Insertion of Lithium Ions into TiO\u3csub\u3e2\u3c/sub\u3e (rutile) Crystals: An Electron Paramagnetic Resonance Study of the Li-associated Ti\u3csup\u3e3+\u3c/sup\u3e Small Polaron

Electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) are used to identify a Ti3+-Li+ complex in TiO2 crystals having the rutile structure. This defect consists of an interstitial Li+ ion adjacent to a substitutional Ti3+ ion (the unpaired electron on the Ti3+ ion provides charge compensation for the Li+ ion). The neutral Ti3+-Li+ complex is best described as a donor-bound small polaron and is similar in structure to the recently reported neutral fluorine and hydrogen donors in TiO2 (rutile). Lithium ions are diffused into the crystals at temperatures near 450 °C. Following the diffusion, an EPR spectrum containing groups of four closely spaced lines is observed at 36 K without laser illumination. ENDOR data verify that the four lines within each group are due to a weak hyperfine interaction with one lithium nucleus. Spin-Hamiltonian parameters are obtained from the angular dependence of the EPR spectra. Principal values are 1.9688, 1.9204, and 1.9323 for the g matrix and –2.14, –2.20, and +3.44 MHz for the 7Li hyperfine matrix

Sandstone matrix acidizing knowledge and future development

To meet rising global demands for energy, the oil and gas industry continuously strives to develop innovative oilfield technologies. With the development of new enhanced oil recovery techniques, sandstone acidizing has been significantly developed to contribute to the petroleum industry. Different acid combinations have been applied to the formation, which result in minimizing the near wellbore damage and improving the well productivity. A combination of hydrofluoric acid and hydrochloric acid (HF:HCl) known as mud acid has gained attractiveness in improving the porosity and permeability of the reservoir formation. However, high-temperature matrix acidizing is now growing since most of the wells nowadays become deeper and hotter temperature reservoirs, with a temperature higher than 200 °F. As a result, mud acid becomes corrosive, forms precipitates and reacts rapidly, which causes early consumption of acid, hence becoming less efficient due to high pH value. However, different acids have been developed to combat these problems where studies on retarded mud acids, organic-HF acids, emulsified acids, chelating agents have shown their effectiveness at different conditions. These acids proved to be alternative to mud acid in sandstone acidizing, but the reaction mechanism and experimental analysis have not yet been investigated. The paper critically reviews the sandstone acidizing mechanism with different acids, problems occurred during the application of different acids and explores the reasons when matrix stimulation is successful over fracturing. This paper also explores the future developing requirement for matrix acidizing treatments and new experimental techniques that can be useful for further development, particularly in developing new acids and acidizing techniques, which would provide better results and information of topology, morphology and mineral dissolution and the challenges associated with implementing these “new” technologies

Interstitial Silicon Ions in Rutile TiO\u3csub\u3e2\u3c/sub\u3e Crystals

Electron paramagnetic resonance (EPR) is used to identify a new and unique photoactive silicon-related point defect in single crystals of rutile TiO2. The importance of this defect lies in its assignment to interstitial silicon ions and the unexpected establishment of silicon impurities as a major hole trap in TiO2. Principal g values of this new S=1/2 center are 1.9159, 1.9377, and 1.9668 with principal axes along the [¯110],[001], and [110] directions, respectively. Hyperfine structure in the EPR spectrum shows the unpaired spin interacting equally with two Ti nuclei and unequally with two Si nuclei. These silicon ions are present in the TiO2 crystals as unintentional impurities. Principal values for the larger of the two Si hyperfine interactions are 91.4, 95.4, and 316.4 MHz with principal axes also along the [¯110],[001], and [110] directions. The model for the defect consists of two adjacent Si ions, one at a tetrahedral interstitial site and the other occupying a Ti site. Together, they form a neutral nonparamagnetic [Siint−SiTi]0 complex. When a crystal is illuminated below 40 K with 442-nm laser light, holes are trapped by these silicon complexes and form paramagnetic [Siint−SiTi]+ defects, while electrons are trapped at oxygen vacancies. Thermal anneal results show that the [Siint−SiTi]+ EPR signal disappears in two steps, coinciding with the release of electrons from neutral oxygen vacancies and singly ionized oxygen vacancies. These released electrons recombine with the holes trapped at the silicon complexes

