Hole traps and thermoluminescence in Li2B4O7:Be

A trapped-hole centre with a high thermal stability is studied in Li₂B₄O₇:Be. EPR spectrum demonstrates a hyperfine splitting due to interaction of the trapped hole with a ⁹Be nucleus. The hole is trapped at the common vertex (bridging oxygen) of two adjacent BO₄ tetrahedra when Be²⁺ substitutes for B³⁺ in one of them. The centre is stable up to ≈500 K. The high-temperature thermoluminescence peak at 510–575 K occurs when the released holes recombine with trapped electrons. This peak shows an ultraviolet exciton-like luminescence band and also luminescence bands of casual impurities.     

Recombination luminescence of CaSO4:Tb3+ and CaSO4:Gd3+phosphors

A comparative study of the excitation of luminescence by VUV radiation as well as of thermally and photostimulated luminescence has been carried out for CaSO₄:Tb³⁺ and CaSO₄:Gd³⁺ phosphors, where Na⁺ or F⁻ ions are used for charge compensation. The distinction in hole processes for the phosphors with Na⁺ or F⁻ compensators is determined by the differing thermal stability of the holes localized at/near Tb³⁺Na⁺ and Gd³⁺Na⁺ (up to 100–160 K) or at/near Tb³⁺F⁻ V _Ca and Gd³⁺F⁻ V _Ca centers involving also a cation vacancy (up to 400–550 K). Tunnel luminescence in the pairs of localized electrons and holes nearby Tb³⁺ or Gd³⁺ has been detected. The mechanisms of electron-hole, hole-electron and tunnel recombination luminescence as well as a subsequent released energy transfer to RE³⁺ ions are considered.     

Franck–Hertz effect in cathodo- and photoluminescence of wide-gap materials

A brief overview of previously obtained and novel data on the manifestations of an analogue of Franck–Hertz effect in photo- and cathodoluminescence of wide-gap inorganic materials is presented. On the example of NaCl:Tl⁺ and MgO:Cr³⁺ single crystals, the excitation processes of the luminescence of 6s² Tl⁺ ions and 3d³ Cr³⁺ ions by 5–15 keV electrons or 5–20 eV photons at 6–420 K have been studied. The rapid processes of the direct energy transfer to Tl⁺ by hot conduction electrons or to Cr³⁺ centers by hot electrons and/or hot valence holes have been separated from rapid excitonic and more inertial electron–hole processes.     

Transient optical absorption and luminescence of lithium triborate LiB<Subscript>3</Subscript>O<Subscript>5</Subscript>

The transient optical absorption and luminescence of LiB₃O₅ (LBO) nonlinear crystals in the visible and UV spectral ranges were studied. Measurements made using absorption optical spectroscopy with nsscale time resolution revealed that the transient optical absorption (TOA) in LBO originates from optical transitions in hole centers and that the kinetics of optical density relaxation are rate-limited by interdefect nonradiative tunneling recombination involving these hole centers and the Li⁰ electronic centers, which represent neutral lithium atoms. At 290 K, the Li⁰ centers can migrate in a thermally stimulated, one-dimensional manner, a process which is not accompanied by carrier delocalization into the conduction or valence band. It is shown that the pulsed LBO cathodoluminescence kinetics is rate-limited by a recombination process involving two competing valence-band-mediated hole centers and shallow B²⁺ electronic centers. The radiative recombination accounts for the characteristic σ-polarized LBO luminescence in the 4.0-eV region.     

Luminescence of [Be] centre in MgO:Be

Doping of MgO single crystals with Be results in the formation of numerous Be-containing paramagnetic centres, easily detectable by EPR, and creates an intensive luminescence band at 6.2 eV, observable at T<200 K, and gives rise to new thermoluminescence peaks at 147 and 190 K. A paramagnetic centre with a rhombic symmetry that decays at 160 K was identified as a [Be]⁺ (i.e. O⁻–Be²⁺) centre—a hole trapped by O²⁻ lattice ion near a Be²⁺ perturbing defect. The luminescence excitation and isochronal annealing studies led to the conclusion that the 6.2 eV luminescence arises at the radiative decay of electron excitations near Be²⁺. These excitations can be created at the recombination of electrons with the holes localised in the [Be]⁺ centres, at the recombination of holes with the electrons trapped in the Be¹⁺ centre or at a direct excitation of oxygen near the Be²⁺ ion.     

Farbzentren in Ammoniumhalogeniden

Color centers produced by X-rays in ammonium halides at various temperatures between 20°K and room temperature have been investigated by means of paramagnetic resonance and by optical methods. Two kinds of paramagnetic defects were found to be predominant, the self-trapped hole (V _K-center) and another electron deficiency center involving a NH₃ ⁺-radical. The electronic structure of theV _K-center is the same as in the alkali halides, except that the orientation of the molecular axis is along [100] instead of [110]. The kinetics of the thermally activated motion of theV _K-centers and of their recombination with electrons has been studied. The electronic structure of the second center was derived from the hyperfine spectrum of the paramagnetic resonance. The rotation of the NH₃ ⁺ ion and its connection with the order-disorder transition in NH₄Cl has been studied.     

