Luminescence in Lithium Borates

Spectrometry methods are used to identify and characterize point defects in single crystals of lithium tetraborate (Li2B4O7) and lithium triborate (LiB3O5) doped with silver or copper, and explore the role of these point defects in luminescence. New defects are identified in Ag-doped including: lithium vacancy substitutional-silver-ion defect-pairs (hole trap); isolated lithium vacancies (hole trap); isolated oxygen vacancies (electron trap); interstitial-silver-ion substitutional-silver-ion defect pairs (electron trap); isolated interstitial silver ions (electron trap); and interstitial-silver-ion lithium-vacancy defect pairs (electron trap). Defect models are proposed, and adjustments made to defect models known defects. Defects in Ag-doped LiB3O5 and Cu-doped LiB3O5 are identified including: two species of interstitial-silver-ions (electron traps); isolated-substitutional-silver-ion (hole trap); lithium vacancy substitutional-silver-ion defect pairs (hole trap); interstitial-silver-ion substitutional-silver-ion defect pairs (electron trap); a species of interstitial-copper-ion (electron trap); isolated-substitutional-copper-ion (hole trap); and lithium vacancy substitutional-copper-ion defect pairs (hole trap). Based on this assessment, Ag-doped LiB3O5 is a promising TL and OSL dosimetry material while Cu-doped LiB3O5 is not

Gallium Vacancies in β-Ga\u3csub\u3e2\u3c/sub\u3eO\u3csub\u3e3\u3c/sub\u3e Crystals

The gallium vacancy, an intrinsic acceptor, is identified in β-Ga2O3 using electron paramagnetic resonance (EPR). Spectra from doubly ionized (V2−Ga) and singly ionized (V−Ga) gallium vacancies are observed at room temperature, without photoexcitation, after an irradiation with high-energy neutrons. The V2−Ga centers (with S = 1/2) have a slight angular variation due to a small anisotropy in the g matrix (principal values are 2.0034, 2.0097, and 2.0322). The V2−Ga centers also exhibit a resolved hyperfine structure due to equal and nearly isotropic interactions with the 69,71Ga nuclei at two Ga sites (the hyperfine parameters are 1.28 and 1.63 mT for the 69Ga and 71Ga nuclei, respectively, when the field is along the a direction). Based on these g-matrix and hyperfine results, the model for the ground state of the doubly ionized vacancy (V2−Ga) has a hole localized on one threefold-coordinated oxygen ion. The vacancy is located at one of the three neighboring gallium sites, and the remaining two gallium neighbors are responsible for the equal hyperfine interactions. The singly ionized (V−Ga) gallium vacancies are also paramagnetic. In this latter acceptor, the two holes are localized on separate oxygen ions adjacent to one gallium vacancy. Their spins align parallel to give a triplet S = 1 EPR spectrum with resolved hyperfine structure from interactions with gallium neighbors

Self-trapped Holes in β-Ga\u3csub\u3e2\u3c/sub\u3eO\u3csub\u3e3\u3c/sub\u3e Crystals

We have experimentally observed self-trapped holes (STHs) in a β-Ga2O3 crystal using electron paramagnetic resonance (EPR). These STHs are an intrinsic defect in this wide-band-gap semiconductor and may serve as a significant deterrent to producing usable p-type material. In our study, an as-grown undoped n-type β-Ga2O3 crystal was initially irradiated near room temperature with high-energy neutrons. This produced gallium vacancies (acceptors) and lowered the Fermi level. The STHs (i.e., small polarons) were then formed during a subsequent irradiation at 77 K with x rays. Warming the crystal above 90 K destroyed the STHs. This low thermal stability is a strong indicator that the STH is the correct assignment for these new defects. The S = 1/2 EPR spectrum from the STHs is easily observed near 30 K. A holelike angular dependence of the g matrix (the principal values are 2.0026, 2.0072, and 2.0461) suggests that the defect\u27s unpaired spin is localized on one oxygen ion in a nonbonding p orbital aligned near the a direction in the crystal. The EPR spectrum also has resolved hyperfine structure due to equal and nearly isotropic interactions with 69,71Ga nuclei at two neighboring Ga sites. With the magnetic field along the a direction, the hyperfine parameters are 0.92 mT for the 69Ga nuclei and 1.16 mT for the 71Ga nuclei

