Chemical Vapour Transport of Bismuth and Antimony Chalcogenides M2Q3 (M = Sb, Bi, Q = Se, Te)

Schöneich, Michael; Schmidt, Marcus; Schmidt, Peer

doi:10.1002/zaac.201000149

Cited by 19 publications

(8 citation statements)

References 32 publications

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“…The vapor-phase deposition of BiTeI can be described as a decomposition sublimation (ϑ 2 = 530 °C to ϑ 1 = 490 °C). If the substance amount of BiTeI within area IV is much lower than needed for saturation of the respective equilibrium pressure (below curve IV , Figure ), the vapor transport of Bi 2 Te 3 (ϑ 2 = 500 °C to ϑ 1 = 450 °C) can be performed without condensation of BiTeI . According to our calculations, area V is preferred for deposition of Bi 2 TeI besides BiTeI.…”

Section: Resultsmentioning

confidence: 80%

Modular Design with 2D Topological-Insulator Building Blocks: Optimized Synthesis and Crystal Growth and Crystal and Electronic Structures of Bi_xTeI (x = 2, 3)

et al. 2017

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Structural engineering of topological bulk materials is systematically explored with regard to the incorporation of the buckled bismuth layer [Bi 2 ], which is a 2D topological insulator per se, into the layered BiTeI host structure. The previously known bismuth telluride iodides, BiTeI and Bi 2 TeI, offer physical properties relevant for spintronics. Herewith a new cousin, Bi 3 TeI (sp.gr. R3m, a = 440.12(2) pm, c = 3223.1(2) pm), joins the ranks and expands this structural family. Bi 3 TeI = [Bi 2 ][BiTeI] represents a stack with strictly alternating building blocks. Conditions for reproducible synthesis and crystal-growth of Bi 2 TeI and Bi 3 TeI are ascertained, thus yielding platelet-like crystals on the millimeter size scale and enabling direct measurements. The crystal structures of Bi 2 TeI and Bi 3 TeI are examined by X-ray diffraction and electron microscopy. DFT calculations predict metallic properties of Bi 3 TeI and an unconventional surface state residing on various surface terminations. This state emerges as a result of complex hybridization of atomic states due to their strong intermixing. Our study does not support the existence of new stacking variants Bi x TeI with x > 3; instead, it indicates a possible homogeneity range of Bi 3 TeI. The series BiTeI−Bi 2 TeI−Bi 3 TeI illustrates the influence of structural modifications on topological properties.

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Section: Resultsmentioning

confidence: 80%

Modular Design with 2D Topological-Insulator Building Blocks: Optimized Synthesis and Crystal Growth and Crystal and Electronic Structures of Bi_xTeI (x = 2, 3)

et al. 2017

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“…Another approach of vapor deposition is the chemical vapor transport (CVT) in a sealed ampule. Investigations of the CVT of bismuth chalcogenides (Bi 2 Ch 3 ; Ch = S, Se, Te) , considered mostly the vapor transport by using a transport agent to achieve high mass flow rates. For bismuth chalcogenides it can be distinguished between vapor transport with transport agent and decomposition sublimation.…”

Section: Introductionmentioning

confidence: 99%

Catalyst-free Growth of Single Crystalline Bi₂Se₃ Nanostructures for Quantum Transport Studies

Nowka

Veyrat

Gorantla

et al. 2015

Crystal Growth & Design

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In this work we report on the growth of single crystalline Bi 2 Se 3 nanostructures (nanoribbons, nanoflakes, and nanowires) by catalyst-free decomposition sublimation in sealed silica ampules. The nanostructures directly grow on Si/ SiO 2 substrates by a vapor−solid growth mechanism and show high degree of crystallinity with dimensions of >10 μm in length and simultaneously <10 nm in height (nanoribbons). In order to optimize the growth process in a reproducible way, thermodynamic calculations were realized. The high quality of as-grown nanostructures was confirmed by transmission electron microscopy including selected area electron diffraction as well as electrical transport measurements. Our electrical transport data are evidence, on the one hand, of the high crystal quality and efficiency of the synthesis by decomposition sublimation. On the other hand, the catalyst-free approach offers the chance to investigate crystals with high purity and to measure surface state properties. ■ INTRODUCTIONRecently, topological insulators (TI) have attracted great interest in the physics community, due to their unique surface states. Topological insulators exhibit a band gap in the bulk but have gapless edge states or metallic states on their surface. The surface states are stable against nonmagnetic disorder and protected by time-reversal symmetry (TRS). Moreover surface states exhibit fascinating electronic properties since they host Dirac Fermions with a locked spin-momentum behavior. These characteristics allow investigation of new physical phenomena which are specific to three-dimensional (3D) TI's surface states. 1−3 TI were theoretically predicted 4−6 and experimentally confirmed for the 3D-TI Bi 2 Se 3 and Bi 2 Te 3 by angle-resolved photoemission spectroscopy (ARPES) 7,8 and electrical transport measurements. 9,10The observation of quantum oscillations known as Shubnikov−de Haas (SdH) 11,12 oscillations allows a quantitative and systematic investigation of the two-dimensional (2D) surface states and bulk states by the precise determination of the Fermi wave vector k F of a given charge carrier population. Nevertheless, crystals with a very high quality are required in order to study quantum oscillations by electrical transport. Nanostructures are preferred for the specific study of the surface states, because they have many advantages compared to their bulk counterpart. Nanostructures of TI materials show a wide variety of morphologies, for instance, nanowires, nanotriangles, and nanoribbons. The large surface-to-volume ratio of nanostructures in comparison to the bulk material allow studies of surface effects 13 as well. The natural doping in Bi 2 Se 3 due to the presence of Se-vacancies leads to a contribution of the bulk carrier density to the conductivity. Therefore, for investigations of the surface states, ultrathin layers of Bi 2 Se 3 must be prepared. 14 Several methods for the fabrication of TI nanostructures are reported, for instance, mechanical exfoliation, 15,16 molecular beam epitaxy (MBE), 17−19 and ...

