TlHgInS3: An Indirect-Band-Gap Semiconductor with X-ray

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Chemistry of Materials

TlHgInS3: An Indirect Band Gap Semiconductor with X-Ray Photoconductivity Response Hao Li,1 Christos D. Malliakas,2 Fei Han,1 Duck Young Chung,1 and Mercouri G. Kanatzidis*1,2

1

Materials Science Division, Argonne National Laboratory, Argonne, Illinois, 60439, USA

2

Department of Chemistry, Northwestern University, Evanston, IL, 60208, USA

ACS Paragon Plus Environment


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Abstract The quaternary compound TlHgInS3 crystallizes in a new structure type of space group C2/c with cell parameters: a = 13.916(3) Å, b = 3.9132(8) Å, c = 21.403(4) Å, β = 104.16(3)°, V = 1130.1(8) Å3 and ρ = 7.241 g/cm3. The structure is a unique three-dimensional framework with parallel tunnels, which is formed by 1͚[InS33-] infinite chains bridged by linearly coordinated Hg2+ ions. TlHgInS3 is a semiconductor with a band gap of 1.74 eV and resistivity of ~4.32 GΩ cm. TlHgInS3 single crystals exhibit photocurrent response when exposed to Ag X-rays. The mobility-lifetime product (µτ) of the electrons and holes estimated from the photocurrent measurements are (µτ)e ~ 3.6×10-4 cm2/V and (µτ)h ~ 2.0 ×10-4 cm2/V. Electronic structure calculations at the Density Functional Theory level indicate an indirect band gap and a relatively small effective mass for both electrons and holes. Based on the photoconductivity data, TlHgInS3 is a potential material for radiation detection applications.


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Introduction Heavy metal (Hg, Tl, Pb, Bi, etc) halide and chalcogenide crystals are of great interest for potential applications in hard radiation detection,1-17 thermoelectric energy conversion,18-21 solid state solar cells,22-24 superconductivity,25-27 etc. For hard radiation detection applications at room temperature, the candidate material should fulfill the following basic requirements: a) large band gap (>1.5 eV), b) large atomic number (Z) giving rise to high density, c) high mobility lifetime product (µτ) of charge carriers which is the figure of merit for X-ray and γ-ray detection. In this regard, Cd1-xZnxTe (CZT), HgI2, and TlBr have been extensively studied as radiation detectors in last decades.28 CZT is the commercial benchmark solid state semiconductor for γ-ray detector which possesses high µτ products for electrons and holes as a measure of their performance in radiation detection, (µτ)e ~ 4.5 × 10-2 cm2/V and (µτ)h ~ 1 × 10-4 cm2/V.6 TlBr29 and HgI26 also show high values of (µτ)e ~ 6.5 × 10-3 cm2V-1 and (µτ)h ~ 4 × 10-4 cm2V-1 for TlBr and (µτ)e ~ 8 × 10-4 cm2V-1 and (µτ)h ~ 3 × 10-5 cm2V-1 for HgI2. However, these materials have their own disadvantages such as poor hole charge transport properties and high cost for CZT single crystals,7,30-33 phase transitions from red α-phase to yellow β-phase over ~127 oC for HgI2,34 and polarization for TlBr.35 Because of these issues, new superior detector grade materials are in demand.17,28,36 In search for new materials which may replace the current detector materials, compounds containing Tl and Hg are particularly attractive because the two elements are strong γ-ray absorbers which enables the effective detection using smaller crystals of material, thus relaxing the (µτ) requirements.37 From a chemical point of view, Tl is often considered as a pseudo alkali metal because of the preferred +1 oxidation state and similar ionic radius to K+/Rb+,.20,38-41 Hg on the other hand adopts flexible coordination geometry from linear, trigonal planar, tetrahedral and even octahedral, resulting in diverse structure types.5,42-48 Several halide and chalcogenide compounds containing both Tl and Hg elements such as TlHgAs3S6,35 Hg3Y2TlX3(Y =As, Sb; X=Cl, Br),49 Tl2HgMQ4 (M= Si, Ge, Sn; Q= Se, Te)20,50-52 have been reported but not investigated in detail except Tl4HgI653 (with respect to the radiation detection). Previously, we have identified Tl2Hg3Q4 (Q = S, Se, Te) as promising detector materials using the “dimensional reduction” approach,10 and TlHg6Q4Br5 (Q = S, Se) using the “lattice hybridization” approach.39



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Here we report a new Tl and Hg containing material, the indirect band gap semiconductor TlHgInS3. We report the synthesis, crystal growth, optical and photo-electrical characterization of TlHgInS3.

