Characterization of Point Defects in Lithium Aluminate (LiAlO2) Single Crystals

Lithium aluminate (LiAlO2) is an insulating wide-band gap material currently under development for tritium breeding and radiation detection and dosimetry applications. Point defects are imperfections in a crystal lattice localized over a few atomic lengths that can alter the electrical, mechanical, or optical properties of materials. An understanding of point defect behavior is a necessary precursor for optimizing lithium aluminate for nuclear applications. This dissertation has identified and characterized the major point defects created and induced through x-ray and neutron radiation using electron paramagnetic resonance and fluorescence spectroscopy, thermoluminescence, and optical absorption. This dissertation explains for the first time the mechanism responsible for OSL in copper-diffused LiAlO2 and characterizes for the first time the hole (Li vacancies) and electron-trapping (F and F+ centers and transition-metal ions) defects. These results should prove useful to any researcher that utilizes LiAlO2 in applications involving radiation

Oxygen Vacancies in LiAlO\u3csub\u3e2\u3c/sub\u3e Crystals

Singly ionized oxygen vacancies are produced in LiAlO2 crystals by direct displacement events during a neutron irradiation. These vacancies, with one trapped electron, are referred to as V+O centers. They are identified and characterized using electron paramagnetic resonance (EPR) and optical absorption. The EPR spectrum from the V+O centers is best monitored near 100 K with low microwave power. When the magnetic field is along the [001] direction, this spectrum has a g value of 2.0030 and well-resolved hyperfine interactions of 310 and 240 MHz with the two 27Al nuclei that are adjacent to the oxygen vacancy. A second EPR spectrum, also showing hyperfine interactions with two 27Al nuclei, is attributed to a metastable state of the V+O center. An optical absorption band peaking near 238 nm is assigned to V+O centers. Bleaching light from a Hg lamp converts a portion of the V+O centers to V0O centers (these latter centers are oxygen vacancies with two trapped electrons). The V0O centers have an absorption band peaking near 272 nm, a photoluminescence band peaking near 416 nm, and a photoluminescence excitation band peaking near 277 nm. Besides the oxygen-vacancy EPR spectra, a holelike spectrum with a resolved, but smaller, hyperfine interaction with one 27Al nucleus is present in LiAlO2 after the neutron irradiation. This spectrum is tentatively assigned to doubly ionized aluminum vacancies

Lithium and Gallium Vacancies in LiGaO\u3csub\u3e2\u3c/sub\u3e Crystals

Lithium gallate (LiGaO2) is a wide-band-gap semiconductor with an optical gap greater than 5.3 eV. When alloyed with ZnO, this material offers broad functionality for optical devices that generate, detect, and process light across much of the ultraviolet spectral region. In the present paper, electron paramagnetic resonance (EPR) is used to identify and characterize neutral lithium vacancies (V0Li) and doubly ionized gallium vacancies (V2−Ga) in LiGaO2 crystals. These S = 1/2 native defects are examples of acceptor-bound small polarons, where the unpaired spin (i.e., the hole) is localized on one oxygen ion adjacent to the vacancy. Singly ionized lithium vacancies (V−Li) are present in as-grown crystals and are converted to their paramagnetic state by above-band-gap photons (x rays are used in this study). Because there are very few gallium vacancies in as-grown crystals, a post-growth irradiation with high-energy electrons is used to produce the doubly ionized gallium vacancies (V2−Ga). The EPR spectra allow us to establish detailed models for the two paramagnetic vacancies. Anisotropy in their g matrices is used to identify which of the oxygen ions adjacent to the vacancy has trapped the hole. Both spectra also have resolved structure due to hyperfine interactions with 69Ga and 71Ga nuclei. The V0Li acceptor has nearly equal interactions with Ga nuclei at two Ga sites adjacent to the trapped hole, whereas the V2−Ga acceptor has an interaction with Ga nuclei at only one adjacent Ga site

Copper Doping of ZnO Crystals by Transmutation of \u3csup\u3e64\u3c/sup\u3eZn to \u3csup\u3e65\u3c/sup\u3eCu: An Electron Paramagnetic Resonance and Gamma Spectroscopy Study

