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

The Electronic Structure and Secondary Pyroelectric Properties of Lithium Tetraborate

We review the pyroelectric properties and electronic structure of Li2B4O7(110) and Li2B4O7(100) surfaces. There is evidence for a pyroelectric current along the [110] direction of stoichiometric Li2B4O7 so that the pyroelectric coefficient is nonzero but roughly 103 smaller than along the [001] direction of spontaneous polarization. Abrupt decreases in the pyroelectric coefficient along the [110] direction can be correlated with anomalies in the elastic stiffness C_33^D contributing to the concept that the pyroelectric coefficient is not simply a vector but has qualities of a tensor, as expected. The time dependent surface photovoltaic charging suggests that surface charging is dependent on crystal orientation and doping, as well as temperature

The Electronic Structure and Secondary Pyroelectric Properties of Lithium Tetraborate

We review the pyroelectric properties and electronic structure of Li2B4O7(110) and Li2B4O7(100) surfaces. There is evidence for a pyroelectric current along the [110] direction of stoichiometric Li2B4O7 so that the pyroelectric coefficient is nonzero but roughly 103 smaller than along the [001] direction of spontaneous polarization. Abrupt decreases in the pyroelectric coefficient along the [110] direction can be correlated with anomalies in the elastic stiffness contributing to the concept that the pyroelectric coefficient is not simply a vector but has qualities of a tensor, as expected. The time dependent surface photovoltaic charging suggests that surface charging is dependent on crystal orientation and doping, as well as temperature

Rare Earth Dopant (Nd, Gd, Dy, and Er) Hybridization in Lithium Tetraborate

The four dopants (Nd, Gd, Dy, and Er) substitutionally occupy the Li+ sites in lithium tetraborate (Li2B4O7: RE) glasses as determined by analysis of the extended X-ray absorption fine structure. The dopants are coordinated by 6-8 oxygen at a distance of 2.3 to 2.5 Å, depending on the rare earth. The inverse relationship between the RE-O coordination distance and rare earth (RE) atomic number is consistent with the expected lanthanide atomic radial contraction with increased atomic number. Through analysis of the X-ray absorption near edge structure, the rare earth dopants adopt the RE3+ valence state. There are indications of strong rare earth 5d hybridization with the trigonal and tetrahedral formations of BO3 and BO4 based on the determination of the rare earth substitutional Li+ site occupancy from the X-ray absorption near edge structure data. The local oxygen disorder around the RE3+ luminescence centers evident in the structural determination of the various glasses, and the hybridization of the RE3+ dopants with the host may contribute to the asymmetry evident in the luminescence emission spectral lines. The luminescence emission spectra are indeed characteristic of the expected f-to-f transitions; however, there is an observed asymmetry in some emission lines

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

The Electronic Structure and Secondary Pyroelectric Properties of Lithium Tetraborate

We review the pyroelectric properties and electronic structure of Li2B4O7(110) and Li2B4O7(100) surfaces. There is evidence for a pyroelectric current along the [110] direction of stoichiometric Li2B4O7 so that the pyroelectric coefficient is nonzero but roughly 103 smaller than along the [001] direction of spontaneous polarization. Abrupt decreases in the pyroelectric coefficient along the [110] direction can be correlated with anomalies in the elastic stiffness C_33^D contributing to the concept that the pyroelectric coefficient is not simply a vector but has qualities of a tensor, as expected. The time dependent surface photovoltaic charging suggests that surface charging is dependent on crystal orientation and doping, as well as temperature

Photoluminescence from Ag\u3csup\u3e2+\u3c/sup\u3e Ions in Lithium Tetraborate (Li\u3csub\u3e2\u3csub\u3eB\u3c/sub\u3e4\u3c/sub\u3eO\u3csub\u3e7\u3c/sub\u3e) Crystals

Excerpt: Two broad photoluminescence (PL) bands peaking near 502 and 725 nm are observed at room temperature in Ag-doped Li2B4O 7 crystals pre-irradiated at room temperature with X-rays.© 2014 Elsevier B.V

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

Rare earth dopant (Nd, Gd, Dy, and Er) hybridization in lithium tetraborate

The four dopants (Nd, Gd, Dy, and Er) substitutionally occupy the Li+ sites in lithium tetra borate (Li2B407: RE) glasses as determined by analysis of the extended X-ray absorption fine structure. The dopants are coordinated by 6-8 oxygen at a distance of 2.3 to 2.5 A. depending on the rare earth. The inverse relationship between the RE-O coordination distance and rare earth (RE) atomic number is consistent with the expected lanthanide atomic radial contraction with increased atomic number. Through analysis of the X-ray absorption near edge structure, the rare earth dopants adopt the RE3+ valence state. There are indications of strong rare earth 5d hybridization with the trigonal and tetrahedral formations of B03 and B04 based on the determination of the rare earth substitutional Li+ site occupancy from the X-ray absorption near edge structure data. The local oxygen disorder around the RE3+ luminescence centers evident in the structural determination of the various glasses, and the hybridization of the RE3+ dopants with the host may contribute to the asymmetry evident in the luminescence emission spectral lines. The luminescence emission spectra are indeed characteristic of the expected f-to-f transitions; however, there is an observed asymmetry in some emission lines