Experimental Section Syntheses. The following reagents were used as received: (i) Indium metal, 99.99%, Cerac, Milwaukee, WI; (ii) Mercury metal, 99.999%, Alfa Aesar, Ward Hill, MA; (iii) Sulfur shot, 99.99%, 5N Plus Inc, St-Laurent, QC, Canada; (iv) Thallium metal, 99.99%, Alfa Aesar, Ward Hill, MA; Warning: Because both Tl and Hg are highly toxic, great care should be exerted with appropriate protective equipment in both the synthesis and handling of the TlHgInS3 crystals, all manipulations should be done in a glove box or fume hood. HgS was prepared by the method described previously.2,39,42 Two other binary precursors Tl2S and In2S3 were generated by stoichiometric mixtures of Tl/S and In/S, respectively, in fused quartz tubes which were sealed under vacuum (~ 10-4 mbar), followed by heating at 300 oC for 48 hrs. All HgS, Tl2S and In2S3 precursors obtained were ground into powder for synthesis of target compounds. A stoichiometric reaction of Tl2S, HgS and In2S3 with a ratio 1:2:1 (~ 3 g total mixture) was used to synthesize the crystals. The mixture was heated at 800 oC for 24 h and then cooled to room temperature in 3 h. Dark red chunky rod shaped crystals, yellow plate crystals and black block crystals were found in the product. Semiquantitative Energy-Dispersive (EDS) analysis on several dark red crystals was performed by using Hitachi S-3400 scanning electron microscope (SEM) equipped with a PGT energy dispersive X-ray analyzer with an accelerating voltage of 25 kV and a 60 s accumulation time for data acquisition. An average composition of the dark red crystals is Tl1.0Hg0.9In1.2S3.7. The yellow plate crystals and black block crystals turned out to be known phases, TlInS2 and Tl2Hg3S4, respectively. The yield of TlHgInS3 was ~30% and several dark red crystals formed with length up to ~3 mm (Figure 1). They were handpicked from the reaction products and ground into powder for phase identification by powder Xray diffraction using a PanAlytical X’Pert Pro powder diffractometer (Cu Kα radiation, λ = 1.5418 Å) over the 2 θ range of 10-70o with a step size of 0.017o. The diffractometer was operated at 45 kV/40 mA.


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Structure Determination. The crystal structure was determined by single crystal X-ray diffraction methods. A rectangular crystal with dark red color was mounted on tip of glass fiber. Single crystal intensity data were collected by performing ω scans on a STOE imaging plate diffraction system (IPDS-2T) using graphite-monochromated Mo-Kα radiation (λ = 0.71073 Ǻ) operating at 50 kV and 40 mA. Individual frames were collected with a 5 min exposure time and a 1.0° ω rotation. The X-AREA, X-RED and X-SHAPE software packages were used to perform the data collection, integration and analytical absorption corrections. The SHELXL54 software package was used to solve and refine the structure. The parameters for data collection and the details of the structure refinement are given in Table 1. Atomic coordinates and equivalent isotropic thermal parameters are given in Table 2. Differential Thermal Analysis. Differential Thermal Analysis (DTA) was performed on a Shimadzu DTA-50 thermal analyzer. Hand-picked crystals were ground and sealed in silica ampoule under vacuum. Another ampoule containing similar mass of α-Al2O3 was used as a reference. The sample was heated to 800 oC at a rate of 5 oC/min and cooled at a rate of 5 oC/min to 50 oC. The procedure was repeated to confirm the result. Residue of the DTA experiment was examined by powder X-ray diffraction. Diffuse Reflectance. The optical energy band gap of TlHgInS3 was determined by optical diffuse-reflectance spectroscopy on finely ground powder samples. The measurements were performed at room temperature using a Shimadzu Model UV-3101PC double-beam, doublemonochromator spectrophotometer. BaSO4 was used as a 100% reflectance standard. The absorption data were calculated based on the obtained reflectance spectra using the KubelkaMunk equations.55-57 Electrical Resistivity and Photoconductivity Measurement. A rod-shaped single crystal (0.8 x 0.4 x 0.3 mm3) of TlHgInS3 was selected for the DC resistivity measurements by a two probe method using a Keithley 617 electrometer. Silver paste (TED PELLA, Inc.) was applied on the ends of the rod crystal as electrode contact. The crystal is stable in air and no degradation or change of crystal property was observed during the whole process of measurement after application of Ag paste. The electrical current from the two electrodes on the crystal sample was measured while voltage was applied from -200 V to 200 V.



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Photoconductivity measurement was carried out using a homemade setup.16-17 The crystal was irradiated by Ag Kα X-ray (40 kV, 20 mA) and the photocurrent was recorded as a function of positive and negative bias voltage using a Keithley 6517B Electrometer. A qualitative measurement of the X-ray response was conducted using the same setup, the bias voltage was set constant at 10 V, 25 V, 50 V, 75 V, 100 V, and 200 V respectively, while the shutter on the Xray source was switched ON and OFF manually. The resulting current was recorded as a function of time. Electronic Band Structure Calculations. Electronic band structure calculations were performed using the self-consistent full-potential linearized augmented plane wave method (LAPW)58 within density functional theory (DFT),59-60 and the generalized gradient approximation (GGA) of Perdew, Burke, and Ernzerhof61 for the exchange and correlation potential. The values of the atomic radii were taken to be 2.3 a.u. for Tl, In, and Hg atoms, and 2.1 a.u. for S atoms, where a.u. is the atomic unit (0.529 Å). Convergence of the self-consistent iterations was performed for 891 k points inside the irreducible Brillouin zone to within 0.0001 Ry with a cutoff of -6.0 Ry between the valence and the core states. Scalar relativistic corrections were included and a spin-orbit interaction was incorporated using a second variational procedure.62 The modified Becke-Johnson exchange potential63 was applied to the LDA calculation for a better estimation of the band-gap. The calculations were performed using the WIEN2k program using the experimentally obtained cell constants and atomic coordinates.64

