Bi Se Research Articles

Understanding the Structure and Properties of Sesqui‐Chalcogenides (i.e., V2VI3 or Pn2Ch3 (Pn = Pnictogen, Ch = Chalcogen) Compounds) from a Bonding Perspective

A number of sesqui-chalcogenides show remarkable properties, which make them attractive for applications as thermoelectrics, topological insulators, and phase-change materials. To see if these properties can be related to a special bonding mechanism, seven sesqui-chalcogenides (Bi2 Te3 , Bi2 Se3 , Bi2 S3 , Sb2 Te3 , Sb2 Se3 , Sb2 S3 , and β-As2 Te3 ) and GaSe are investigated. Atom probe tomography studies reveal that four of the seven sesqui-chalcogenides (Bi2 Te3 , Bi2 Se3 , Sb2 Te3 , and β-As2 Te3 ) show an unconventional bond-breaking mechanism. The same four compounds evidence a remarkable property portfolio in density functional theory calculations including large Born effective charges, high optical dielectric constants, low Debye temperatures and an almost metal-like electrical conductivity. These results are indicative for unconventional bonding leading to physical properties distinctively different from those caused by covalent, metallic, or ionic bonding. The experiments reveal that this bonding mechanism prevails in four sesqui-chalcogenides, characterized by rather short interlayer distances at the van der Waals like gaps, suggestive of significant interlayer coupling. These conclusions are further supported by a subsequent quantum-chemistry-based bonding analysis employing charge partitioning, which reveals that the four sesqui-chalcogenides with unconventional properties are characterized by modest levels of charge transfer and sharing of about one electron between adjacent atoms. Finally, the 3D maps for different properties reveal discernible property trends and enable material design.

The Bi2Se3–Bi2Te3–BiI3 system: Synthesis and characterization of the BiTe1-xSexI solid solutions

This paper describes the phase relationships and ternary solubility of the binary and ternary compounds in the Bi2Se3–Bi2Te3–BiI3 system. Differential thermal analysis (DTA), powder X-ray diffraction (PXRD) and scanning electron microscope equipped with energy dispersive X-ray spectrometer (SEM-EDS) were main tools for experimental investigations of the equilibrated samples of the system. This system is found to be quasi-ternary plane of the quaternary Bi–Se–Te–I system. An isothermal section at 300 K, a liquidus surface projection and four isopleth sections of the system were plotted based on experimental and literature data. The existence of the BiTe1-xSexI solid solutions series (γ1 and γ2) in the wide range of composition of BiSeI–BiTeI section was revealed and characterized. No new quaternary compound was found in the system. The primary crystallization fields and homogeneity range of all the existing phases, as well as character and temperature of all the non- and monovariant equilibria of the system were determined.

Biomodal Tumor‐Targeted and Redox‐Responsive Bi2Se3 Hollow Nanocubes for MSOT/CT Imaging Guided Synergistic Low‐Temperature Photothermal Radiotherapy

Hyperthemia (>50 °C) induced heating damage of nearby normal organs and inflammatory diseases are the main challenges for photothermal therapy (PTT) of cancers. To overcome this limitation, a redox-responsive biomodal tumor-targeted nanoplatform is synthesized, which can achieve multispectral optoacoustic tomography/X-ray computed tomography imaging-guided low-temperature photothermal-radio combined therapy (PTT RT). In this study, Bi2 Se3 hollow nanocubes (HNCs) are first fabricated based on a mild cation exchange way and Kirkendall effect and then modified with hyaluronic acid (HA) through redox-cleavable linkage (-s-s-), thus enabling the HNC to target cancer cells overexpressing CD-44 and control the cargo release profile. Finally, gambogic acid (GA), a type of heat-shock protein (HSP) inhibitor, which is vital to cells resisting heating-caused damage is loaded, into Bi2 Se3 HNC. Such HNC-s-s-HA/GA under a mild NIR laser irradiation can induce efficient cancer cell apoptosis, achieving PTT under relatively low temperature (≈43 °C) with remarkable cancer cell damage efficiency. Furthermore, enhanced radiotherapy (RT) can also be experienced without depth limitation based on RT sensitizer Bi2 Se3 HNC. This research designs a facile way to synthesize Bi2 Se3 HNC-s-s-HA/GA possessing theranostic functionality and cancer cells-specific GSH, but also shows a low-temperature PTT RT method to cure tumors in a minimally invasive and highly efficient way.

