Doctor of Philosophy / Department of Chemical Engineering / James H. Edgar / The sublimation recondensation crystal growth of aluminum nitride, titanium nitride, and yttrium nitride were explored experimentally and theoretically. Single crystals of these nitrides are potentially suitable as substrates for AlGaInN epitaxial layers, which are employed in ultraviolet optoelectronics including UV light-emitting diodes and laser diodes, and high power high frequency electronic device applications. A thermodynamic analysis was applied to the sublimation crystal growth of aluminum nitride to predict impurities transport (oxygen, carbon, and hydrogen) and to study the aspects of impurities incorporation for different growth conditions. A source purification procedure was established to minimize the impurity concentration and avoid degradation of the crystal’s properties. More than 98% of the oxygen, 99.9% of hydrogen and 90% of carbon originally in the source was removed. The AlN crystal growth process was explored in two ways: self-seeded growth with spontaneous nucleation directly on the crucible lid or foil, and seeded growth on SiC and AlN. The oxygen concentration was 2 ~ 4 x 1018cm-3, as measured by secondary ion mass spectroscopy in the crystals produced by self-seeded growth. Crystals grown from AlN seeds have visible grain size expansion. The initial AlN growth on SiC at a low temperature range (1400°C ~1600°C) was examined to understand the factors controlling nucleation. Crystals were obtained from c-plane on-axis and off-axis, Si-face and C-face, as well as m-plane SiC seeds. In all cases, crystal growth was fastest perpendicular to the c-axis. The growth rate dependence on temperature and pressure was determined for TiN and YN crystals, and their activation energies were 775.8±29.8kJ/mol and 467.1±21.7kJ/mol respectively. The orientation relationship of TiN (001) || W (001) with TiN [100] || W [110], a 45o angle between TiN [100] and W [100], was seen for TiN crystals deposited on both (001) textured tungsten and randomly orientated tungsten. Xray diffraction confirmed that the YN crystals were rock-salt structure, with a lattice constant of 4.88Å. Cubic yttria was detected in YN sample from the oxidation upon its exposed to air for limited time by XRD, while non-cubic yttria was detected in YN sample for exposures more than one hour by Raman spectra.

Master of Science / Department of Chemical Engineering / James H. Edgar / Boron nitride is a purely synthetic material that has been known for over 150 years but only recently has sparked interest as a semiconductor material due to its potential in ultraviolet lasing and neutron detection. Thin-layer hexagonal boron nitride (hBN) is probably most attractive as a complementary material to graphene during its intense research endeavors. But for hBN to be successful in the realm of semiconductor technology, methods for growing large single crystals are critical, and its properties need to be accurately determined. In this study, hBN crystals were grown from metal solvents. The effects of soak temperature, soak time, source materials and their proportions on hBN crystal size and properties were investigated. The largest crystals of hBN measured five millimeters across and about 30 micrometers thick by precipitation from BN powder dissolved in a nickel-chromium solvent at 1700°C. High temperatures promoted outward growth of the crystal along the a-axis, whereas low temperatures promoted growth along the c-axis. Crystal growth at high temperatures also caused bulk hBN to adopt a triangular habit rather than a hexagonal one. A previously unreported method of synthesizing hBN was proven successful by substituting BN powder with elemental boron and a nitrogen ambient. XRD and Raman spectroscopy confirmed hBN from solution growth to be highly crystalline, with an 8.0 cm[superscript]-1 FWHM of the Raman peak being the narrowest reported. Photoluminescence spectra exhibited peaks mid-gap and near the band edge, suggesting impurities and defects in the hBN samples. However, high-purity reactants and post-growth annealing showed promise for synthesizing semiconductor-grade hBN. Several etchants were explored for defect-selective etching of hBN. A molten eutectic mixture of KOH/NaOH was the most effective defect-selective etchant of hBN at temperatures of 430-450°C for about one minute. The two prevalent hexagonal etch pit morphologies observed were deep, pointed-bottom pits and shallow, flat-bottom pits. TEM and SAED confirmed basal plane twists and dislocations in hBN crystals, but due to the highly anisotropic nature of hBN, their existence may be inevitable no matter the growth technique.