Results and Discussion Synthesis and thermal stability. Several experimental conditions at different combinations of material mixture, temperature, and cooling rate were attempted but were unsuccessful in yielding single phase of TlHgInS3. The highest yield of dark red single crystals of TlHgInS3 was achieved at about 30% by a stoichiometric reaction of Tl2S, HgS and In2S3 at 800 oC followed by fast cooling in 3 hrs. The cooling rate is an important parameter to control the yield and faster cooling gives rise to higher yield. Because of the incongruently melting behavior of TlHgInS3, slow cooling favors formation of ternary bi-product phases. This was confirmed by the results of DTA experiments. No apparent endothermic peak on the heating process was observed while one exothermic event showed up clearly at 423 oC on the cooling process (Figure S1). The residue of


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DTA was examined with powder X-ray diffraction (Figure 2), and showed Tl2Hg3S410 and TlInS265, indicating that TlHgInS3 decomposes during heating. Efforts to synthesize the analogous compounds TlHgBiS3, TlHgSbS3 and TlHgInSe3 with the same synthetic approach gave only the ternary compounds Tl2Hg3S4 and Tl2Hg3Se4,10 TlBiS2,66 TlSbS2,67 and TlInSe2.68 Structure description TlHgInS3 crystallizes in a new structure type. It features a threedimensional anionic framework of [Hg2In2S6]2- with Tl atoms found in parallel tunnels (Figure 3). The structure consists of [In2S6]n3n- infinite straight chains composed of edge-shared [InS6] octahedra along the b-axis (Figure 4a). The [In2S6]n3n- chains are interconnected by linear Hg atoms (Figure 4b,c) which form large tunnels occupied by two rows of Tl atoms. Selected bond distances and angles for TlHgInS3 are summarized in Table 3. The asymmetric unit of TlHgInS3 contains one Tl atom, two Hg atoms, one In atom and three S atoms. The Tl atom is coordinated by six S atoms in a distorted octahedral geometry (Figure 4d) with bond distances ranging from 3.017(3) Å to 3.359(3) Å, which are comparable to Tl–S distances (2.940(6) Å to 3.430 Å) in Tl2Hg3S410 and TlHgAs3S635. The two Hg atoms are each coordinated by two S atoms in a nearly linear geometry as found in other chalcogenides such as HgS (cinnabar)69, Na2Hg3S4,70 Cs2Hg6S7,71 and Ba8Hg3U3S18,72 etc. The In atom is bonded to six S atoms forming the [InS6] octahedron. The Hg-S distances (2.342(2) Å to 2.360(3) Å) and In-S distances (2.562(3) Å to 2.700(2) Å) are normal. Because of the compact crystal structure with heavy elements Tl (ZTl=81) and Hg (ZHg=80), TlHgInS3 has a high calculated density of 7.241 g/cm3, which provides high stopping powder for hard radiation. The attenuation coefficient as a function of radiation energy was calculated using the atomic attenuation coefficient tabulated by NIST73-74 and is shown in Figure 5. Compared to CZT, the title compound has a much shorter attenuation length over most of the energy range, especially at high photon energy of 102 to 104 keV. For example, at the energy of 137Cs (i.e. 662 keV), the attenuation length of CZT is 2.3 cm, while TlHgInS3 is 1.4 cm, confirming the much higher absorption coefficient compared to CZT at this energy range; thus smaller crystals of the TlHgInS3 can be used to stop high energy photons. Optical properties The optical band gap of TlHgInS3 was determined by solid-state UV-Vis optical spectroscopy using ground crystals and the absorption spectrum is shown in Figure 6. The band gap is 1.74 eV, which is in agreement with the dark red color of the crystals. The band



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gap of TlHgInS3 is in the range of 1.6 to 3 eV suitable for hard radiation detection at room temperature.75-76 The relatively shallow slope of the rising absorption edge suggests an indirect transition which is also supported by the electronic band structure calculations discussed below. An indirect band gap is beneficial for longer lifetime of the carriers when compared to the direct band gap, since the recombination of the excited holes and electrons needs the assistance of phonons from the crystal lattice. Electronic band structure The calculated electronic band structure of TlHgInS3 shown in Figure 7(a) suggests the presence of an indirect band gap of around 2.1 eV calculated between the top of valence band, located between the V-point and L-point, and the B-point at the bottom of the conduction band. The theoretical band gap is in relatively good agreement with the experimental value of 1.74 eV. The valence and conduction bands show fairly good dispersion (~0.5 eV) suggesting a relative small effective mass for both electrons and holes. The partial density of states (DOS) plot (Figure 7b.) indicates that the valence bands are predominantly composed of S p-orbitals near the Fermi level with a small contribution from Tl orbitals and an even smaller fraction from In and Hg orbitals. The bottom of the conduction bands consist of comparable contributions from Tl, Hg, In, and S orbitals. Resistivity, photoconductivity and detection properties. The electrical resistivity of TlHgInS3 single crystal was measured at room temperature using the two probe method. Figure 8 shows a typical Current-Voltage curve, which has a linear ohmic behavior. The resistivity calculated from the slope of the I-V curve based on the dimensions of the crystal was 4.32 GΩ·cm and is relatively high compared to CsHgInS3, CsCdInQ3 crystals,4-5. The GΩ·cm range resistivity of TlHgInS3 is high enough to suppress dark leakage current at room temperature and can sustain higher applied electrical fields. The carrier mobility-lifetime product (µτ) is a figure of merit for detection performance. A poor µτ product results in a short drift length given by λ = µτE, which leads to a lower spectrum resolution.28,76 We performed photoconductivity measurements on the TlHgInS3 rod shaped single crystal (0.8 x 0.5 x 2.0 mm3) using Ag Kα X-ray (40 kV, 20 mA) radiation. Silver paste contact was put on the two side of the rod sample and different voltage polarities were applied. The electron and hole photoconductivity curves for TlHgInS3 single crystal are shown in Figure