Spin-Orbit Torque Switching of a Nearly Compensated Ferrimagnet by Topological Surface States.

Utilizing spin-orbit torque (SOT) to switch a magnetic moment provides a promising route for low-power-dissipation spintronic devices. Here, the SOT switching of a nearly compensated ferrimagnet Gdx (FeCo)1- x by the topological insulator [Bi2 Se3 and (BiSb)2 Te3 ] is investigated at room temperature. The switching current density of (BiSb)2 Te3 (1.20 × 105 A cm-2 ) is more than one order of magnitude smaller than that in conventional heavy-metal-based structures, which indicates the ultrahigh efficiency of charge-spin conversion (>1) in topological surface states. By tuning the net magnetic moment of Gdx (FeCo)1- x via changing the composition, the SOT efficiency has a significant enhancement (6.5 times) near the magnetic compensation point, and at the same time the switching speed can be as fast as several picoseconds. Combining the topological surface states and the nearly compensated ferrimagnets provides a promising route for practical energy-efficient and high-speed spintronic devices.

Optical and transport properties of few quintuple-layers of Bi2-xSbxSe3 nanoflakes synthesized by hydrothermal method

Hydrothermal synthesis as a commonly bottom-up growth method has considerable advantages for manufacturing thermoelectric nanomaterials with advanced thermoelectric properties. However, the hydrothermally synthesized thermoelectric nanostructures often show a low thermoelectric performance due to their low power factor. In this work, we report on using a hydrothermal method for the growth of n-type Bi2-xSbxSe3 nanoflakes with a fixed thickness of ∼16 quintuple-layers. The controlling of the stoichiometric composition, phase purity and crystallinity of the Bi2-xSbxSe3 nanoflakes are demonstrated by the X-ray diffraction, Raman spectroscopy, and high resolution transmission electron microscopy. We further prove that adding of antimony into Bi2Se3 compound mostly influences the in-plane vibration mode. The optical energy gap is sharply increased as the Sb content increases. The effect of the antimony incorporation on the electrical conductivity, Seebeck coefficient and power factor of Bi2-xSbxSe3 nanoflakes is systematically investigated. The Bi1.92Sb0.08Se3 sample is found to have the highest power factor ∼13.17 μW/cm.K2 at 470 K which is much higher than those published for other various nanostructured or bulk Bi2Se3 compounds. The results propose a great prospect for further enhancing the thermoelectric power factor of the Bi2Se3 nanostructures synthesized by this hydrothermal method. Taking into consideration the progress in Bi–Se compounds, the results of this work advocate the promise of Bi–Se nanostructures towards producing high performance thermoelectric devices.

Near‐Infrared Annihilation of Conductive Filaments in Quasiplane MoSe2/Bi2Se3 Nanosheets for Mimicking Heterosynaptic Plasticity

It is desirable to imitate synaptic functionality to break through the memory wall in traditional von Neumann architecture. Modulating heterosynaptic plasticity between pre- and postneurons by another modulatory interneuron ensures the computing system to display more complicated functions. Optoelectronic devices facilitate the inspiration for high-performance artificial heterosynaptic systems. Nevertheless, the utilization of near-infrared (NIR) irradiation to act as a modulatory terminal for heterosynaptic plasticity emulation has not yet been realized. Here, an NIR resistive random access memory (RRAM) is reported, based on quasiplane MoSe2 /Bi2 Se3 heterostructure in which the anomalous NIR threshold switching and NIR reset operation are realized. Furthermore, it is shown that such an NIR irradiation can be employed as a modulatory terminal to emulate heterosynaptic plasticity. The reconfigurable 2D image recognition is also demonstrated by an RRAM crossbar array. NIR annihilation effect in quasiplane MoSe2 /Bi2 Se3 nanosheets may open a path toward optical-modulated in-memory computing and artificial retinal prostheses.