Master of Science / Department of Chemical Engineering / James H. Edgar / Hexagonal boron nitride has been used as an inert, refractory material with excellent resistance to thermal decomposition and oxidation for more than fifty years. In the past few years, hBN has been targeted for potential electrical and optical devices such as neutron detectors, ultraviolet light emitters, deep ultraviolet light detectors, and substrates for graphene and other atomically-thin two-dimensional materials. All of these potential applications benefit from high quality, single crystals, with thicknesses varying from nanometers to microns. This research was undertaken to investigate four aspects of hBN crystal growth and recovery. (1) In an effort to optimize hBN crystal growth from a nickel-chromium flux, a series of stepped cooling experiments were undertaken. The temperature profile was stepped in a way as to promote growth in both the a and c directions, at their optimal growth conditions. Crystals were found to be typically 100-500 µm across and thickness of approximately 20-30 µm with a pyramid-like crystal habit. (2) A method for the removal of hBN crystals prior to freezing of the metal flux was demonstrated using a specialized hot pressed boron nitride crucible capable of removing hBN crystals from the flux in situ. (3) Growth of isotopically pure hBN crystals was undertaken. By modifying the crucible material for solution growth, enrichment of hBN crystals over 90% was accomplished. (4) Exfoliation of hBN has many potential applications, specifically as graphene-hBN heterostructures where layers approaching thicknesses of single atoms are most effective surface to interact with graphene as an electronic device. Several methods were tested toward exfoliating a single crystal resulting in few-layered hexagonal boron nitride nanosheets. As a result of these investigations a greater understanding of hBN bulk growth, its isotopic enrichment, its recovery, and its exfoliation was obtained.

Semiconductor devices are the building blocks of electronics and communication technology in the modern world. The charge, mass and spin of charge carriers in the semiconductor devices lay the foundations of the technology developments in the modern age. But to date only the electronic charge of the semiconductors has been exploited for such applications. The significance of the spin of charge carriers is completely ignored because in a semiconductor the half of the carriers are in spin-up state and the remainder are in spin-down state. A new electronics termed as spintronics, spin-transport based electronics, is focused to utilise the spin degree of freedom of the charge carriers in addition to its electronic charge. The devices based on these have the potential for various technological advancements like non-volatility, increased data processing speed, decreased electronic power consumption and increased integration densities as compared to the conventional semiconductor devices. In this study, the author intended to study the growth and properties of magnetic impurity doped antimony based III-V compounds and compare these results with those of the films grown by MBE. This thesis is organised into seven chapters. The first introductory chapter gives a brief review of the work on spintronics, diluted magnetic semiconductors, Ferromagnetic / paramagnetic semiconductor hybrid structures with special emphasis on the properties of antimonides which have already been reported in the literature. This is followed by the scope of the thesis. The second chapter deals with technical details of various instruments used in the present research work. Third chapter describes the growth and structural properties of bulk crystals grown by Bridgman method and thin films grown by liquid phase epitaxy (LPE). Bulk crystals of InSb and GaSb doped with magnetic elements such as Mn and Fe are grown with different doping concentrations. Thin films of InSb and GaSb doped Mn with different doping concentrations are grown by LPE. The grown crystals are processed by slicing, lapping, polishing and chemical etching methods. X-ray diffraction studies are carried out to confirm alloy formation and to find the change in lattice parameter if any. From the powder diffraction patterns, the lattice parameter is refined with the help of Retvield refinement program. A systematic change of lattice parameter with the incorporation of magnetic impurities into InSb and GaSb is observed. Scanning electron microscopy and energy dispersive x-ray analysis are carried out to identify the secondary phases and their composition respectively. Chapter 4 gives the detailed magnetotransport studies carried out on InSb and GaSb crystals doped with Mn and Fe. Also, the magnetotransport studies carried out on thin films grown by liquid phase epitaxy are presented here. This chapter is divided into three sections of which the first section deals with Mn doped bulk crystals of InSb and GaSb, the second section deals with Fe doped bulk crystals of InSb and GaSb and the third section deals with Mn doped InSb and GaSb films grown on GaAs by Liquid Phase Epitaxy. Temperature dependence of zero field resistivity, magnetoresistance and Hall measurements are carried out from 1.4 to 300K. All the samples show p type conduction throughout the temperature range studied except for Fe doped InSb. Mn doped crystals show negative magnetoresistance and anomalous Hall effect