Liquid-phase exfoliation of bismuth telluride iodide (BiTeI): structural and optical properties of single-/few-layer flakes

Bismuth telluride halides (BiTeX) are Rashba-type crystals with several potential applications ranging from spintronics and nonlinear optics to energy. Their layered structures and low cleavage energies allow their production in a two-dimensional form, opening the path to miniaturized device concepts. The possibility to exfoliate bulk BiTeX crystals in the liquid represents a useful tool to formulate a large variety of functional inks for large-scale and cost-effective device manufacturing. Nevertheless, the exfoliation of BiTeI by means of mechanical and electrochemical exfoliation proved to be challenging. In this work, we report the first ultrasonication-assisted liquid-phase exfoliation (LPE) of BiTeI crystals. By screening solvents with different surface tension and Hildebrandt parameters, we maximize the exfoliation efficiency by minimizing the Gibbs free energy of the mixture solvent/BiTeI crystal. The most effective solvents for the BiTeI exfoliation have a surface tension close to 28 mN m(-1) and a Hildebrandt parameter between 19 and 25 MPa0.5. The morphological, structural, and chemical properties of the LPE-produced single-/few-layer BiTeI flakes (average thickness of & SIM;3 nm) are evaluated through microscopic and optical characterizations, confirming their crystallinity. Second-harmonic generation measurements confirm the non-centrosymmetric structure of both bulk and exfoliated materials, revealing a large nonlinear optical response of BiTeI flakes due to the presence of strong quantum confinement effects and the absence of typical phase-matching requirements encountered in bulk nonlinear crystals. We estimated a second-order nonlinearity at 0.8 eV of |chi((2))| & SIM; 1 nm V-1, which is 10 times larger than in bulk BiTeI crystals and is of the same order of magnitude as in other semiconducting monolayers (e.g., MoS2)

Rast monokristala germanijuma u univerzalnom multizonskom kristalizatoru primenom elektronske Bridgman-Stocbarger metode

This paper examines the possibility of the application of multizone furnace, i.e. universal multizone crystallizator furnace in obtaining germanijum (Ga added) single crystal using electronic Bridgman-Stocbarger method. As a result of a proper control of furnace parameters and of the control of basic crystalization process parameters a single crystal with the extraordinary high homogeneity degree has been obtained, in both axial and radial direction.U ovom radu ispitivana je mogućnost primene multizonske peći, odnosno univerzalnog multizonskog kristalizatora za dobijanje monokristala germanijuma sa dodatkom galijuma, pri čemu je korišćena elektronska Bridgman-Stocbarger metoda. Kao rezultat dobre kontrole parametara peći, a time i osnovnih parametara procesa kristalizacije, dobijen je monokristal sa izuzetno visokim stepenom homogenosti u aksijalnom i radijalnom pravcu

Interrupted ageing of Al-Mg-Si-Cu alloys

This thesis systematically investigates the effects of a recently developed modified ageing procedure of aluminium alloys, termed the T6I6 temper, on the microstructural development and mechanical properties of the Al Mg Si - Cu alloy 6061. For the T6I6 temper, a conventional single stage T6 temper is interrupted by an ageing period at a reduced temperature (65ºC) to facilitate secondary precipitation, before resuming the final ageing at the temperature of the initial T6 treatment. The T6I6 temper was found to cause simultaneous increases in tensile properties, hardness, and toughness as compared with 6061 T6.Al Mg Si Cu alloys are medium strength alloys widely used in the automotive industry and their further improvement is underpinned by stringent demands for weight reduction placed on the transportation industry in recent years. The potential for further improvement of the mechanical properties was found in the control of secondary precipitation that may take place even in some fully aged alloys when exposed to reduced temperatures.The overall improvement in the mechanical properties of 6061 T6I6 was attributed to the formation of finer and more densely dispersed precipitates in the final microstructure. The refinement of precipitates was facilitated by control of the precipitation processes and gradual evolution of the microstructure throughout each stage of the T6I6 treatment. The results indicated that the concentration and the chemical environment of the vacancies controlled the precipitation processes in this alloy. Findings also show that the proportion of the different precipitate phases present in the final microstructure, as well as the amount of the solute in these precipitates, can be controlled and modified utilizing secondary precipitation.A number of analytical techniques were used in this study. The evolution of the microstructure was studied using Transmission Electron Microscopy (TEM), High Resolution TEM (HRTEM) and Three Dimensional Atom Probe (3DAP). Vacancy-solute interactions were studied using Positron Annihilation Lifetime Spectroscopy (PALS) and 3DAP. The distribution of the solute was studied using 3DAP and Nuclear Magnetic Resonance (NMR). Differential Scanning Calorimetry (DSC) was used to identify precipitation reactions and to determine the stability of vacancy-associated aggregates

Thermal Stability and Anisotropic Sublimation of Two-Dimensional Colloidal Bi₂Te₃ and Bi₂Se₃ Nanocrystals