Ultrafast Spin-to-Charge Conversion at the Surface of Topological Insulator Thin Films.

Strong spin-orbit coupling, resulting in the formation of spin-momentum-locked surface states, endows topological insulators with superior spin-to-charge conversion characteristics, though the dynamics that govern it have remained elusive. Here, an all-optical method is presented, which enables unprecedented tracking of the ultrafast dynamics of spin-to-charge conversion in a prototypical topological insulator Bi2 Se3 /ferromagnetic Co heterostructure, down to the sub-picosecond timescale. Compared to pure Bi2 Se3 or Co, a giant terahertz emission is observed in the heterostructure that originates from spin-to-charge conversion, in which the topological surface states play a crucial role. A 0.12 ps timescale is identified that sets a technological speed limit of spin-to-charge conversion processes in topological insulators. In addition, it is shown that the spin-to-charge conversion efficiency is temperature independent in Bi2 Se3 as expected from the nature of the surface states, paving the way for designing next-generation high-speed optospintronic devices based on topological insulators at room temperature.

Suppression of structural instability in LaOBiS2−xSex by Se substitution

Isovalent substitution of S by Se in LaOBiS2−xSex has a substantial effect on its electronic structure and thermoelectric properties. To investigate the possible role of BiS2 structural instability, we have studied the local structure of LaOBiS2−xSex () using temperature dependent Bi L3-edge extended x-ray absorption fine structure measurements. The results reveal that the local structure of the two compounds is significantly different. The BiS2 sub-lattice is largely distorted in LaOBiS2 (x = 0.0), with two in-plane Bi–S1 distances separated by ∼0.4 Å instead LaOBiSSe (x = 1.0) showing much smaller local disorder with two in-plane Bi–Se distances in the plane being separated by ∼0.2 Å. Temperature dependent study shows that the two Bi–S1 distances are characterized by different bond strength in LaOBiS2 (x = 0.0) while it is similar for the Bi–Se distances in LaOBiSSe (x = 1.0). The out of plane Bi–S2 bond is harder in LaOBiSSe indicating that the structural instability of BiS2 layer has large effect on the out-of-plane atomic correlations. The results suggest that the local structure of LaOBiS2−xSex is an important factor to describe differing electronic and thermal transport of the two compounds.

Synthesis, Structure and Application of Intramolecularly-Coordinated Gallium Chalcogenides: Suitable Single-Source precursors for Gax Sey Materials.

Studies have been focused on the synthesis of N→Ga-coordinated organogallium selenides and tellurides [L1 Ga(μ-Se)]2 (1), [L2 Ga(μ-Se)]2 (2) and [L1 Ga(μ-Te)]2 (3), respectively, containing either N,C,N- or C,N-chelating ligands L1, 2 (L1 is {2,6-(Me2 NCH2 )2 C6 H3 }- and L2 is {2-(Et2 NCH2 )-4,6-tBu2 -C6 H2 }- ) having Ga/E (E=Se or Te) atoms in 1/1 ratio. To change the Ga/E ratio, an unusual N→Ga-coordinated organogallium tetraselenide L1 Ga(κ2 -Se4 ) (4) was prepared. An unprecedented complex (L1 Ga)2 (μ-Te2 )(μ-Te) (5), as the result of the non-stability of 3, was also isolated. Compound 2 is a suitable single-source precursor for the preparation of amorphous GaSe thin films by the spin coating. Moreover, simple heating of an octadecylamine solution of 2 provided, after work up, monoclinic Ga2 Se3 crystals with different crystallinity according to conditions used. Therefore, compound 2 may be also used as a source of Ga2 Se3 in the low-temperature doping process of Bi2 Se3 .