below 10K. Anisotropy in magnetoresistance is also observed at low temperatures in InMnSb crystals. On the other hand, Fe doped samples exhibit positive magnetoresistance throughout the temperature range and no anomalous Hall effect is observed. Chapter 5 describes the magnetic properties of bulk InMnSb, GaMnSb, InFeSb and GaFeSb crystals so also the thin films of InMnSb/GaAs. DC magnetization measurements are carried out in the temperature range 2 - 300K. The Mn doped InSb and GaSb crystals as well as InMnSb/GaAs films, show a magnetic ordering below 10K which could arise from the InMnSb and GaMnSb alloy formation. Also, saturation in magnetization observed even at room temperature suggests the existence of ferromagnetic MnSb clusters in the crystals which has been verified by scanning electron microscopy studies. In Fe doped InSb crystals, the temperature dependent DC magnetization shows irreversibility under field cooled and zero field cooled conditions below 12K, suggesting a spin glass-like behaviour. Also, magnetization measurement shows the coexistence of ferromagnetic and paramagnetic phases throughout the temperature range studied. Existence of ferromagnetic phase could arise from secondary phases Fe1-xInx or FeSb2 present in the crystal as clusters and paramagnetic phase could arise from the randomly distributed Fe atoms in the InSb matrix. Fe doped GaSb crystals show interesting magnetic property that arises from the FeGa alloy (secondary phase) present in it. The EPR studies on Ga0.98Mn0.02Sb cluster-free (?) crystal suggest that the dominant Mn impurity in GaMnSb is Mn2+ (d5), described as ionized acceptor A−. This conclusion was derived from EPR experiments, which reveal a strong absorption line with an effective g factor very close to 2.00, the value typical for centre A−. The absence of EPR signal typical for neutral Mn acceptor A0 suggests that this center is absent in the crystal under investigation. The observed behavior is similar to that of Ga1-xMnxAs and In1-xMnxAs epilayers. EPR studies also reveal that the competition between antiferromagnetic and ferromagnetic phases exists in the studied crystal. Chapter 6 describes the optical measurements carried out on bulk Ga1-xMnxSb crystals and their films with different Mn doping concentrations. FTIR studies are carried out in the temperature range 4 - 300 K. From the FTIR studies, it is found that intra valance spin – orbit splitting band absorption is dominant compared to the fundamental absorption in doped crystals. In higher doped crystals (x > 0.01), fundamental band absorption merges with split-off band and could not be resolved. Free carrier absorption studies are also carried out in the energy range below the band gap. FTIR studies on GaMnSb/GaAs films suggest band gap narrowing effect due to Mn doping. Furthermore the Photoluminescence measurements are carried out in the temperature range 10 – 300 K for all the Mn doped GaSb crystals. PL studies also support the band gap narrowing and band filling effects. A comprehensive summary of this research investigation and scope for the further work are presented in the last chapter.

The semiconducting compounds CdTe and CdZnTe have important applications in high-energy radiation detectors and as substrates for infrared devices. The materials offer large band gaps, high resistivity, and excellent charge transport properties; however all of these properties rely on very precise control of the material composition. Growing bulk crystals by the travelling heater method (THM) offers excellent compositional control and fewer defects compared to gradient freezing, but it is also much slower and more expensive. A particular challenge is the current need to grow new crystals onto existing seeds of similar size and quality. Simulations and experiments are used in this work to investigate the feasibility of growing these materials by THM without the use of large seed crystals. A new fixed-grid, multiphase finite element model was developed based on the level set method and used to calculate the mass transport regime and interface shapes inside the growth ampoule. The diffusivity of CdTe in liquid tellurium was measured through dissolution experiments, which also served to validate the model. Simulations of tapered THM growth find conditions similar to untapered growth with interface shapes that are sensitive to strong thermosolutal convection. Favourable growth conditions are achievable only if convection can be controlled. In preliminary experiments, tapered GaSb crystals were successfully grown by THM and large CdTe grains were produced by gradient freezing. Beginning with this seed material, 25 mm diameter CdTe and CdZnTe crystals were grown on 10 mm diameter seeds, and 65 mm diameter CdTe on 25 mm seeds. Unseeded THM growth was also investigated, as well as ampoule rotation and a range of thermal conditions and ampoule surface coatings. Outward growth beyond one or two centimeters was achieved only at small diameters and included secondary grains and twin defects; however, limited outward growth of larger seeds and agreement between experimental and numerical results suggest that tapered growth may be achievable in the future. This would require active temperature control at the base of the crystal and reduction of convection through thermal design or by rotation of the ampoule or applied magnetic fields. / Graduate / 0346 / 0794 / 0548 / jordan.roszmann@gmail.com