Hole-electron mechanism of F-H pair generation in RbCl crystals with impurity electron traps

Production of F, Cl ₃ ⁻ , Ag⁰, and Tl⁰ centers in RbCl:Ag and RbCl:Tl crystals by photons having energies ranging from 5 to 10 eV has been studied at 295 and 180 K. It is shown that creation of near-impurity excitations is accompanied by formation of F centers localized in the vicinity of Ag⁺ and Tl⁺ ions. F centers are produced in direct optical generation of self-trapped excitons. In addition to the well-known mechanism of F-H pair production in nonradiative recombination of electrons with self-trapped holes, a hole-electron process has been revealed for the first time to operate in RbCl:Ag having deep electron traps. By this mechanism, F-H pairs appear in the following sequence of stages: thermally stimulated unfreezing of hopping diffusion of self-trapped holes (V _K centers), tunneling electron transfer from Ag⁰ to the approaching V _K centers, and subsequent nonradiative decay of triplet self-trapped excitons near Ag⁺ ions. Fiz. Tverd. Tela (St. Petersburg) 40, 1238–1245 (July 1998)     

Intrinsic luminescence centers in γ- and θ-alumina nanoparticles

In this study, we investigate the photoluminescence(PL) properties of γ and θ-alumina nanoparticles synthesized by the chemical wet method followed by annealing. The obtained experimental results indicate the presence of some favorable near ultraviolet(NUV)-orange luminescent centers for usage in various luminescence applications, such as oxygen vacancies(F, F~+_2, F~(2+)_2, and F_2centers), OH related defects, cation interstitial centers, and some new luminescence bands attributed to trapped-hole centers or donor–acceptor centers. The energy states of each defect are discussed in detail. The defects mentioned could alter the electronic structure by producing some energy states in the band gap that result in the optical absorption in the middle ultraviolet(MUV) region. Spectra show that photoionazation of F and F_2 centers plays a crucial role in providing either free electrons for the conduction band, or the photoconversions of aggregated oxygen vacancies into each other, or mobile electrons for electrons-holes recombination process by the Shockley–Read–Hall(SRH)mechanism.     

Metastable optical absorption of relaxed electronic excitations in BeO-Zn crystals

Spectra of metastable optical absorption and its relaxation kinetics have been studied in zinc-doped BeO crystals by time-resolved pulsed absorption spectroscopy. A comparison of the observed induced optical absorption of self-trapped excitons and small-radius excitons bound to the zinc impurity suggests that their hole components have similar structures and reveals distinctive features of “forbidden” optical transitions in the electronic components. Metastable optical absorption in Zn⁺ centers has been discovered. It is shown that the small-radius excitons bound to the zinc impurity form in the hole stages of thermally stimulated tunneling recombination processes involving Zn⁺ electronic centers. It has been found that the high recombination probability of the electronic and hole centers created in BeO-Zn crystals by an electron beam may be due to the high degree of their spatial correlation. Fiz. Tverd. Tela (St. Petersburg) 41, 601–605 (April 1999)     

Radiation-stimulated pulse conductivity of CsBr crystals

The radiation-stimulated pulse conductivity of CsBr crystals is investigated upon picosecond excitation with electron beams (0.2 MeV, 50 ps, 0.1–10 kA/cm²). The time resolution of the measuring technique is ～150 ps. It is shown that the lifetime of conduction band electrons is limited by their bimolecular recombination with autolocalized holes (V _k centers). A delay in the conduction current pulse build-up is revealed. This effect is explained within the proposed model, according to which the Auger recombination of valence band electrons and holes of the upper core band substantially contributes to the generation of conduction band electrons.     

Two hydrogenic trapped-hole species in α-quartz

EPR studies of single crystal α-quartz at ca. 25 K, which had been X-irradiated, have revealed the presence of two new trapped-hole impurity centers. One of these is thought to be formed by trapping of an electron hole at an oxygen ion adjacent to a silicon 4+ ion vacancy occupied by four protons. The second center is similar with only three protons present. The Zeeman splitting (g) matrices for the two species have been determined and are compared to those for analogous aluminum hole species.     