Bifunctional Au@Bi2 Se3 Core-Shell Nanoparticle for Synergetic Therapy by SERS-Traceable AntagomiR Delivery and Photothermal Treatment.

For the first time, topological insulator bismuth selenide nanoparticles (Bi2 Se3 NP) are core-shelled with gold (Au@Bi2 Se3 ) i) to represent considerably small-sized (11 nm) plasmonic nanoparticles, enabling accurate bioimaging in the near-infrared region; ii) to substantially improve Bi2 Se3 biocompatibility, iii) water dispersibility, and iv) surface functionalization capability through straightforward gold-thiol interaction. The Au@Bi2 Se3 is subsequently functionalized for v) effective targeting of SH-SY5Y cancer cells, vi) disrupting the endosome/lysosome membrane, vii) traceable delivery of antagomiR-152 and further synergetic oncomiR knockdown and photothermal therapy (PTT). Unprecedentedly, it is observed that the Au shell thickness has a significant impact on evoking the exotic plasmonic features of Bi2 Se3 . The Au@Bi2 Se3 possesses a high photothermal conversion efficiency (35.5%) and a remarkable surface plasmonic effect (both properties are approximately twofold higher than those of 50 nm Au nanoparticles). In contrast to the siRNA/miRNA delivery methods, the antagomiR delivery is based on strand displacement, in which the antagomiR-152 is displaced by oncomiR-152 followed by a surface-enhanced Raman spectroscopy signal drop. This enables both cancer cell diagnosis and in vitro real-time monitoring of the antagomiR release. This selective PTT nanoparticle can also efficiently target solid tumors and undergo in vivo PTT, indicating its potential clinical applications.

Gas-Generating Nanoplatforms: Material Chemistry, Multifunctionality, and Gas Therapy.

The fast advances of theranostic nanomedicine enable the rational design and construction of diverse functional nanoplatforms for versatile biomedical applications, among which gas-generating nanoplatforms (GGNs) have emerged very recently as unique theranostic nanoplatforms for broad gas therapies. Here, the recent developments of the rational design and chemical construction of versatile GGNs for efficient gas therapies by either exogenous physical triggers or endogenous disease-environment responsiveness are reviewed. These gases involve some therapeutic gases that can directly change disease status, such as oxygen (O2 ), nitric oxide (NO), carbon monoxide (CO), hydrogen (H2 ), hydrogen sulfide (H2 S) and sulfur dioxide (SO2 ), and other gases such as carbon dioxide (CO2 ), dl-menthol (DLM), and gaseous perfluorocarbon (PFC) for supplementary assistance of the theranostic process. Abundant nanocarriers have been adopted for gas delivery into lesions, including poly(d,l-lactic-co-glycolic acid), micelles, silica/mesoporous silica, organosilica, MnO2 , graphene, Bi2 Se3 , upconversion nanoparticles, CaCO3 , etc. Especially, these GGNs have been successfully developed for versatile biomedical applications, including diagnostic imaging and therapeutic use. The biosafety issue, challenges faced, and future developments on the rational construction of GGNs are also discussed for further promotion of their clinical translation to benefit patients.

TCNQ Physisorption on the Topological Insulator Bi2 Se3.

Topological insulators are promising candidates for spintronic applications due to their topologically protected, spin-momentum locked and gapless surface states. The breaking of the time-reversal symmetry after the introduction of magnetic impurities, such as 3d transition metal atoms embedded in two-dimensional molecular networks, could lead to several phenomena interesting for device fabrication. The first step towards the fabrication of metal-organic coordination networks on the surface of a topological insulator is to investigate the adsorption of the pure molecular layer, which is the aim of this study. Here, the effect of the deposition of the electron acceptor 7,7,8,8-tetracyanoquinodimethane (TCNQ) molecules on the surface of a prototypical topological insulator, bismuth selenide (Bi2 Se3 ), is investigated. Scanning tunneling microscope images at low-temperature reveal the formation of a highly ordered two-dimensional molecular network. The essentially unperturbed electronic structure of the topological insulator observed by photoemission spectroscopy measurements demonstrates a negligible charge transfer between the molecular layer and the substrate. Density functional theory calculations confirm the picture of a weakly interacting adsorbed molecular layer. These results reveal significant potential of TCNQ for the realization of metal-organic coordination networks on the topological insulator surface.