Electron Paramagnetic Resonance Study of Neutral Mg Acceptors in β-Ga\u3csub\u3e2\u3c/sub\u3eO\u3csub\u3e3\u3c/sub\u3e Crystals

Electron paramagnetic resonance (EPR) is used to directly observe and characterize neutral Mg acceptors (Mg0Ga) in a β-Ga2O3 crystal. These acceptors, best considered as small polarons, are produced when the Mg-doped crystal is irradiated at or near 77 K with x rays. During the irradiation, neutral acceptors are formed when holes are trapped at singly ionized Mg acceptors (Mg−Ga). Unintentionally present Fe3+ (3d5) and Cr3+ (3d3) transition-metal ions serve as the corresponding electron traps. The hole is localized in a nonbonding p orbital on a threefold-coordinated oxygen ion adjacent to an Mg ion at a sixfold-coordinated Ga site. These Mg0Ga acceptors (S = 1/2) have a slightly anisotropic g matrix (principal values are 2.0038, 2.0153, and 2.0371). There is also partially resolved 69Ga and 71Ga hyperfine structure resulting from unequal interactions with the two Ga ions adjacent to the hole. With the magnetic field along the a direction, hyperfine parameters are 2.61 and 1.18 mT for the 69Ga nuclei at the two inequivalent neighboring Ga sites. TheMg0Ga acceptors thermally convert back to their nonparamagnetic Mg−Ga charge state when the temperature of the crystal is raised above approximately 250 K

Defect-related Optical Absorption Bands in CdSiP\u3csub\u3e2\u3c/sub\u3e Crystals

When used as optical parametric oscillators, CdSiP2 crystals generate tunable output in the mid-infrared. Their performance, however, is often limited by unwanted optical absorption bands that overlap the pump wavelengths. A broad defect-related optical absorption band peaking near 800 nm, with a shoulder near 1 µm, can be photoinduced at room temperature in many CdSiP2 crystals. This absorption band is efficiently produced with 633 nm laser light and decays with a lifetime of ∼0.5 s after removal of the excitation light. The 800 nm band is accompanied by a less intense absorption band peaking near 1.90 µm. Data from eight CdSiP2crystals grown at different times show that the singly ionized silicon vacancy (V-Si) is responsible for the photoinduced absorption bands. Electron paramagnetic resonance (EPR) is used to identify and directly monitor these silicon vacancies. © 2017 Optical Society of Americ

Electron Traps in Ag-doped Li\u3csub\u3e2\u3c/sub\u3eB\u3csub\u3e4\u3c/sub\u3eO\u3csub\u3e7\u3c/sub\u3e Crystals: The role of Ag Interstitial Ions

Electron paramagnetic resonance (EPR) is used to establish models for electron traps in Ag-doped lithium tetraborate (Li2B4O7) crystals. When exposed at room temperature to ionizing radiation, electrons are trapped at interstitial Ag+ ions and holes are trapped at Ag+ ions on Li+ sites. The trapped electrons occupy a 5s1 orbital on the interstitial Ag ions (some of the unpaired spin density is also on neighboring ions). Three EPR spectra are assigned to electrons trapped at interstitial Ag ions. Their g values are near 1.99 and they have resolved hyperfine structure from 107Ag and 109Ag nuclei. The spectrum representing the largest concentration of trapped electrons has the unpaired spin shared by the interstitial Ag ion and an adjacent boron ion at its regular lattice site. A 10B enriched crystal verifies this assignment and an analysis of spin-Hamiltonian parameters yields information about the Ag and B orbitals occupied by the unpaired spin. The second spectrum has the unpaired spin shared equally by two Ag ions, one at an interstitial site and the other at an adjacent Li site. The third spectrum has a large Ag hyperfine interaction and a weak Li interaction. Optical absorption bands associated with the trapped electrons are observed between 225 and 500 nm. Thermal release of electrons from these traps is responsible for a prominent thermoluminescence peak near 150 °C, whereas optical release of the electrons at room temperature produces intense optically stimulated luminescence. Radiative recombination occurs at Ag2+ ions with emission peaking near 270 nm