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9. The photocurrent can be modeled by Hecht equation, from which the (µτ) product can be obtained:77-78

I µτV I (V ) = 0 2 L

−L  1 − e µτV   2

   

(1)

where I0 is saturation current, L is the sample thickness, and V is the applied voltage. Fitting the data to formula (1), the µτ and I0 values obtained for electrons and holes are summarized in Table 4. The electron µτ product for the TlHgInS3 crystal was estimated at (µτ)e = 3.6 × 10-4 cm2/V. This value is lower than those of the commercial grade CZT ((µτ)e = 4.5 × 10-2 cm2/V)6 and TlBr ((µτ)e = 6.5 × 10-3 cm2/V)29. However, the estimated µτ products of both carriers for the title compound are comparable to other promising detector-grade crystals such as HgI2 ((µτ)e = 8 × 10-4 cm2/V, (µτ)h = 3 × 10-5 cm2/V)6 and PbI2 ((µτ)e = 5 × 10-4 cm2/V, (µτ)h = 2 × 10-6 cm2/V). TlHgInS3 single crystal exhibited strong response when exposed to Ag X-ray. The dark current and photocurrent under different bias voltage (10 V, 25 V, 50 V, 75 V, 100 V, 200 V) were recorded when the X-ray was turned ON-OFF manually (Figure 10a). For example, under 200V bias, the dark current was about 0.008 nA and when X-ray was turned on the photocurrent increased to the saturation value of 0.35 nA, indicating the photocurrent is > 40 times larger than the dark current. The X-ray photocurrent was larger under higher bias voltage and consistent with the photocurrent data used to obtain the µτ product. The photocurrent measurements were repeated (Figure 10b) and the values of the dark current and photocurrent remained unchanged, implying good stability of the TlHgInS3 crystal.

Concluding remarks The new quaternary compound TlHgInS3 exhibits a novel tunneled 3-D structure with Tl atoms residing in tunnels. It features high density (7.24g/cm-3), band gap (1.74 eV) and high resistivity (4.32 GΩ·cm) which are suitable for the X/γ-ray detection. The µτ products of TlHgInS3 are comparable to HgI2. The compound melts incongruently, which makes it difficult to grow large single crystal growth directly from stoichiometric melt by Bridgman technique. However, growth of large single crystal may be realized by flux methods. TlHgInS3 single crystal shows a



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response to Ag X-ray radiation. Further research on optimization of growth conditions for large size single crystals of this compound as well as exploration of new the Tl and Hg containing materials for hard radiation detection are underway.


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ASSOCIATED CONTENT Supporting Information. The Supporting Information includes the following information: Figure S1, the DTA curve of the TlHgInS3. Also, the crystallographic information files (CIF). This materials is available free of charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION Corresponding author *Email: [email protected] Note The authors declare no competing financial interest.

ACKNOWLEDGEMENTS This work is supported by the Office of Nonproliferation and Verification Research and Development under National Nuclear Security Administration the U.S. Department of Energy under contract No DE-AC02-06CH11357. Use of the Center for Nanoscale Materials, including resources in the Electron Microscopy Center, was supported by the U. S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357



