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Title: Mercury Chalcohalide Semiconductor Hg 3Se 2Br 2 for Hard Radiation Detection

Abstract

We present Hg 3Se 2Br 2 that has a wide band gap semiconductor (2.22 eV) with high density (7.598 g/cm 3) and crystallizes in the monoclinic space group C2/m with cell parameters of a = 17.496 (4) Å, b = 9.3991 (19) Å, c = 9.776(2) Å, β = 90.46(3)°, V = 1607.6(6) Å 3. It melts congruently at a low temperature, 566°C, which allows for an easy single crystal growth directly from the stoichiometric melt. Single crystals of Hg 3Se 2Br 2 up to 1 cm long have been grown using the Bridgman method. Hg 3Se 2Br 2 single crystals exhibit a strong photocurrent response when exposed to Ag X-ray and blue diode laser. The resistivity of Hg 3Se 2Br 2 measured by the two probe method is on the order of 10 11 Ω·cm, and the mobility-lifetime product (μτ) of the electron and hole carriers estimated from the energy spectroscopy under Ag X-ray radiation are (μτ) e ≈ 1.4 × 10 –4cm 2/V and (μτ) h ≈ 9.2 × 10 –5cm 2/V. Electronic structure calculations at the density functional theory level indicate a direct band gap and a relatively small effective mass for carriers. Lastly, on the basismore » of the photoconductivity and hard X-ray spectrum, Hg 3Se 2Br 2 is a promising candidate for X-ray and γ-ray radiation detection at room temperature.« less

Authors:
 [1];  [1];  [2];  [3];  [1];  [4];  [2]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division; Northwestern Univ., Evanston, IL (United States). Department of Chemistry
  3. Northwestern Univ., Evanston, IL (United States). Department of Materials Science and Engineering
  4. Northwestern Univ., Evanston, IL (United States). Department of Materials Science and Engineering and Department of Electrical Engineering and Computer Science
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE NA Office of Nonproliferation and Verification Research and Development (NA-22)
OSTI Identifier:
1352593
Grant/Contract Number:
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Crystal Growth and Design
Additional Journal Information:
Journal Volume: 16; Journal Issue: 11; Journal ID: ISSN 1528-7483
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; X-ray detector; chalcohalide; crystal growth; mobility-lifetime product; photoconductivity; γ-ray detector

Citation Formats

Li, Hao, Meng, Fang, Malliakas, Christos D., Liu, Zhifu, Chung, Duck Young, Wessels, Bruce, and Kanatzidis, Mercouri G.. Mercury Chalcohalide Semiconductor Hg3Se2Br2 for Hard Radiation Detection. United States: N. p., 2016. Web. doi:10.1021/acs.cgd.6b01118.
Li, Hao, Meng, Fang, Malliakas, Christos D., Liu, Zhifu, Chung, Duck Young, Wessels, Bruce, & Kanatzidis, Mercouri G.. Mercury Chalcohalide Semiconductor Hg3Se2Br2 for Hard Radiation Detection. United States. doi:10.1021/acs.cgd.6b01118.
Li, Hao, Meng, Fang, Malliakas, Christos D., Liu, Zhifu, Chung, Duck Young, Wessels, Bruce, and Kanatzidis, Mercouri G.. Wed . "Mercury Chalcohalide Semiconductor Hg3Se2Br2 for Hard Radiation Detection". United States. doi:10.1021/acs.cgd.6b01118. https://www.osti.gov/servlets/purl/1352593.
@article{osti_1352593,
title = {Mercury Chalcohalide Semiconductor Hg3Se2Br2 for Hard Radiation Detection},
author = {Li, Hao and Meng, Fang and Malliakas, Christos D. and Liu, Zhifu and Chung, Duck Young and Wessels, Bruce and Kanatzidis, Mercouri G.},
abstractNote = {We present Hg3Se2Br2 that has a wide band gap semiconductor (2.22 eV) with high density (7.598 g/cm3) and crystallizes in the monoclinic space group C2/m with cell parameters of a = 17.496 (4) Å, b = 9.3991 (19) Å, c = 9.776(2) Å, β = 90.46(3)°, V = 1607.6(6) Å3. It melts congruently at a low temperature, 566°C, which allows for an easy single crystal growth directly from the stoichiometric melt. Single crystals of Hg3Se2Br2 up to 1 cm long have been grown using the Bridgman method. Hg3Se2Br2 single crystals exhibit a strong photocurrent response when exposed to Ag X-ray and blue diode laser. The resistivity of Hg3Se2Br2 measured by the two probe method is on the order of 1011 Ω·cm, and the mobility-lifetime product (μτ) of the electron and hole carriers estimated from the energy spectroscopy under Ag X-ray radiation are (μτ)e ≈ 1.4 × 10–4cm2/V and (μτ)h ≈ 9.2 × 10–5cm2/V. Electronic structure calculations at the density functional theory level indicate a direct band gap and a relatively small effective mass for carriers. Lastly, on the basis of the photoconductivity and hard X-ray spectrum, Hg3Se2Br2 is a promising candidate for X-ray and γ-ray radiation detection at room temperature.},
doi = {10.1021/acs.cgd.6b01118},
journal = {Crystal Growth and Design},
number = 11,
volume = 16,
place = {United States},
year = {Wed Sep 28 00:00:00 EDT 2016},
month = {Wed Sep 28 00:00:00 EDT 2016}
}

