Yihui He

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.

Cs2PbI2Cl2, All-Inorganic Two-Dimensional Ruddlesden–Popper Mixed Halide Perovskite with Optoelectronic Response

The two-dimensional Ruddlesden-Popper (RP) phases are an important class of halide perovskites with versatile optoelectronic properties. So far, only organic-inorganic hybrid RP phases involving long organic spacers were reported in this class. Here, we report an all-inorganic RP phase lead halide perovskite, Cs2PbI2Cl2 (1, I4/ mmm space group; a = 5.6385(8) Å, c = 18.879(4) Å), synthesized by a solid-state method. The compound exhibits a band gap of Eg ∼ 3.04 eV and photoconductivity. We find an anomalous band gap evolution in Cs2Pb1- xSn xI2Cl2 solid solutions. Our combined density functional theory and experimental study supports the thermodynamically stable nature of 1 as a unique ordered phase in the Cs2PbX4 (X = Cl, Br, I) system. The calculations suggest that 1 is a direct bandgap semiconductor with relatively small effective carrier mass along the in-plane direction, consistent with the experimentally observed in-plane UV-light photoresponse. We also demonstrate that 1 is promising for radiation detection capable of α-particle counting. Moreover, 1 shows markedly ambient and thermal stability.

Cu2I2Se6: A Metal-Inorganic-Framework Wide-bandgap Semiconductor for Photon Detection at Room Temperature

Cu2I2Se6 is a new wide-bandgap semiconductor with high stability and great potential toward hard radiation and photon detection. Cu2I2Se6 crystallizes in the rhombohedral R3̅m space group with a density of d = 5.287 g·cm-3 and a wide bandgap Eg of 1.95 eV. First-principles electronic band structure calculations at the density functional theory level indicate an indirect bandgap and a low electron effective mass me* of 0.32. The congruently melting compound was grown in centimeter-size Cu2I2Se6 single crystals using a vertical Bridgman method. A high electric resistivity of ∼1012 Ω·cm is readily achieved, and detectors made of Cu2I2Se6 single crystals demonstrate high photosensitivity to Ag Kα X-rays (22.4 keV) and show spectroscopic performance with energy resolutions under 241Am α-particles (5.5 MeV) radiation. The electron mobility is measured by a time-of-flight technique to be ∼46 cm2·V-1·s-1. This value is comparable to that of one of the leading γ-ray detector materials, TlBr, and is a factor of 30 higher than mobility values obtained for amorphous Se for X-ray detection.

Abrupt Thermal Shock of (NH4)2Mo3S13 Leads to Ultrafast Synthesis of Porous Ensembles of MoS2 Nanocrystals for High Gain Photodetectors

Ultrafast synthesis of high-quality transition-metal dichalcogenide nanocrystals, such as molybdenum disulfide (MoS2), is technologically relevant for large-scale production of electronic and optoelectronic devices. Here, we report a rapid solid-state synthesis route for MoS2 using the chemically homogeneous molecular precursor, (NH4)2Mo3S13·H2O, resulting in nanoparticles with estimated size down to 25 nm only in 10 s at 1000 °C. Despite the extreme nonequilibrium conditions, the resulting porous MoS2 nanoparticles remain aggregated to preserve the form of the original rod shape bulk morphology of the molecular precursor. This ultrafast synthesis proceeds through the rapid decomposition of the precursor and rearrangement of Mo and S atoms coupled with simultaneous efficient release of massive gaseous species, to create nanoscale porosity in the resulting isomorphic pseudocrystals, which are composed of the MoS2 nanoparticles. Despite the very rapid escape of massive amounts of NH3, H2O, H2S, and S gases from the (NH4)2Mo3S13·H2O mm sized crystals, they retain their original shape as they convert to MoS2 rather than undergo explosive destruction from the rapid escape process of the gases. The obtained pseudocrystals are made of aggregated MoS2 nanocrystals exhibit a Brunauer-Emmett-Teller surface area of ∼35 m2/g with an adsorption average pore width of ∼160 Å. The nanoporous MoS2 crystals are solution processable by dispersing in ethanol and water and can be cast into large-area uniform composite films. Photodetectors fabricated from these films show more than 2 orders of magnitude higher conductivity (∼6.25 × 10-6 S/cm) and photoconductive gain (20 mA/W) than previous reports of MoS2 composite films. The optoelectronic properties of this nanoporous MoS2 imply that the shallow defects that originate from the ultrafast synthesis act as sensitizing centers that increase the photocurrent gain via two-level recombination kinetics.