Neutral Nitrogen Acceptors in ZnO: The \u3csup\u3e67\u3c/sup\u3eZn Hyperfine Interactions

Electron paramagnetic resonance (EPR) is used to characterize the 67Zn hyperfine interactions associated with neutral nitrogen acceptors in zinc oxide. Data are obtained from an n-type bulk crystal grown by the seeded chemical vapor transport method. Singly ionized nitrogen acceptors (N−) initially present in the crystal are converted to their paramagnetic neutral charge state (N0) during exposure at low temperature to 442 or 633 nm laser light. The EPR signals from these N0 acceptors are best observed near 5 K. Nitrogen substitutes for oxygen ions and has four nearest-neighbor cations. The zinc ion along the [0001] direction is referred to as an axial neighbor and the three equivalent zinc ions in the basal plane are referred to as nonaxial neighbors. For axial neighbors, the 67Zn hyperfine parameters are A‖ = 37.0 MHz and A⊥ = 8.4 MHz with the unique direction being [0001]. For nonaxial neighbors, the 67Zn parameters are A1 = 14.5 MHz, A2 = 18.3 MHz, and A3 = 20.5 MHz with A3 along a [10ˉ10] direction (i.e., in the basal plane toward the nitrogen) and A2 along the [0001] direction. These 67Zn results and the related 14N hyperfine parameters provide information about the distribution of unpaired spin density at substitutional neutral nitrogen acceptors in ZnO

Hydrogen Donors and Ti\u3csup\u3e3+\u3c/sup\u3e ions in reduced TiO\u3csub\u3e2\u3c/sub\u3e crystals

Electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) are used to identify and characterize the neutral hydrogen donor in TiO2 crystals having the rutile structure. These spectra are best observed near 5 K. The neutral donors are present without photoexcitation in crystals that have been slightly reduced at high temperature in a nitrogen atmosphere. The same defects can be photoinduced at low temperature in oxidized crystals. The neutral hydrogen donor in this lattice consists of a substitutional Ti3+ ion adjacent to a substitutional OH– molecular ion. The axis of the OH– molecule lies in the basal plane with the hydrogen ion extending out from the oxygen in a direction perpendicular to the Ti-O bonds. Spin-Hamiltonian parameters are obtained from the angular dependence of the EPR and ENDOR spectra (principal values are 1.9732, 1.9765, and 1.9405 for the g matrix and –0.401, + 0.616, and –0.338 MHz for the 1H hyperfine matrix). The principal axis associated with the + 0.616 MHz principal value is in the basal plane 22.9° from a [110] direction and the principal axis associated with the –0.338 MHz principal value is along the [001] direction. Our results show that interstitial Ti3+ ions are not the dominant shallow donors in slightly reduced TiO2 (rutile) crystals

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

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

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

Observation Of Singly Ionized Selenium Vacancies In Znse Grown By Molecular Beam Epitaxy

Electron paramagnetic resonance(EPR) has been used to investigate singly ionized selenium vacancy V Se + centers in ZnSe epilayers grown by molecular beam epitaxy(MBE). The study included undoped and nitrogen-doped films. Spectra taken at 8 K and 9.45 GHz, as the magnetic field was rotated in the plane from [100] to [010], showed an isotropic signal at g =2.0027±0.0004 with a linewidth of 5.8 G. In the two samples where this signal was observed, estimates of concentration were approximately 1.1×10 17 and 6.3×10 17 cm −3 . The appearance of the EPR signal correlated with an increase in the Zn/Se beam equivalent pressure ratio (during growth) in undoped films and with an increase in the nitrogen concentration in doped films. We conclude that the singly ionized selenium vacancy may be a dominant point defect in many MBE-grown ZnSe layers and that these defects may play a role in the compensation mechanisms in heavily nitrogen-doped ZnSe thin films

Transition-metal ions in β-Ga\u3csub\u3e2\u3c/sub\u3eO\u3csub\u3e3\u3c/sub\u3e crystals: Identification of Ni acceptors

Excerpt: Transition-metal ions (Ni, Cu, and Zn) in β-Ga2O3 crystals form deep acceptor levels in the lower half of the bandgap. In the present study, we characterize the Ni acceptors in a Czochralski-grown crystal and find that their (0/−) level is approximately 1.40 eV above the maximum of the valence band