Transmutation of 64Zn to 65Cu has been observed in a ZnO crystal irradiated with neutrons. The crystal was characterized with electron paramagnetic resonance (EPR) before and after the irradiation and with gamma spectroscopy after the irradiation. Major features in the gamma spectrum of the neutron-irradiated crystal included the primary 1115.5 keV gamma ray from the 65Zn decay and the positron annihilation peak at 511 keV. Their presence confirmed the successful transmutation of 64Zn nuclei to 65Cu. Additional direct evidence for transmutation was obtained from the EPR of Cu2+ ions (where 63Cu and 65Cu hyperfine lines are easily resolved). A spectrum from isolated Cu2+ (3d9) ions acquired after the neutron irradiation showed only hyperfine lines from 65Cu nuclei. The absence of 63Cu lines in this Cu2+ spectrum left no doubt that the observed 65Cu signals were due to transmuted 65Cu nuclei created as a result of the neutron irradiation. Small concentrations of copper, in the form of Cu+-H complexes, were inadvertently present in our as-grown ZnO crystal. These Cu+-H complexes are not affected by the neutron irradiation, but they dissociate when a crystal is heated to 900 °C. This behavior allowed EPR to distinguish between the copper initially in the crystal and the copper subsequently produced by the neutron irradiation. In addition to transmutation, a second major effect of the neutron irradiation was the formation of zinc and oxygen vacancies by displacement. These vacancies were observed with EPR

Identification of the Zinc-oxygen Divacancy in ZnO Crystals

An electron paramagnetic resonance (EPR) spectrum in neutron-irradiated ZnO crystals is assigned to the zinc-oxygen divacancy. These divacancies are observed in the bulk of both hydrothermally grown and seeded-chemical-vapor-transport-grown crystals after irradiations with fast neutrons. Neutral nonparamagnetic complexes consisting of adjacent zinc and oxygen vacancies are formed during the irradiation. Subsequent illumination below ∼150 K with 442 nm laser light converts these (V2−Zn − V2+O)0 defects to their EPR-active state (V−Zn − V2+O)+ as electrons are transferred to donors. The resulting photoinduced S = 1/2 spectrum of the divacancy is holelike and has a well-resolved angular dependence from which a complete g matrix is obtained. Principal values of the g matrix are 2.00796, 2.00480, and 2.00244. The unpaired spin resides primarily on one of the three remaining oxygen ions immediately adjacent to the zinc vacancy, thus making the electronic structure of the (V−Zn − V2+O)+ ground state similar to the isolated singly ionized axial zinc vacancy. The neutral (V2−Zn − V2+O)0 divacancies dissociate when the ZnO crystals are heated above 250 °C. After heating above this temperature, the divacancy EPR signal cannot be regenerated at low temperature with light

Radiation-induced Defects in LiAlO\u3csub\u3e2\u3c/sub\u3e Crystals: Holes Trapped by Lithium Vacancies and Their Role in Thermoluminescence

Excerpt: Electron paramagnetic resonance (EPR) is used to identify the primary hole trap in undoped lithium aluminate (LiAlO2) crystals. Our interest in this material arises because it is a candidate for radiation detection applications involving either optically stimulated luminescence (OSL) or thermoluminescence (TL). © 2016 Elsevier B.V

Identification of defects responsible for optically stimulated luminescence (OSL) from copper-diffused LiAlO2 crystals

Excerpt:A large optically stimulated luminescence (CW-OSL) response has been observed from bulk lithium aluminate (LiAlO2) crystals that have been copper-diffused. © 2015 Elsevier B.V

Green Luminescence from Cu-diffused LiGaO\u3csub\u3e2\u3c/sub\u3e Crystals

An intense green luminescence is observed from single crystals of LiGaO2 doped with copper. Czochralski-grown undoped crystals are wrapped in thin copper foil and then held at 900 °C for 1 h in a flowing nitrogen atmosphere. Large concentrations of Cu+ ions enter the crystals during this process and occupy Li+ sites. These copper-diffused crystals are characterized with optical absorption, photoluminescence (PL), photoluminescence excitation (PLE), thermoluminescence (TL), and electron paramagnetic resonance (EPR). An optical absorption band peaking near 350 nm is assigned to the Cu+ ions at Li+ sites and represents an excitation from a 3d10 ground state to a 3d94s1 excited state. A broad PL emission from these excited Cu+ ions has a peak near 523 nm and the related PLE band has a peak near 356 nm (this PLE band links the emission to the optical absorption band). Illuminating a Cu-diffused crystal at room temperature with 325 nm laser light converts a portion of the Cu+ ions to Cu2+ ions. EPR spectra from these 3d9 ions are easily seen at low temperatures and their angular dependence is used to determine the g matrix and the 63Cu hyperfine matrix. Subsequent heating produces a TL peak near 122 °C with a maximum in its spectral dependence near 535 nm. Correlated EPR measurements show that this TL peak occurs when trapped electrons are thermally released from unintentionally present transition-metal ions (most likely Fe) and recombine with holes at the Cu2+ ions. © 2015 Elsevier B.V. All rights reserved