Experimental and Theoretical Study of Bi2O2Se Under Compression

We report a joint experimental and theoretical study of the structural, vibrational, elastic, optical, and electronic properties of the layered high-mobility semiconductor Bi2O2Se at high pressure. A good agreement between experiments and ab initio calculations is observed for the equation of state, the pressure coefficients of the Raman-active modes and the bandgap of the material. In particular, a detailed description of the vibrational properties is provided. Unlike other Sillen-type compounds which undergo a tetragonal to collapsed tetragonal pressure-induced phase transition at relatively low pressures, Bi2O2Se shows a remarkable structural stability up to 30 GPa; however, our results indicate that this compound exhibits considerable electronic changes around 4 GPa, likely related to the progressive shortening and hardening of the long and weak Bi–Se bonds linking the Bi2O2 and Se atomic layers. Variations of the structural, vibrational, and electronic properties induced by these electronic changes a...

Electrochemical Biosensor Composed of Silver Ion‐Mediated dsDNA on Au‐Encapsulated Bi2Se3 Nanoparticles for the Detection of H2O2 Released from Breast Cancer Cells

A newly developed electrochemical biosensor composed of a topological insulator (TI) and metallic DNA (mDNA) is fabricated. The bismuth selenide nanoparticle (Bi2 Se3 NP) is synthesized and sandwiched between the gold electrode and another Au-deposited thin layer (Bi2 Se3 @Au). Then, eight-silver-ion mediated double-stranded DNA (mDNA) is immobilized onto the substrate (Bi2 Se3 @Au-mDNA) for the further detection of hydrogen peroxide. The Bi2 Se3 NP acts as the electrochemical-signal booster, while unprecedentedly its encapsulation by the Au thin layer keeps the TI surface states protected, improves its electrochemical-signal stability and provides an excellent platform for the subsequent covalent immobilization of the mDNA through Au-thiol interaction. Electrochemical results show that the fabricated biosensor represents much higher Ag+ redox current (≈10 times) than those electrodes prepared without Bi2 Se3 @Au. The characterization of the Bi2 Se3 @Au-mDNA film is confirmed by atomic force microscopy, scanning tunneling microscopy, and cyclic voltammetry. The proposed biosensor shows a dynamic range of 00.10 × 10-6 m to 27.30 × 10-6 m, very low detection limit (10 × 10-9 m), unique current response (1.6 s), sound H2 O2 recovery in serum, and substantial capability to classify two breast cancer subtypes (MCF-7 and MDA-MB-231) based on their difference in the H2 O2 generation, offering potential applications in the biomedicine and pharmacology fields.

Role of lattice inhomogeneities on the electronic properties of selenium deficient Bi2Se3

Inter-layer coupling is widely considered to play a crucial role in tuning electronic properties of 3D topological insulators. The aim of this study is to evaluate the role of crystallographic defects on inter-layer coupling in the Se deficient Bi2Se3 (0 0 3) crystal using extended x-ray absorption fine structure spectroscopy (EXAFS) technique. EXAFS measurements at Se–K and Bi–L3 edges reveal distinct local geometry around these atomic sites. It has been observed that short inter-layer Bi–Se and Se–Se bonds emerge in the sample. This additional structural motif coexists with the conventional crystallographic arrangement. Within the quintuple layer Bi–Se bonds are preserved with slight compression in intra-planer Bi–Bi and Se–Se distance and overall reduction in c/a ratio. These findings suggest formation of deformed lattice region, localized and dispersed inhomogeneously within the sample. Such inhomogeneities have also resulted in interesting transport properties such as quantum Hall effect (QHE), large linear magnetoresistance and π-Berry phase in Shubnikov-de Haas (SdH) oscillations of bulk crystals. Detailed analyses of magnetotransport measurements suggest that tuning of inter-layer coupling by local lattice deformation is the key factor for unusual transport properties. Role of axial strain, and stacking faults generated due to defects and charged Se vacancies are discussed to understand the observed electronic properties.