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  • Here, we assess the mercury chalcohalide compound, β-Hg 3S 2Cl 2, as a potential semiconductor material for X-ray and γ-ray detection. It has a high density (6.80 g/cm 3) and wide band gap (2.56 eV) and crystallizes in the cubic Pm4more » $$\bar{3}$$n space group with a three-dimensional structure comprised of [Hg 12S 8] cubes with Cl atoms located within and between the cubes, featuring a trigonal pyramidal SHg3 as the main building block. First-principle electronic structure calculations at the density functional theory level predict that the compound has closely lying indirect and direct band gaps. We have successfully grown transparent, single crystals of β-Hg 3S 2Cl 2 up to 7 mm diameter and 1 cm long using a new approach by the partial decomposition of the quaternary Hg 3Bi 2S 2Cl 8 compound followed by the formation of β-Hg 3S 2Cl 2 and an impermeable top layer, all happening in situ during vertical Bridgman growth. The decomposition process was optimized by varying peak temperatures and temperature gradients using a 2 mm/h translation rate of the Bridgman technique. Formation of the quaternary Hg 3Bi 2S 2Cl 8 followed by its partial decomposition into β-Hg 3S 2Cl 2 was confirmed by in situ temperature-dependent synchrotron powder diffraction studies. The single crystal samples obtained had resistivity of 10 10 Ω·cm and mobility-lifetime products of electron and hole carriers of 1.4(4) × 10 –4 cm 2/V and 7.5(3) × 10 –5 cm 2/V, respectively. Further, an appreciable Ag X-ray photoconductivity response was observed showing the potential of β-Hg 3S 2Cl 2 as a hard radiation detector material.« less
  • The salts (({mu}-TePh){sub 6}(HgPR{prime}{sub 3}){sub 3}(Hg))(ClO{sub 4}){sub 2} (R{prime} = Ph, 4-C{sub 6}H{sub 4}Me, 4-C{sub 6}H{sub 4}Cl) are preparable from Hg(TePh){sub 2}, Mg(PR{prime}{sub 3}){sub 2}(ClO{sub 4}){sub 2}, and PR{prime}P{sub 3} in a 3:1:1 ratio in CH{sub 2}Cl{sub 2} or CHCl{sub 3}. The new cations have been characterized in CH{sub 2}Cl{sub 2} and DMF by multinuclear ({sup 31}P, {sup 125}Te, {sup 199}Hg) magnetic resonance and shown to be of adamantanoid structure with novel tellurolate bridging. These spectra provide clear evidence for preferential formation of one (R{prime} = Ph) or a mixture of both (R{prime} = 4-C{sub 6}H{sub 4}Cl, in DMF solution)more » of the two C{sub 3} isomers that are possible for adamantane-like ({mu}-TeR){sub 6}M{sub 4} as a result of inversion at the pyramidal Te atoms. Such preferential isomer formation has not been demonstrated previously for any adamantanoid chalcogenate-bridge ({mu}-ER){sub 6}M{sub 4} in solution. Isomer formation at various temperatures is reported. For the cations with R = Ph, the rate of inversion at Te varies with R{prime} in the order alkyl > 4-C{sub 6}H{sub 4}Me > Ph > 4-C{sub 6}H{sub 4}Cl. When R = Ph, R{prime} = 4-C{sub 6}H{sub 4}Me, NMR spectra ({sup 31}P, {sup 77}Se, {sup 125}Te, {sup 199}Hg) of mixtures of ((TeR){sub 6}(HgPR{prime}{sub 3}){sub 4}){sup 2+} and (({mu}-ER){sub 6}(HgPR{prime}{sub 3}){sub 4}){sup 2+} (E = S, Se) provide evidence for the formation of the mixed-chalcogen cores ({mu}-Te){sub 6-m}({mu}-E){sub m}Hg{sub 4}. 35 refs., 8 figs., 3 tabs.« less