Excimer-laser etching on silicon

Studies have been made of poly- and single Si etching induced by excimer-laser irradiation of the silicon surfaces in halogenated gases. Etching was investigated for different conduction types, impurity concentrations and crystallographic planes. Chlorine atoms accept electrons generated in photoexcited, undoped p-type Si, thus becoming negative ions which are pulled into the Si. However, the n⁺-type Si is etched spontaneously by Cl^– as a result of the availability of conduction electrons. Fluorine atoms, with the highest electronegativity, take in electrons independent of whether the material is n- or p-type. And thus, the easy F^– ion penetration into Si causes spontaneous etching in both types. New anisotropic etching for n⁺ poly-Si is investigated because of its importance to microfabrication technology. Methyl methacrylate (MMA) gas, which reacts with Cl atoms, produces a deposition film on the n⁺ poly-Si surface. The surface, from which the film is removed by KrF (5 eV) laser irradiation, is etched by Cl atoms, while the film remains on the side wall to protect undercutting. However, with the higher photon energy for the ArF (6.4 eV) laser, the Si-OH bonds are broken and electron traps are formed. These electrontrapping centers are easily annealed out in comparison to the plasma-induced centers. Pattern transfer etching for n⁺ poly-Si has been realized using reflective optics. The problems involved in obtaining finer resolution etching are discussed.     

Calculation of anharmonic effects in the unimolecular dissociation of M2+(H2O)2 (M = Be,Mg, and Ca)

The anharmonic and harmonic rate constants of the unimolecular dissociation of M²⁺(H₂O)₂ (M = Be, Mg, and Ca) were calculated using the Rice–Ramsperger–Kassel–Marcus theory. The anharmonic effects of the reactions were investigated. The results show that the energy barrier of the dissociation of Be²⁺(H₂O)₂ is 68.47 kcal/mol, and the anharmonic (T_4000K = 4.28×10⁸ s^?1) and harmonic (T_4000K = 4.22×10⁸ s^?1) rate constants were close in value in both the canonical and microcanonical systems. The energy barriers of the two steps for the dissociation, Mg²⁺(H₂O)₂ → MgOH⁺+H₃O⁺, were 37.41 and 11.39 kcal/mol, and those for the dissociation, Ca²⁺(H₂O)₂ → CaOH⁺+H₃O⁺, were 21.15 and 26.42 kcal/mol. The anharmonic effect of the two reactions is significant and cannot be neglected in both the canonical and microcanonical systems. The comparison also shows that the rate constants of the dissociation of Ca²⁺(H₂O)₂ have the maximum values, while those of Be²⁺(H₂O)₂ have the minimum values in the three reactions; however, the anharmonic effect also shows the similar trend in the comparison.     

Electron paramagnetic resonance and thermoluminescence study of Ag ions in Li2B4O7 crystals

Electron paramagnetic resonance (EPR) is used to investigate the effects of ionizing radiation on Ag-doped lithium tetraborate (Li₂B₄O₇) crystals. Two similar, yet distinct, trapped-hole centers (Ag²⁺ ions substituting for Li⁺ ions) are produced by 60 kV x rays. One Ag²⁺ ion, labeled Center A, has no nearby defects and the other Ag²⁺ ion, labeled Center B, has a neighboring impurity which is most likely a Ag⁺ ion substituting for a Li⁺ ion. The production and thermal decay properties of the two Ag²⁺ ions are described and their g matrices and ¹⁰⁷Ag and ¹⁰⁹Ag hyperfine matrices are obtained from the EPR angular dependences. The principal values of the g matrices are similar for the two centers, but the hyperfine principal values differ significantly (Center B has smaller values than Center A). There are also differences in the directions of the principal axes for the two centers. Together, these results imply (1) that the unpaired spin is less localized for Center B and (2) that the ground-state positions of the neighboring oxygen ions are different for Centers A and B. This explains why the peaks of the Ag²⁺ charge-transfer photoluminescence bands associated with Centers A and B occur at different wavelengths (502 and 725 nm, respectively). An isochronal pulsed thermal anneal shows that these radiation-induced Ag²⁺ ions serve as the recombination site for the intense thermoluminescence peak observed near 152 °C.     

Stability of the positively charged manganese centre in GaAs heterostructures examined theoretically by the effective mass approximation calculation near the Γ critical point

This paper describes an n-i-p-i-n model heterostructure with a manganese (Mn)-doped p-type base region to check the stability of a positively charged manganese A_Mn⁺ centre with two holes weakly bound by a negatively charged 3d⁵(Mn) core of a local spin S=5/2 in the framework of the effective mass approximation near the Γ critical point (k～0). By including the carrier screening effect, the ground state energy and the binding energy of the second hole in the positively charged centre A_Mn⁺ are calculated within a hole concentration range from 1 × 10¹⁶ cm^-3 to 1 × 10¹⁷ cm^-3, which is achievable by biasing the structure under photo-excitation. For comparison, the ground-state energy of a single hole in the neutral A_Mn⁰ centre is calculated in the same concentration range. It turns out that the binding energy of the second hole in the A_Mn⁺ centre varies from 9.27 meV to 4.57 meV. We propose that the presence of the A_Mn⁺ centre can be examined by measuring the photoluminescence from recombination of electrons in the conduction band with the bound holes in the A_Mn⁺ centre since a high frequency dielectric constant of varepsilon _∞ =10.66 can be safely adopted in this case. The novel feature of the ability to tune the impurity level of the A_Mn⁺ centre makes it attractive for optically and electrically manipulating local magnetic spins in semiconductors.     