Chemical Intercalation of Topological Insulator Grid Nanostructures for High-Performance Transparent Electrodes.

2D layered nanomaterials with strong covalent bonding within layers and weak van der Waals' interactions between layers have attracted tremendous interest in recent years. Layered Bi2 Se3 is a representative topological insulator material in this family, which holds promise for exploration of the fundamental physics and practical applications such as transparent electrode. Here, a simultaneous enhancement of optical transmittancy and electrical conductivity in Bi2 Se3 grid electrodes by copper-atom intercalation is presented. These Cu-intercalated 2D Bi2 Se3 electrodes exhibit high uniformity over large area and excellent stabilities to environmental perturbations, such as UV light, thermal fluctuation, and mechanical distortion. Remarkably, by intercalating a high density of copper atoms, the electrical and optical performance of Bi2 Se3 grid electrodes is greatly improved from 900 Ω sq-1 , 68% to 300 Ω sq-1 , 82% in the visible range; with better performance of 300 Ω sq-1 , 91% achieved in the near-infrared region. These unique properties of Cu-intercalated topological insulator grid nanostructures may boost their potential applications in high-performance optoelectronics, especially for infrared optoelectronic devices.

Tuning chemical potential in the dirac cone by compositional engineering

To realize fully topological transport for any device applications it is essential to tune the chemical potential in the bulk gap of the Dirac cone. Bi2Se3 (BS) and Bi2Te3 (BT) thin films do not show in general topological transport as the chemical potential doesn’t lie entirely in the bulk gap. We report the successful formation of bulk insulating ternary topological insulators Bi2Se2Te (BST) by double target pulsed laser deposition technique. The films were deposited with sequential ablation of separate BS and BT targets. From the X-ray diffraction analysis and temperature dependent resistivity, we were able to conclude that the as-grown thin films have ordered chalcogen layers and the chemical potential in these thin films lie in the bulk gap. We have been able to achieve this fully topological transport in our sample grown by this technique. Our Magnetotransport data exhibits pronounced two-dimensional weak-antilocalization behavior (WAL) at low temperatures. It was possible to tune the chemical potential at will in the gap by depositing thin films through pulsed laser deposition technique using this simple and cost effective double target approach to grow quaternary TI thin films.

Synthesis and magnetotransport properties of Bi2Se3 nanowires**Project supported by the National Key Basic Research Program of China (Grant Nos. 2014CB921103 and 2013CB921103), the National Natural Science Foundation of China (Grant Nos. 11274003 and 91421109), and Collaborative Innovation Center of Solid-State Lighting and Energy-Saving Electronics,China.

Bi2Se3, as a three-dimensional topological insulator, has attracted worldwide attention for its unique surface states which are protected by time-reversal symmetry. Here we report the synthesis and characterization of high-quality single-crystalline Bi2 Se3 nanowires. Bi2Se3 nanowires were synthesized by chemical vapor deposition (CVD) method via gold-catalyzed vapor-liquid-solid (VLS) mechanism. The structure and morphology were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), x-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. In magnetotransport measurements, the Aharonov—Bohm (AB) effect was observed in a nanowire-based nanodevice, suggesting the existence of surface states in Bi2Se3 nanowires.

Poly(Vinylpyrollidone)- and Selenocysteine-Modified Bi2 Se3 Nanoparticles Enhance Radiotherapy Efficacy in Tumors and Promote Radioprotection in Normal Tissues.