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References (1) Peters, J. A.; Cho, N. K.; Liu, Z. F.; Wessels, B. W.; Li, H.; Androulakis, J.; Kanatzidis, M. G. Investigation of defect levels in Cs2Hg6S7 single crystals by photoconductivity and photoluminescence spectroscopies. J Appl Phys 2012, 112. (2) Li, H.; Peters, J. A.; Liu, Z. F.; Sebastian, M.; Malliakas, C. D.; Androulakis, J.; Zhao, L. D.; Chung, I.; Nguyen, S. L.; Johnsen, S.; Wessels, B. W.; Kanatzidis, M. G. Crystal Growth and Characterization of the X-ray and gamma-ray Detector Material Cs2Hg6S7. Cryst Growth Des 2012, 12, 3250. (3) Stoumpos, C. C.; Malliakas, C. D.; Peters, J. A.; Liu, Z. F.; Sebastian, M.; Im, J.; Chasapis, T. C.; Wibowo, A. C.; Chung, D. Y.; Freeman, A. J.; Wessels, B. W.; Kanatzidis, M. G. Crystal Growth of the Perovskite Semiconductor CsPbBr3: A New Material for High-Energy Radiation Detection. Cryst Growth Des 2013, 13, 2722. (4) Li, H.; Malliakas, C. D.; Peters, J. A.; Liu, Z. F.; Im, J.; Jin, H.; Morris, C. D.; Zhao, L. D.; Wessels, B. W.; Freeman, A. J.; Kanatzidis, M. G. CsCdInQ(3) (Q = Se, Te): New Photoconductive Compounds As Potential Materials for Hard Radiation Detection. Chem Mater 2013, 25, 2089. (5) Li, H.; Malliakas, C. D.; Liu, Z. F.; Peters, J. A.; Jin, H.; Morris, C. D.; Zhao, L. D.; Wessels, B. W.; Freeman, A. J.; Kanatzidis, M. G. CsHgInS3: a New Quaternary Semiconductor for gamma-ray Detection. Chem Mater 2012, 24, 4434. (6) Kargar, A.; Ariesanti, E.; McGregor, D. S. A Comparison between Spectroscopic Performance of Hgi2 and Cdznte Frisch Collar Detectors. Nucl Technol 2011, 175, 131. (7) Szeles, C. Advances in the crystal growth and device fabrication technology of CdZnTe room temperature radiation detectors. Ieee T Nucl Sci 2004, 51, 1242. (8) Biswas, K.; Du, M. H.; Singh, D. J. Electronic structure and defect properties of Tl6SeI4: Density functional calculations. Phys Rev B 2012, 86. (9) Im, J.; Jin, H.; Li, H.; Peters, J. A.; Liu, Z. F.; Wessels, B. W.; Kanatzidis, M. G.; Freeman, A. J. Formation of native defects in the gamma-ray detector material Cs2Hg6S7. Appl Phys Lett 2012, 101. (10) Johnsen, S.; Peter, S. C.; Nguyen, S. L.; Song, J.-H.; Jin, H.; Freeman, A. J.; Kanatzidis, M. G. Tl2Hg3Q4(Q = S, Se, and Te): High-Density, Wide-Band-Gap Semiconductors. Chem Mater 2011, 23, 4375. (11) Liu, Z. F.; Peters, J. A.; Wessels, B. W.; Johnsen, S.; Kanatzidis, M. G. Thallous chalcogenide (Tl6I4Se) for radiation detection at X-ray and gamma-ray energies. Nucl Instrum Meth A 2011, 659, 333. (12) Liu, Z. F.; Peters, J. A.; Zang, C.; Cho, N. K.; Wessels, B. W.; Johnsen, S.; Peter, S.; Androulakis, J.; Kanatzidis, M. G.; Song, J. H.; Jin, H.; Freeman, A. J. Tl-based wide gap semiconductor materials for x-ray and gamma ray detection. Chemical, Biological, Radiological, Nuclear, and Explosives (Cbrne) Sensing Xii 2011, 8018. (13) Carcelen, V.; Rodriguez-Fernandez, J.; Vijayan, N.; Hidalgo, P.; Piqueras, J.; Sochinskii, N. V.; Perez, J. M.; Dieguez, E. Development of CdZnTe doped with Bi for gamma radiation detection. Crystengcomm 2010, 12, 507. (14) Androulakis, J.; Peter, S. C.; Li, H.; Malliakas, C. D.; Peters, J. A.; Liu, Z. F.; Wessels, B. W.; Song, J. H.; Jin, H.; Freeman, A. J.; Kanatzidis, M. G. Dimensional Reduction: A Design Tool for New Radiation Detection Materials. Adv Mater 2011, 23, 4163. (15) Fiederle, M.; Ebling, D.; Eiche, C.; Hofmann, D. M.; Salk, M.; Stadler, W.; Benz, K. W.; Meyer, B. K. Comparison of Cdte, Cd0.9zn0.1te and Cdte0.9se0.1 Crystals - Application for Gamma-Ray and X-RayDetectors. J Cryst Growth 1994, 138, 529. (16) Johnsen, S.; Liu, Z. F.; Peters, J. A.; Song, J. H.; Peter, S. C.; Malliakas, C. D.; Cho, N. K.; Jin, H. S.; Freeman, A. J.; Wessels, B. W.; Kanatzidis, M. G. Thallium Chalcogenide-Based Wide-Band-Gap Semiconductors: TlGaSe2 for Radiation Detectors. Chem Mater 2011, 23, 3120.