Pulse characteristics of Hg0.8Cd0.2Te n +-p junctions

The pulse characteristics of Hg_0.8Cd_0.2Te n ⁺-p junctions are investigated. It is shown that the shape of the voltage pulse appearing in a junction on passage of a forward (reverse) current is determined by the recombination (generation) of nonequilibrium electrons in the hole region. An increase in the current pulse causes the appearance of an electric field, which draws electrons into the interior of the base region, and leads to variation of their lifetime because of the complex structure of the n ⁺-p junction. Zh. Tekh. Fiz. 67, 130–133 (July 1997     

Polar-center phase nuclei in He+-irradiated CuO single crystals

Irradiation of various single-crystal CuO faces [ac,bc,(110)] with 4.6-MeV He⁺ ions has been found to result in reduction of CuO to Cu₂O and Cu on the irradiated and unirradiated sides, lifting of forbiddenness from optical transitions in the [CuO₄]⁷⁻ electron center in the 0.7–0.95-eV energy range, a change in dichroism near the bands corresponding to transitions in the hole centers, [CuO₄]⁵⁻, and electron centers, [CuO₄]⁷⁻, as well as in a resonant increase of absorption at 0.95–1.30 eV with an unusual polarization dependence. The results of He⁺ irradiation of CuO single crystals are discussed in terms of a model of the nucleation of the phase of polar (electron and hole) centers in copper-oxygen systems. Fiz. Tverd. Tela (St. Petersburg) 40, 419–424 (March 1998)     

Light-induced intrinsic defects in PLZT ceramics

This paper reports on an EPR study of a ferroelectric, 1.8/65/35, and an antiferroelectric, 2/95/5, of optically transparent Pb_1?y La_yZr_1?x Ti_xO₃ (PLZT) ceramics within a broad temperature range (20–300 K) after illumination at a wavelength of 365–725 nm. Illumination with ultraviolet light, whose photon energy corresponds to the band gap of these materials, at T<50 K creates a number of photoinduced centers: Ti³⁺, Pb⁺, and Pb³⁺. It is shown that these centers are generated near a lanthanum impurity, which substitutes for both the Pb²⁺ and, partially, Ti⁴⁺ ions through carrier trapping from the conduction or valence band into lattice sites. The temperature ranges of the stability of these centers are measured, and the position of their local energy levels in the band gap is determined. The most shallow center is Ti³⁺, with its energy level lying 47 meV below the conduction band bottom. The Pb³⁺ and Pb⁺ centers produce deeper local levels and remain stable in the 2/95/5 PLZT ceramics up to room temperature. The migration of localized carriers is studied for both ceramic compositions. It is demonstrated that, under exposure to increased temperature or red light, the electrons ionized into the conduction band from Ti³⁺ are retrapped by the deeper Pb⁺ centers, thus hampering the carrier drift in the band and the onset of photoconduction. The part played by localized charges in the electrooptic phenomena occurring in the PLZT ceramics is discussed.     

X-ray stimulated luminescence in MgO

Studies have been made of the emission spectrum of MgO crystals induced by X-irradiation at 90 K. Two bands (half-widths ～0.8 eV) were observed to peak at 4.95 and 3.2 eV, respectively, in high purity crystals. Doping with 100 ppm or greater of Fe, Co, Cr, Cu, Mn, and Ni suppressed the luminescence, though in the MgO:Ni crystal the 2.3 eV Ni²⁺ band due to the ¹T_2g→³A_2g transition was observed. In deuterium-doped crystals the ratio of the intensity of 3.2–4.95 eV emission was found to be 1.2 as compared to 8 for the undoped crystals. Prior exposure of the pure crystals to ionizing radiation enhances the 4.95 eV band by a factor of three while not affecting the 3.2 eV band. This enhancement of intensity decays in several stages upon standing at room temperature in a way that reflects the thermal stability of the various components of the composite V-band absorption. These facts together with the observation that the 210 K thermoluminescence peak is composed entirely of 4.95 eV emission indicate that this luminescence band is associated with the recombination of an electron with a hole located in a V-type center, i.e. O?□ + e → (O²?□)1 → O²?□ + 4.95 eV, where the square indicates that the perturbing positive ion vacancy is adjacent to the oxugen ion which has captured the hole. In MgO:Li⁺, which exhibits no V-type centers upon irradiation, the 4.95 eV band was absent and a 2.9 eV emission which may be associated with recombination at the [Li]⁰ center was observe.