  • Multinuclear magnetic resonance has been used to characterize the new adamantane-like anions (({mu}-ER){sub 6}(HgX){sub 4}){sup 2{minus}} (ER = SPr{sup n}, SPh, SePh, TePh; X = Cl, Br, I), which are formed in CH{sub 2}Cl{sub 2} and (or) DMF from Hg(ER){sub 2}, HgX{sub 2} and (R{sub 4}N)X in the correct stoichiometric ratio. The products (Et{sub 4}N){sub 2}(({mu}-EPh){sub 6}(HgCl){sub 4}) (E = Se, Te) have been isolated analytically pure. At ambient probe temperature, only the complexities (({mu}-TePh){sub 6}(HgX){sub 4}){sup 2{minus}} are stable to dissociation of the ({mu}-ER){sub 6}Hg{sub 4} core. However, at 213 K, only the core of (({mu}-SPh){sub 6}(HgCl){sub 4}){sup 2{minus}}more » is measurably dissociated. Overall, the stability of the complexes to dissociation varies with E in the order Te > Se > S. At reduced temperature inversion at Te is slow on the NMR time scale in (({mu}-TePh){sub 6}(HgX){sub 4}){sup 2{minus}}, and these complexes are shown to exist as on predominant configurational isomer or an equilibrium mixture of, probably, two such isomers. Similar behavior is found for (({mu}-SePh){sub 6}(HgX){sub 4}){sup 2{minus}} (X = Cl, Br), which are the first examples of SeR-bridged adamantanoid clusters to exhibit inversion at Se that is slow on the NMR time scale. Metal ({sup 113}Cd, {sup 199}Hg) NMR data for (({mu}-SPr{sup n}){sub 6}(MI){sub 4}){sup 2{minus}}/(({mu}-SPr{sup n}){sub 6}(M{prime}I){sub 4}){sup 2{minus}} (M = Hg, M{prime} = Cd, Zn; M = Zn, M{prime} = Cd) mixtures at 213 K show that an approximately statistical metal redistribution occurs to give (({mu}-SPr{sup n}){sub 6}(MI){sub 4{minus}n}(M{prime}I){sub n}){sup 2{minus}}. 37 refs., 1 fig., 4 tabs.« less
  • Several series of complexes of the types (MeHg(SR)) and (Hg(SR){sub 2}) have been synthesized, where the ligands are members of new classes of sterically hindered thiolates, including (triorganosilyl)methanethiols, 2-(triorganosilyl)benzenethiols, 3-(triorganosilyl)pyridine-2-thiols, and bis(2-mercaptophenyl) derivatives. Detailed {sup 1}H, {sup 13}C, and {sup 199}Hg NMR studies revealed several general trends. The {sup 199}Hg chemical shifts moved upfield in the order (MeHg(SR)) < (Hg(SCR{prime}R{double prime}R{prime}{double prime}){sub 2}) < (Hg(S-aryl){sub 2}) < (Hg(S-pyridyl){sub 2}). For the (MeHg(SR)) series of complexes, {sup 1}J(Hg-C) correlates with {delta}({sup 13}C(methyl)) and with the type of thiolate ligand. Anomalous behavior is observed for oligomeric species. There is only a limitedmore » correlation of {delta}({sup 199}Hg) with steric cone angles for a subset of the complexes. Crystal data for the complexes are reported. 86 refs., 7 figs., 11 tabs.« less
  • A new method is described to synthesize the semiconductor Cs2Hg6S7 and its alloy with Cd. Using the as-synthesized material, large single crystals have been grown by the Bridgman method under an improved set of crystal growth parameters. In addition, Cd alloying in the form of Cs(2)Hg(6)xCd(x)S(7) (x = 0.25, 0.5, 0.75, etc.) as well as doping with In, Cl was investigated and the influence on the electronic properties was studied. Cd alloying increases the band gap of Cs2Hg6S7 from 1.63 to 1.84 eV. Doping with In and Cl however creates electron carriers and changes p-type samples of Cs2Hg6S7 into nmore » type. A 30-fold increase in the resistivity of the single crystals from 2 X 10(6) to 0.65 X 10(8) Omega cm has been achieved. The carrier mobility-lifetime product of the Cs(2)Hg6S7 crystals has been increased to 1.7 X 10(-3) cm2/V for electrons (mu t)(e) and 2.4 X 10(-3) cm2/V for holes (mu t)(h) (HgCl2 doped). The measured (mu t)e value is comparable to the commercial CdZnTe crystal while the (mu t)h is 10 times higher. Detection of Ag X-ray radiation is demonstrated using the as-grown Cs2Hg6S7 crystals.« less