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(17) Johnsen, S.; Liu, Z. F.; Peters, J. A.; Song, J. H.; Nguyen, S.; Malliakas, C. D.; Jin, H.; Freeman, A. J.; Wessels, B. W.; Kanatzidis, M. G. Thallium Chalcohalides for X-ray and gamma-ray Detection. J Am Chem Soc 2011, 133, 10030. (18) Wolfing, B.; Kloc, C.; Teubner, J.; Bucher, E. High performance thermoelectric Tl9BiTe6 with an extremely low thermal conductivity. Physical Review Letters 2001, 86, 4350. (19) Hsu, K. F.; Chung, D. Y.; Lai, S.; Mrotzek, A.; Kyratsi, T.; Hogan, T.; Kanatzidis, M. G. CsMBi3Te6 and CsM2Bi3Te7 (M=Pb, Sn): New thermoelectric compounds with low-dimensional structures. J Am Chem Soc 2002, 124, 2410. (20) McGuire, M. A.; Scheidemantel, T. J.; Badding, J. V.; DiSalvo, F. J. Tl(2)AXTe(4) (A = Cd, Hg, Mn; X = Ge, Sn): Crystal structure, electronic structure, and thermoelectric properties. Chem Mater 2005, 17, 6186. (21) Chung, D. Y.; Uher, C.; Kanatzidis, M. G. Sb and Se Substitution in CsBi4Te6: The Semiconductors CsM(4)Q(6) (M = Bi, Sb; Q = Te, Se), Cs(2)Bi(10)Q(15), and CsBi(5)Q(8). Chem Mater 2012, 24, 1854. (22) Hao, F.; Stoumpos, C. C.; Chang, R. P. H.; Kanatzidis, M. G. Anomalous Band Gap Behavior in Mixed Sn and Pb Perovskites Enables Broadening of Absorption Spectrum in Solar Cells. J Am Chem Soc 2014, 136, 8094. (23) Umari, P.; Mosconi, E.; De Angelis, F. Relativistic GW calculations on CH3NH3PbI3 and CH3NH3SnI3 Perovskites for Solar Cell Applications. Sci. Rep. 2014, 4. (24) Stoumpos, C. C.; Malliakas, C. D.; Kanatzidis, M. G. Semiconducting Tin and Lead Iodide Perovskites with Organic Cations: Phase Transitions, High Mobilities, and Near-Infrared Photoluminescent Properties. Inorg Chem 2013, 52, 9019. (25) Malliakas, C. D.; Chung, D. Y.; Claus, H.; Kanatzidis, M. G. Superconductivity in the Narrow-Gap Semiconductor CsBi4Te6. J Am Chem Soc 2013, 135, 14540. (26) Fang, L.; Im, J.; Stoumpos, C. C.; Shi, F.; Dravid, V.; Leroux, M.; Freeman, A. J.; Kwok, W.-K.; Chung, D. Y.; Kanatzidis, M. Two-Dimensional Mineral [Pb2BiS3][AuTe2]: High-Mobility Charge Carriers in SingleAtom-Thick Layers. J Am Chem Soc 2015, 137, 2311. (27) Ye, F.; Chi, S.; Bao, W.; Wang, X. F.; Ying, J. J.; Chen, X. H.; Wang, H. D.; Dong, C. H.; Fang, M. H. Common Crystalline and Magnetic Structure of Superconducting A(2)Fe(4)Se(5) (A = K, Rb, Cs, Tl) Single Crystals Measured Using Neutron Diffraction. Physical Review Letters 2011, 107. (28) Owens, A. Semiconductor materials and radiation detection. J Synchrotron Radiat 2006, 13, 143. (29) Hitomi, K.; Shoji, T.; Ishii, K. Advances in TlBr detector development. J Cryst Growth 2013, 379, 93. (30) Zhang, T.; Tkaczyk, J. E.; Andreini, K.; Pan, F.; Williams, Y. Z.; Du, Y.; Chen, H.; Bindley, G. Modular Sensor Pack for large Thickness Cadmium Zinc Telluride (CZT) Gamma Radiation Detectors. Ieee Nucl Sci Conf R 2010, 3776. (31) Luke, P. N. Single-Polarity Charge Sensing in Ionization Detectors Using Coplanar Electrodes. Appl Phys Lett 1994, 65, 2884. (32) Barrett, H. H.; Eskin, J. D.; Barber, H. B. Charge Transport in Arrays of Semiconductor Gamma-Ray Detectors. Physical Review Letters 1995, 75, 156. (33) Shor, A.; Eisen, Y.; Mardor, I. Optimum spectroscopic performance from CZT γ- and X-ray detectors with pad and strip segmentation. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment 1999, 428, 182. (34) Piechotka, M. Mercuric iodide for room temperature radiation detectors. Synthesis, purification, crystal growth and defect formation. Mat Sci Eng R 1997, 18, 1. (35) Engel, P.; Nowacki, W.; Baliczunic, T.; Scavnicar, S. The Crystal-Structure of Simonite, Tlhgas3s6. Z Kristallogr 1982, 161, 159. (36) Owens, A.; Peacock, A. Compound semiconductor radiation detectors. Nucl Instrum Meth A 2004, 531, 18.