The development of a new generation of nanoscaled radiosensitizers that can not only enhance radiosensitization of tumor tissues, but also increase radioresistance of healthy tissue is highly desirable, but remains a great challenge. Here, this paper reports a new versatile theranostics based on poly(vinylpyrollidone)- and selenocysteine-modified Bi2 Se3 nanoparicles (PVP-Bi2 Se3 @Sec NPs) for simultaneously enhancing radiotherapeutic effects and reducing the side-effects of radiation. The as-prepared nanoparticles exhibit significantly enhanced free-radical generation upon X-ray radiation, and remarkable photothermal effects under 808 nm NIR laser irradiation because of their strong X-ray attenuation ability and high NIR absorption capability. Moreover, these PVP-Bi2 Se3 @Sec NPs are biodegradable. In vivo, part of selenium can be released from NPs and enter the blood circulation system, which can enhance the immune function and reduce the side-effects of radiation in the whole body. As a consequence, improved superoxide dismutase and glutathione peroxidase activities, promoted secretion of cytokines, increased number of white blood cell, and reduced marrow DNA suppression are found after radiation treatment in vivo. Moreover, there is no significant in vitro and in vivo toxicity of PVP-Bi2 Se3 @Sec NPs during the treatment, which demonstrates that PVP-Bi2 Se3 @Sec NPs have good biocompatibility.

Hansblockite, (Cu,Hg)(Bi,Pb)Se2, the monoclinic polymorph of grundmannite: a new mineral from the Se mineralization at El Dragón (Bolivia)

AbstractHansblockite, ideally (Cu,Hg)(Bi,Pb)Se2, is a new selenide from the El Dragón mine, Bolivia. It typically occurs in thin subparallel plates intergrown with two unnamed Cu–Hg–Pb–Bi–Se species, clausthalite, Corich penroseite and petrovicite.It also forms subhedral to anhedral grains up to 150 μm long and 50 μm wide. Hansblockite is non-fluorescent, black and opaque with a metallic lustre and black streak. It is brittle, with an irregular fracture and no obvious parting and cleavage. The VHN20 values range from37 to 50 (mean 42) kg mm–2 (Mohs hardness 2–2½). In plane-polarized incident light, hansblockite is cream to light grey in colour, weakly bireflectant and weakly pleochroic from greyish cream to cream. Under crossed polars, hansblockite is weakly anisotropic withkhaki to pale blue rotation tints. The reflectance values in air for the Commission on Ore Mineralogy (COM) standard wavelengths are: 47.3–48.1 (470 nm), 47.4–49.9 (546 nm), 47.1–49.0 (589 nm) and 46.6–48.5 (650 nm). The mean composition is Cu 9.31, Ag 0.73, Hg 11.43,Pb 3.55, Ni 0.17, Co 0.03, Bi 31.17, Se 34.00, total 100.39 wt.%. The mean empirical formula (based on 4 apfu) is (Cu0.68Hg0.27Ag0.03Ni0.01)∑=0.99(Bi0.69Pb0.31)∑=1.00Se2.01. The simplifiedformula is (Cu,Hg) (Bi,Pb)Se2. Hansblockite is monoclinic, space group P21/c, with a = 6.853(1), b = 7.635(1), c = 7.264(1) Å, β = 97.68(1)°, V = 376.66(9) Å3 and Z = 4. Density is 8.26 gcm–3. The five strongest powder X-ray diffraction lines [d in Å (I/I0) (hkl)] are: 3.97 (90) (111), 3.100 (40) (121), 2.986 (100) (211), 2.808 (50) (112) and 2.620 (50) (022). Hansblockite represents the monoclinic polymorph ofgrundmannite, CuBiSe2, with Hg and Pb being essential in stabilizing the monoclinic structure via the coupled substitution Cu+ + Bi3+⇔ Hg2+ + Pb2+. The mineral name is in honour of Hans Block (1881–1953), in recognition of hisimportant role in boosting Bolivian ore mining.