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“…The basic principles of this method are long known: a thermal gradient drives the crystallization from a vapor, formed from a source of raw materials heated up to high temperature. If the vapor partial pressure of one or more components is too low, (for practical purposes, a relevant transport occurs only when p ≥ 0.1 * 10 -3 mbar [8]) a chemical substance is added to the initial mixture in order to favor the formation of more volatile species. For this process, the equilibrium constants of the reaction between the non-volatile material and the transport agent should have an appropriate value.…”

Section: Introductionmentioning

confidence: 99%

Improved chemical vapor transport growth of transition metal dichalcogenides

Ubaldini

Giannini

2014

Journal of Crystal Growth

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In the crystal growth of transition metal dichalcogenides by the Chemical Vapor Transport method (CVT), the choice of the transport agent plays a key role. We have investigated the effect of various chemical elements and compounds on the growth of TiSe 2 , MoSe 2 , TaS 2 and TaSe 2 and found that pure I 2 is the most suitable for growing TiSe 2 , whereas transition metal chlorides perform best with Mo-and Ta-chalcogenides. The use of TaCl 5 as a transport agent in the CVT process allows to selectively growth either polymorph of TaS 2 and TaSe 2 and the optimum growth conditions are reported. Moreover, by using TaCl 5 and tuning the temperature and the halogen starting ratio, it was possible to grow whiskers of the compounds

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Chemical Vapour Transport of Bismuth and Antimony Chalcogenides M₂Q₃ (M = Sb, Bi, Q = Se, Te)

Cited by 19 publications

References 32 publications

Modular Design with 2D Topological-Insulator Building Blocks: Optimized Synthesis and Crystal Growth and Crystal and Electronic Structures of Bi_xTeI (x = 2, 3)

Modular Design with 2D Topological-Insulator Building Blocks: Optimized Synthesis and Crystal Growth and Crystal and Electronic Structures of Bi_xTeI (x = 2, 3)

Catalyst-free Growth of Single Crystalline Bi₂Se₃ Nanostructures for Quantum Transport Studies

Improved chemical vapor transport growth of transition metal dichalcogenides

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Chemical Vapour Transport of Bismuth and Antimony Chalcogenides M2Q3 (M = Sb, Bi, Q = Se, Te)

Cited by 19 publications

References 32 publications

Modular Design with 2D Topological-Insulator Building Blocks: Optimized Synthesis and Crystal Growth and Crystal and Electronic Structures of BixTeI (x = 2, 3)

Modular Design with 2D Topological-Insulator Building Blocks: Optimized Synthesis and Crystal Growth and Crystal and Electronic Structures of BixTeI (x = 2, 3)

Catalyst-free Growth of Single Crystalline Bi2Se3 Nanostructures for Quantum Transport Studies

Improved chemical vapor transport growth of transition metal dichalcogenides

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Chemical Vapour Transport of Bismuth and Antimony Chalcogenides M₂Q₃ (M = Sb, Bi, Q = Se, Te)

Modular Design with 2D Topological-Insulator Building Blocks: Optimized Synthesis and Crystal Growth and Crystal and Electronic Structures of Bi_xTeI (x = 2, 3)

Modular Design with 2D Topological-Insulator Building Blocks: Optimized Synthesis and Crystal Growth and Crystal and Electronic Structures of Bi_xTeI (x = 2, 3)

Catalyst-free Growth of Single Crystalline Bi₂Se₃ Nanostructures for Quantum Transport Studies