Titanium is one of the earth-abundant elements, and its oxides including titanium dioxide (TiO2) and strontium titanium oxide (SrTiO3) are widely used in technologies of electronics, energy conversion, catalysis, sensing, and so on. Generally, the Ti ions in these compounds have a valence of 4+ with the outer shell electron configuration of 3d0. In this thesis, we explore interface and titanite containing Ti3+ ions with 3d1 itinerate electrons, which we believe open new doors towards some new titanite-based technologies.
In the first part of this thesis (Chapter 3), we will discuss the nanoscale chemical and valence evolution at a metal/oxide interface: Ti/SrTiO3. In many devices, metal-oxide interfaces are ubiquitous and play important roles in the performance of a wide range of electronic and optoelectronic devices. This motivated us to examine the microscopic structure of the interfaces between strontium titanium oxide and metals. In this work, one unit cell of cubic perovskite Ti2O3 was observed at the Ti/SrTiO3 interface, and oxygen diffusion depth of ~3.2 nm was observed in the sample fabricated at room temperature. Meanwhile, oxygen vacancy domains in the SrTiO3 substrates was observed and characterized by low angle annular dark field (LAADF) imaging and electron energy loss spectra (EELS).
In the main part of this thesis, we will focus on the structure and physical properties of Ti2O3, a titanite which has received less attention so far in the research community. Different from TiO2 and SrTiO3, Ti2O3 has a much narrower band-gap (~0.1 eV), and we will discuss some preliminary results of its physical properties and potential applications.
In Chapter 4, we will discuss the photothermal application and mid-infrared photodetectors using Ti2O3 nanoparticles based on its ultra-narrow bandgap. Photo-thermal effect via a Ti2O3/membrane structure is further applied to seawater desalination. A high temperature of 70 °C was achieved when this Ti2O3/membrane double layer structure floating on top surface of water subjected to the white light illumination of 7 kW/cm2. Furthermore, room temperature mid-infrared (10 μm) photodetectors based on Ti2O3/graphene hybrid structure was fabricated and studied. The photoresponsivity of this hybrid device, operated from 4.5 to 10 μm, is above ~ 100 A/W, which, to our knowledge, is the highest value for the mid-infrared photodetectors operating in the photocurrent (PC) mode.
In chapter 5, structure, optical, transport properties of Ti2O3 epitaxial thin films on sapphire fabricated by pulsed laser deposition (PLD) will be discussed. By tailoring growth conditions, two different: trigonal and orthorhombic, of Ti2O3 were stabilized on Al2O3 substrates. More interestingly, the orthorhombic Ti2O3 has never been reported, and, moreover, superconductivity (~8 K) and high temperature ferromagnetism (up to 700 K) was discovered in this new stabilized phase. More details of the physical properties of Ti2O3 will be discussed in the following chapters of this dissertation.
|Date of Award
|Nov 8 2016
- Physical Sciences and Engineering
|Tao Wu (Supervisor)
- Titanium Sesquioxide
- Epitaxial Thin Films
- Carrier Behavior