Improvement of the THz response of Zn1−xMnxTe bulk crystals grown by a temperature gradient solution method

As a type of AII1−xMnxBVI alloy, Zn1−xMnxTe ingots with a diameter of 30 mm are grown as large single crystals by a temperature gradient solvent method under Te-rich conditions. The orange-red Zn1−xMnxTe crystals are cut and processed into size-appropriate wafers for fundamental studies, as well as for THz spectroscopy and magnetization response analyses. Mn segregation associated with the growth conditions is identified in the as-grown crystals, and an enriched higher concentration of Mn is observed inside the Te inclusion. To evaluate the effect of Mn on the Zn1−xMnxTe crystal, the site occupation is calculated via an ab initio study, and is further confirmed by electrical and optical property measurements. Mn tends to substitute Zn to form MnZn in Zn1−xMnxTe, which results in a low density of free charge carriers, through which the THz detection sensitivity is enhanced by 15–25% compared to the intrinsic ZnTe. Moreover, evident paramagnetic magnetization behavior is observed at variable temperatures due to the random distribution of an isolated Mn (Mnioct,Te6) spin with S = 5/2. We note that further optimization of the THz performance can be achieved by optimizing the growth process and tailoring the Mn content.

Strategy on removing oxygen impurity for crystal growth of one candidate Tl6SeI4 for room-temperature hard radiation detector(Conference Presentation)

Thallium based chalcogenide and halide semiconductors such as Tl4HgI6, TlGaSe2, Tl6SeI4 and Tl6SI4 are promising materials for room-temperature hard radiation detection. They feature appropriate band gaps, high mass densities and facile growth technology. However, these materials are being plagued by the Tl oxides impurity from Tl precursor or Tl containing binary precursors, which leads to problems including tube breakage, parasitic nucleation and detector performance deterioration. In this work, we present a facile way to chemically reduce Tl oxidations, and then eliminate oxygen impurity by adding high-purity graphite powder during synthesis and crystal growth. We also further investigated the reactivity between Tl oxides and graphite. The detector performance of Tl6SeI4 crystal was dramatically improved after lowering/removing the oxygen impurities. This result not only indicates the significance of removing oxygen impurity for improving detector performance. Our results suggest that the chemical reduction method we developed by adding carbon powder during synthesis is highly effective in substantially reducing oxygen impurities from Tl containing materials.

Crystal growth and characterization of Hg-based chalcogenide compounds(Conference Presentation)

In this work, two Hg-based chalcogenides were investigated in detail to reveal their potential capability of radiation detection at room temperature (RT). Cs2Hg6S7, with a bandgap of 1.63 eV, which is designed by the dimensional reduction theory proposed by our group, were prepared and characterized. α-HgS, with a bandgap of ~2.10 eV, as a precursor used for the ternary compound synthesis, was also proposed and further investigated. For Cs2Hg6S7, the crystals tended to crystallize into needle form with small grains. Here, the conditions of Bridgman melt growth were optimized to obtain relatively large single crystals. The slight excess of Cs2S as a fluxing agent during growth was found to facilitate better crystallization and large grains. Interestingly, no inclusion or secondary phase was found in the as-grown single crystals. The improvement of bulk resistivity from ~10^6 Ωcm to 10^8 Ωcm was also achieved through the control of stoichiometry during crystal growth. For α-HgS crystals, both physical vapor transport and chemical vapor transport methods have been applied. By modifying the transport temperature and transport agent, single crystal with size about 3x1.5 mm^2 was grown with resistivity higher than 10^11 Ωcm. Photoluminescence (PL) revealed that multiple peaks observed in the 1.6-2.3 eV range and excitonic peak from for α-HgS single crystals were observed indicating good crystalline quality. Finally, the planar detectors for both crystals were tested under Co57 gamma ray source. Both of the crystals showed reasonable gamma ray response, while α-HgS crystals could respond at a relatively higher counting rate.