shown advantageous for the fabrication of fully transparent and flexible thin film transistors. After careful device engineering, including post deposition annealing temperature, gate dielectric material, semiconductor thickness and source and drain electrodes material, thin film transistors with record device performance are demonstrated, achieving a field effect mobility >6.7 cm2V-1s-1. Device performance is further improved to reach a field effect mobility of 10.8 cm2V-1s-1 in SnO nanowire field effect transistors fabricated from the sputtered SnO thin films and patterned by electron beam lithography. Downscaling device dimension to nano scale is shown beneficial for SnO field effect devices not only by achieving a higher hole mobility but enhancing the overall device performance including better threshold voltage, subthreshold swing and lower number of interfacial defects. Use of p-type semiconductors in nonvolatile memory applications is then demonstrated by the fabrication of hybrid ferroelectric field effect transistors composed of organic ferroelectric layer polyvinylidene fluoride trifluoroethylene and inorganic p-type semiconductor tin monoxide. Both rigid and flexible devices are demonstrated, showing the advantages of low temperature oxides over polymer semiconductors by achieving much better performance, such as order of magnitude higher hole mobility.

Die vorliegende Arbeit ist eine umfassende Studie über das Wachstum mittels Molekularstrahlepitaxie (MBE) und die gemessenen Seebeck Koeffizienten und Lochtransport Eigenschaften von p‑Typ Oxiden, eine Materialklasse welche die optische Transparenz und die einstellbare Leitfähigkeit verbindet. Insbesondere, Nickeloxid (NiO) und Zinnmonoxid (SnO) wurden mittels plasmaunterstützter MBE unter Einsatz von einer Metall‑Effusionszelle und einem Sauerstoffplasma gewachsen. Für das NiO Wachstum wurden vor allem die Wachstumsgrenzen bei hohen Temperaturen festgelegt, welche von der Substratstabilität im Falle von Magnesiumoxid und Galliumnitrid abhängen. Es wird die Möglichkeit der Qualitätsbewertung mittels Ramanspektroskopie für Natriumchlorid-Strukturen gezeigt. Untersuchung der NiO Dotierung durch Oberflächen-Akzeptoren und der damit verbundenen Oberflächen‑Loch‑Anreicherungsschicht offenbart eine neue Dotierungsmöglichkeit für p‑leitende Oxide im Allgemeinen. Die metastabile Phase des SnO wird mittels PAMBE unter Verwendung bekannter Wachstumskinetik von Zinndioxid und verschiedener in‑situ Methoden stabilisiert, die anwendungsrelevante thermische Stabilität wird untersucht. Anschließende ex‑situ Charakterisierungen durch XRD und Ramanspektroskopie identifizieren das kleine Wachstumsfenster für das epitaktische Wachstum von SnO. Elektrische Messungen bestätigen die p‑Typ Ladungsträger mit vielversprechenden Löcherbeweglichkeiten welche auch für Hall Messungen zugänglich sind. Temperaturabhängige Hall Messungen zeigen einen bandähnlichen Transport welcher auf eine hohe Qualität der gewachsenen Schichten hindeutet. Die Funktionalität der gewachsenen Schichten wird durch verschiedene Anwendungen nachgewiesen. Zum Beispiel werden pn‑Heteroübergänge wurden durch das heteroepitaktische Wachstum der SnO Schichten auf einem Galliumoxid-Substrat erlangt. Die ersten bisher berichteten SnO-basierten pn‑Übergänge mit einem Idealitätsfaktor unter zwei wurden erreicht. / This thesis presents a comprehensive study on the growth by molecular beam epitaxy (MBE) and the measured Seebeck coefficients and hole transport properties of p‑type oxides, a material class which combines transparency and tunable conductivity. Specifically, Nickel oxide (NiO) and tin monoxide (SnO) were grown by plasma‑assisted MBE using a metal effusion cell and an oxygen plasma. For NiO growth, the focus lies on high temperature growth limits which were determined by the substrate stability of magnesium oxide and gallium nitride. Quality evaluation by Raman spectroscopy for rock‑salt crystal structures is demonstrated. Investigations of NiO doping by surface acceptors and the related surface hole accumulation layer reveal a new doping possibility for p‑type oxides in general. The meta‑stable SnO is stabilized by PAMBE utilizing known growth kinetics of tin dioxide and various in‑situ methods, its application-relevant thermal stability is investigated. Following ex‑situ characterizations by XRD and Raman spectroscopy identify secondary phases and a small growth window for the epitaxial growth of SnO. Electrical measurements confirm the p‑type carriers with promising hole mobilities accessible to Hall measurements. Temperature dependent Hall measurements show band‑like transport indicating a high quality of the grown layers. The functionality of the grown layers is proven by various applications. For example, pn‑heterojunctions were achieved by heteroepitaxial growth of the SnO layers on gallium oxide substrates. The first reported SnO based pn‑junction with an ideality factor below two is accomplished.