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 14 of 24

(37) Armantrout, G. A.; Swierkowski, S. P.; Sherohman, J. W.; Yee, J. H. What Can Be Expected from High-Z Semiconductor-Detectors. Ieee T Nucl Sci 1977, 24, 121. (38) Gave, M. A.; Malliakas, C. D.; Weliky, D. P.; Kanatzidis, M. G. Wide compositional and structural diversity in the system TI/Bi/P/Q (Q = S, Se) and observation of vicinal P-TI J coupling in the solid state. Inorg Chem 2007, 46, 3632. (39) Wibowo, A. C.; Malliakas, C. D.; Chung, D. Y.; Im, J.; Freeman, A. J.; Kanatzidis, M. G. Thallium Mercury Chalcobromides, TlHg(6)Q(4)Br(5) (Q = S, Se). Inorg Chem 2013, 52, 11875. (40) Bugaris, D. E.; Choi, E. S.; Copping, R.; Glans, P. A.; Minasian, S. G.; Tyliszczak, T.; Kozimor, S. A.; Shuh, D. K.; Ibers, J. A. Pentavalent and Tetravalent Uranium Selenides, Tl3Cu4USe6 and Tl2Ag2USe4: Syntheses, Characterization, and Structural Comparison to Other Layered Actinide Chalcogenide Compounds. Inorg Chem 2011, 50, 6656. (41) Huang, C.; Hu, C. L.; Xu, X.; Yang, B. P.; Mao, J. G. Tl(VO)(2)O-2(IO3)(3): a new polar material with a strong SHG response. Dalton T 2013, 42, 7051. (42) Axtell, E. A.; Park, Y.; Chondroudis, K.; Kanatzidis, M. G. Incorporation of A(2)Q into HgQ and dimensional reduction to A(2)Hg(3)Q(4) and A(2)Hg(6)Q(7) (A = K, Rb, Cs; Q = S, Se). Access of Li ions in A(2)Hg(6)Q(7) through topotactic ion-exchange. J Am Chem Soc 1998, 120, 124. (43) Islam, S. M.; Im, J.; Freeman, A. J.; Kanatzidis, M. G. Ba2HgS5-A Molecular Trisulfide Salt with Dumbbell-like (HgS2)(2-) Ions. Inorg Chem 2014, 53, 4698. (44) Morris, C. D.; Li, H.; Jin, H.; Malliakas, C. D.; Peters, J. A.; Trikalitis, P. N.; Freeman, A. J.; Wessels, B. W.; Kanatzidis, M. G. Cs(2)M(II)M(3)(IV)Q(8) (Q=S, Se, Te): An Extensive Family of Layered Semiconductors with Diverse Band Gaps. Chem Mater 2013, 25, 3344. (45) Oleneva, O. S.; Olenev, A. V.; Shestimerova, T. A.; Baranov, A. I.; Dikarev, E. V.; Shevelkov, A. V. Reduction of the host cationic framework charge by isoelectronic substitution: Synthesis and structure of Hg7Ag2P8X6 (X=Br, I) and Hg6Ag4P8Br6. Inorg Chem 2005, 44, 9622. (46) Shevelkov, A. V.; Dikarev, E. V.; Popovkin, B. A. Helical 1(Infinity(P(1)-) Chains in the Structures of Hg2p3br and Hg2p3cl. Z Kristallogr 1994, 209, 583. (47) Shevelkov, A. V.; Dikarev, E. V.; Popovkin, B. A. Syntheses and Crystal-Structure of Hg7p4br6. J Solid State Chem 1993, 104, 177. (48) Banda, R. M. H.; Craig, D.; Dance, I. G.; Scudder, M. Tetrahedral Hgs4 and Linear Hgs2 Coordination in the Crystal-Structure of Na2hg3s4(H2o)2. Polyhedron 1991, 10, 41. (49) Beck, J.; Neisel, U. Polycationic Hg-pnictide frameworks with a novel kind of filling in the structures of Hg3As2TlCl3 and Hg3Sb2TlBr3. Z Anorg Allg Chem 2001, 627, 2016. (50) Mozolyuk, M. Y.; Piskach, L. V.; Fedorchuk, A. O.; Olekseyuk, I. D.; Parasyuk, O. V. Physico-chemical interaction in the Tl2Se-HgSe-(DSe2)-Se-IV systems (D-IV - Si, Sn). Mater Res Bull 2012, 47, 3830. (51) Asadov, M. M. The Hgse + Tl2te-Reversible-Hgte + Tl2se Mutual Ternary-System. Inorg Mater+ 1984, 20, 28. (52) Asadov, M. M. Regions of Phase Homogeneity in the System Hgse+Tl2te-Reversible-Hgte+Tl2se. Inorg Mater+ 1984, 20, 1397. (53) Kahler, D.; Singh, N. B.; Knuteson, D. J.; Wagner, B.; Berghmans, A.; McLaughlin, S.; King, M.; Schwartz, K.; Suhre, D.; Gotlieb, M. Performance of novel materials for radiation detection: Tl3AsSe3, TlGaSe2, and Tl4HgI6. Nucl Instrum Meth A 2011, 652, 183. (54) Sheldrick, G. M. SHELXTL version 5.1; Univeristy of Göttingen: Göttingen, Germany, 1997. (55) McCarthy, T. J.; Ngeyi, S. P.; Liao, J. H.; DeGroot, D. C.; Hogan, T.; Kannewurf, C. R.; Kanatzidis, M. G. Molten salt synthesis and properties of three new solid-state ternary bismuth chalcogenides, .beta.CsBiS2, .gamma.-CsBiS2, and K2Bi8Se13. Chem Mater 1993, 5, 331. (56) Hecht, W. W. W. H. G. Reflectance Spectroscopy; Interscience Publisher: New York, 1966.