Ir \u3csup\u3e4+\u3c/sup\u3e Ions in β-Ga\u3csub\u3e2\u3c/sub\u3eO\u3csub\u3e3\u3c/sub\u3e Crystals: An Unintentional Deep Donor

Electron paramagnetic resonance (EPR) and infrared absorption are used to detect Ir4+ ions in β-Ga2O3 crystals. Mg and Fe doped crystals are investigated, and concentrations of Ir4+ ions greater than 1 × 1018 cm−3 are observed. The source of the unintentional deep iridium donors is the crucible used to grow the crystal. In the Mg-doped crystals, the Ir4+ ions provide compensation for the singly ionized Mg acceptors and thus contribute to the difficulties in producing p-type behavior. The Ir4+ ions replace Ga3+ ions at the Ga(2) sites, with the six oxygen neighbors forming a distorted octahedron. A large spin-orbit coupling causes these Ir4+ ions to have a low-spin (5d5, S = 1/2) ground state. The EPR spectrum consists of one broad line with a significant angular dependence. Principal values of the g matrix are 2.662, 1.815, and 0.541 (with principal axes near the crystal a, b, and c directions, respectively). Ionizing radiation at 77 K decreases the Ir4+ EPR signal in Mg-doped crystals and increases the signal in Fe-doped crystals. In addition to the EPR spectrum, the Ir4+ ions have an infrared absorption band representing a d-d transition within the t2g orbitals. At room temperature, this band peaks near 5153 cm−1 (1.94 μm) and has a width of 17 cm−1. The band is highly polarized: its intensity is maximum when the electric field E is parallel to the b direction in the crystal and is nearly zero when E is along the c direction

Possible Detection of Low Energy Solar Neutrons Using Boron Based Materials

Solar neutrons have been detected aboard the International Space Station (ISS), using lithium tetraborate and boron carbide detector elements. We find that evidence of a solar neutron flux, as detected in a neutron calorimeter following subtraction of the proton background, with an energy of about 2 to 4 MeV. This solar neutron flux is likely no more than 250 to 375 neutrons cm−2sec−1, with a lower bound of 50–75 neutrons cm−2sec−1 at one au

Optically Stimulated Luminescence (OSL) from Ag-doped Li\u3csub\u3e2\u3c/sub\u3eB\u3csub\u3e4\u3c/sub\u3eO\u3csub\u3e7\u3c/sub\u3e Crystals

Optically stimulated luminescence (CW-OSL) is observed from Ag-doped lithium tetraborate (Li2B4O7) crystals. Photoluminescence, optical absorption, and electron paramagnetic resonance (EPR) are used to identify the defects participating in the OSL process. As-grown crystals have Ag+ ions substituting for Li++ ions occupying interstitial sites. During a room-temperature exposure to ionizing radiation, holes are trapped at the Ag+ ions that replace Li++ ions, i.e., the radiation forms Ag2+ (4d9 ) ions and Ag0 (4d105s1 ) atoms. These Ag2+ and Ag0 centers have characteristic EPR spectra. The Ag0 centers also have a broad optical absorption band peaking near 370 nm. An OSL response is observed when the stimulation wavelength overlaps this absorption band. Specifically, stimulation with 400 nm light produces an intense OSL response when emission is monitored near 270 nm. Electrons optically released from the Ag0 centers recombine with holes trapped at Ag2+ ions to produce the ultraviolet emission. The OSL response is progressively smaller as the stimulation light is moved to longer wavelengths (i.e., away from the 370 nm peak of the absorption band of the Ag0 electron traps). Oxygen vacancies are also present in the Ag-doped Li2B4O7 crystals, and their role in the OSL process as a secondary relatively short-lived electron trap is described