Defect Antiperovskite Compounds Hg3Q2I2 (Q = S, Se, and Te) for Room-Temperature Hard Radiation Detection.

The high Z chalcohalides Hg3Q2I2 (Q = S, Se, and Te) can be regarded as of antiperovskite structure with ordered vacancies and are demonstrated to be very promising candidates for X- and γ-ray semiconductor detectors. Depending on Q, the ordering of the Hg vacancies in these defect antiperovskites varies and yields a rich family of distinct crystal structures ranging from zero-dimensional to three-dimensional, with a dramatic effect on the properties of each compound. All three Hg3Q2I2 compounds show very suitable optical, electrical, and good mechanical properties required for radiation detection at room temperature. These compounds possess a high density (>7 g/cm3) and wide bandgaps (>1.9 eV), showing great stopping power for hard radiation and high intrinsic electrical resistivity, over 1011 Ω cm. Large single crystals are grown using the vapor transport method, and each material shows excellent photo sensitivity under energetic photons. Detectors made from thin Hg3Q2I2 crystals show reasonable response under a series of radiation sources, including 241Am and 57Co radiation. The dimensionality of Hg-Q motifs (in terms of ordering patterns of Hg vacancies) has a strong influence on the conduction band structure, which gives the quasi one-dimensional Hg3Se2I2 a more prominently dispersive conduction band structure and leads to a low electron effective mass (0.20 m0). For Hg3Se2I2 detectors, spectroscopic resolution is achieved for both 241Am α particles (5.49 MeV) and 241Am γ-rays (59.5 keV), with full widths at half-maximum (FWHM, in percentage) of 19% and 50%, respectively. The carrier mobility-lifetime µτ product for Hg3Q2I2 detectors is achieved as 10-5-10-6 cm2/V. The electron mobility for Hg3Se2I2 is estimated as 104 ± 12 cm2/(V·s). On the basis of these results, Hg3Se2I2 is the most promising for room-temperature radiation detection.

Charge Transport and Observation of Persistent Photoconductivity in Tl6SeI4 Single Crystals.

The chalcohalide compound Tl6SeI4 is a promising wide-bandgap semiconductor for efficient hard radiation detection at room temperature due to its high density, average atomic number and mobility-lifetime product. However, the nature of its charge transport kinetics, especially the role of defects in recombination, has not been examined in detail. To determine the charge transport kinetics in Tl6SeI4 single crystals, electrical conductivity and photoinduced current transient spectroscopy were measured over the temperature range 105-330 K. These measurements reveal the existence of multiple defect states with energy levels in the range 0.10-0.90 eV, within the bandgap of Tl6SeI4. Large persistent photoconductivity (PPC) is observed at low temperature that shows strong thermal quenching at 160 K. The quenching of PPC is described using a configuration coordinate model involving a deep level donor state, which is tentatively attributed to the presence of iodine vacancies or Si interstitial impurities.

Silanones and silanethiones from the reactions of transient silylenes with oxiranes and thiiranes in solution. The direct detection of diphenylsilanethione.

The transient silylenes SiMe(2) and SiPh(2) react with cyclohexene oxide (CHO), propylene oxide (PrO), and propylene sulfide (PrS) in hydrocarbon solvents to form products consistent with the formation of the corresponding transient silanones and silanethiones, respectively. Laser flash photolysis studies show that these reactions proceed via multistep sequences involving the intermediacy of the corresponding silylene-oxirane or -thiirane complexes, which are formed with rate constants close to the diffusion limit in all cases and exhibit UV absorption spectra similar to those of the corresponding complexes with the nonreactive O- and S-donors, tetrahydrofuran and tetrahydrothiophene. The SiMe(2)-PrO and SiPh(2)-PrO complexes both exhibit lifetimes of ca. 300 ns, and are longer-lived than the corresponding complexes with CHO, which are both in the range of 230-240 ns. On the other hand, the silylene-PrS complexes are considerably shorter-lived and vary with silyl substituent; the SiMe(2)-PrS complex decays with the excitation laser pulse (i.e., τ ≤ 25 ns), while the SiPh(2)-PrS complex exhibits τ = 48 ± 3 ns. The decay of the SiPh(2)-PrS complex affords a long-lived transient product exhibiting λ(max) ≈ 275 nm, which has been assigned to diphenylsilanethione (Ph(2)Si═S) on the basis of its second order decay kinetics and absolute rate constants for reaction with methanol, tert-butanol, acetic acid, and n-butyl amine, for which values in the range of 1.4 × 10(8) to 3.2 × 10(9) M(-1) s(-1) are reported. The experimental rate constants for decay of the SiMe(2)-epoxide and -PrS complexes indicate free energy barriers (ΔG(‡)) of ca. 8.5 and ≤7.1 kcal mol(-1) for the rate-determining steps leading to dimethylsilanone and -silanethione, respectively, which are compared to the results of DFT (B3LYP/6-311+G(d,p)) calculations of the reactions of SiH(2) and SiMe(2) with oxirane and thiirane. The calculations predict a stepwise C-O cleavage mechanism involving singlet biradical intermediates for the silylene-oxirane complexes, and a concerted mechanism for silanethione formation from the silylene-thiirane complexes, in agreement with earlier ab initio studies of the SiH(2)-oxirane and -thiirane systems.