Page 15 of 24

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(57) Tandon, S. P.; Gupta, J. P. Measurement of Forbidden Energy Gap of Semiconductors by Diffuse Reflectance Technique. physica status solidi (b) 1970, 38, 363. (58) Singh, D. Planewaves, Pseudopotentials, and LAPW method; KLuwer Academic: Boston, MA, 1994. (59) Kohn, W.; Sham, L. J. Self-Consistent Equations Including Exchange and Correlation Effects. Physical Review 1965, 140, A1133. (60) Hohenberg, P.; Kohn, W. Inhomogeneous Electron Gas. Physical Review 1964, 136, B864. (61) Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized Gradient Approximation Made Simple. Physical Review Letters 1996, 77, 3865. (62) Koelling, D. D.; Harmon, B. N. A technique for relativistic spin-polarised calculations. Journal of Physics C: Solid State Physics 1977, 10, 3107. (63) Cook, B. A.; Kramer, M. J.; Harringa, J. L.; Han, M. K.; Chung, D. Y.; Kanatzidis, M. G. Analysis of Nanostructuring in High Figure-of-Merit Ag1-xPbmSbTe2+m Thermoelectric Materials. Adv Funct Mater 2009, 19, 1254. (64) Blaha, P.; Schwarz, K.; Madsen, G.; Kvasnicka, D.; Luitz , J.; Karlheinz Schwarz, Tech. Univ.: Wien, Vienna, 2001. (65) Nadjafov, A. I.; Alekperov, O. Z.; Guseinov, G. G. Preparation and properties of orthorhombic TlInS2. Inorg Mater+ 2005, 41, 98. (66) Veis, A. N.; Koditsa, D. D.; Popovich, N. S. Optical properties of TlBiS2 monocrystals. physica status solidi (a) 1988, 107, K169. (67) Rouquette, P.; Camassel, J.; Bastide, G.; Martin, L.; Olivier-Fourcade, J.; Philippot, E. Polarization dependence of the Raman spectra of TlSbS2. Solid State Communications 1986, 60, 709. (68) Guseinov, G. D.; Abdullayev, A. G.; Ismailov, M. Z.; Rustamov, V. D. The piezoresistive effect in the p-TlInSe2 single crystals. Mater Res Bull 1977, 12, 115. (69) Huang, T.; Ruoff, A. L. Pressure-Induced Phase-Transition of Hgs. J Appl Phys 1983, 54, 5459. (70) Klepp, K. O. Na2hg3s4 - a Thiomercurate with Layered Anions. J Alloy Compd 1992, 182, 281. (71) Axtell, E. A.; Liao, J. H.; Pikramenou, Z.; Kanatzidis, M. G. Dimensional reduction in II-VI materials: A(2)Cd(3)Q(4) (A=K, Q=S, Se, Te; A=Rb, Q=S, Se), novel ternary low-dimensional cadmium chalcogenides produced by incorporation of A(2)Q in CdQ. Chem-Eur J 1996, 2, 656. (72) Bugaris, D. E.; Ibers, J. A. Ba8Hg3U3S18: A Complex Uranium(+4)/Uranium(+5) Sulfide. Inorg Chem 2012, 51, 661. (73) Seltzer, S. M. Calculation of Photon Mass Energy-Transfer and Mass Energy-Absorption Coefficients. Radiat Res 1993, 136, 147. (74) Rodnyi, P. A. Physical processes in inorganic scintillators; CRC Press: Boca Raton, 1997. (75) McGregor, D. S.; Hermon, H. Room-temperature compound semiconductor radiation detectors. Nucl Instrum Meth A 1997, 395, 101. (76) Schlesinger, T. E.; Toney, J. E.; Yoon, H.; Lee, E. Y.; Brunett, B. A.; Franks, L.; James, R. B. Cadmium zinc telluride and its use as a nuclear radiation detector material. Mat Sci Eng R 2001, 32, 103. (77) Hecht, K. Zum Mechanismus des lichtelektrischen Primärstromes in isolierenden Kristallen. Z. Physik 1932, 77, 235. (78) Uxa, S.; Grill, R.; Belas, E. Evaluation of the mobility-lifetime product in CdTe and CdZnTe detectors by the transient-current technique. J Appl Phys 2013, 114.



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Table 1. Crystal data and structure refinement details for TlHgInS3 at 293(2) K. Empirical formula Formula weight

TlHgInS3 615.96

Temperature

293(2) K

Wavelength Crystal system

0.71073 Å Monoclinic

Space group Unit cell dimensions

C2/c a = 13.916(3) Å, α = 90.00° b = 3.9132(8) Å, β = 104.16(3)° c = 21.403(4) Å, γ = 90.00°

Volume Å3, Z

1130.1(4), 8 Density (calculated) 7.241 g/cm3 Absorption coefficient 60.545 mm-1 F(000) 2064 Crystal size 0.20 x 0.07 x 0.05 mm3 θ range for data collection 1.96 to 25.00° Index ranges -16

TlHgInS3: An Indirect-Band-Gap Semiconductor with X-ray

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