The structural and compositional stabilities of two-dimensional (2D) Bi₂Te₃ and Bi₂Se₃ nanocrystals, produced by both colloidal synthesis and by liquid phase exfoliation, were studied by in situ transmission electron microscopy (TEM) during annealing at temperatures between 350 and 500 °C. The sublimation process induced by annealing is structurally and chemically anisotropic and takes place through the preferential dismantling of the prismatic {011̅0} type planes, and through the preferential sublimation of Te (or Se). The observed anisotropic sublimation is independent of the method of nanocrystal’s synthesis, their morphology, or the presence of surfactant molecules on the nanocrystals surface. A thickness-dependent depression in the sublimation point has been observed with nanocrystals thinner than about 15 nm. The Bi₂Se₃ nanocrystals were found to sublimate below 280 °C, while the Bi₂Te₃ ones sublimated at temperatures between 350 and 450 °C, depending on their thickness, under the vacuum conditions in the TEM column. Density functional theory calculations confirm that the sublimation of the prismatic {011̅0} facets is more energetically favorable. Within the level of modeling employed, the sublimation occurs at a rate about 700 times faster than the sublimation of the {0001} planes at the annealing temperatures used in this work. This supports the distinctly anisotropic mechanisms of both sublimation and growth of Bi₂Te₃ and Bi₂Se₃ nanocrystals, known to preferentially adopt a 2D morphology. The anisotropic sublimation behavior is in agreement with the intrinsic anisotropy in the surface free energy brought about by the crystal structure of Bi₂Te₃ or Bi₂Se₃

Emissive Bi-doped double perovskite Cs2Ag1-xNaxInCl6 Nanocrystals

We report the composition-dependent optical properties of Bi-doped Cs2Ag1 12xNaxInCl6 nanocrystals (NCs) having a double perovskite crystal structure. Their photoluminescence (PL) was characterized by a large Stokes shift, and the PL quantum yield increased with the amount of Na up to 3c22% for the Cs2Ag0.4Na0.6InCl6 stoichiometry. The presence of Bi3+ dopants was crucial to achieve high PL quantum yields (PLQYs) as nondoped NC systems were not emissive. Density functional theory calculations revealed that the substitution of Ag+ with Na+ leads to localization of AgCl6 energy levels above the valence band maximum, whereas doping with Bi3+ creates BiCl6 states below the conduction band minimum. As such, the PL emission stems from trapped emission between states localized in the BiCl6 and AgCl6 octahedra, respectively. Our findings indicated that both the partial replacement of Ag+ with Na+ ions and doping with Bi3+ cations are essential in order to optimize the PL emission of these systems

Alloy CsCdxPb1-xBr3 Perovskite Nanocrystals: The Role of Surface Passivation in Preserving Composition and Blue Emission

Various strategies have been proposed to engineer the band gap of metal halide perovskite nanocrystals (NCs) while preserving their structure and composition and thus ensuring spectral stability of the emission color. An aspect that has only been marginally investigated is how the type of surface passivation influences the structural/color stability of AMX3 perovskite NCs composed of two different M2+ cations. Here, we report the synthesis of blue-emitting Cs-oleate capped CsCdxPb1-xBr3 NCs, which exhibit a cubic perovskite phase containing also Cd-rich domains of Ruddlesden-Popper phases (RP- phases). The RP domains spontaneously transforms into pure orthorhombic perovskite ones upon NC ageing and the emission color of the NCs shifts from blue to green over days. On the other hand, post-synthesis ligand exchange with various Cs-carboxylate or ammonium bromide salts, right after NC synthesis, provides monocrystalline NCs with cubic phase, highlighting the metastability of the RP domains. When the NCs are treated with Cs-carboxylates (including Cs-oleate), most of the Cd2+ ions are expelled from the NCs, the NCs’ phase evolves from cubic to orthorhombic and their emission color changes from blue to green. Instead, when the NCs are coated with ammonium bromides, the loss of Cd2+ ions is suppressed and the NCs tend to retain their blue emission (both in colloidal dispersions and in electroluminescent devices), as well as their cubic phase, over time. The improved compositional and structural stability in these latter cases is ascribed to the saturation of surface vacancies, which may act as channels for the expulsion of Cd2+ ions from the NCs

Alloy CsCd _xPb_{1- x}Br₃Perovskite Nanocrystals:The Role of Surface Passivation in Preserving Composition and Blue Emission

Various strategies have been proposed to engineer the band gap of metal halide perovskite nanocrystals (NCs) while preserving their structure and composition and thus ensuring spectral stability of the emission color. An aspect that has only been marginally investigated is how the type of surface passivation influences the structural/color stability of AMX3 perovskite NCs composed of two different M2+ cations. Here, we report the synthesis of blue-emitting Cs-oleate capped CsCdxPb1-xBr3 NCs, which exhibit a cubic perovskite phase containing Cd-rich domains of Ruddlesden-Popper phases (RP phases). The RP domains spontaneously transform into pure orthorhombic perovskite ones upon NC aging, and the emission color of the NCs shifts from blue to green over days. On the other hand, postsynthesis ligand exchange with various Cs-carboxylate or ammonium bromide salts, right after NC synthesis, provides monocrystalline NCs with cubic phase, highlighting the metastability of RP domains. When NCs are treated with Cs-carboxylates (including Cs-oleate), most of the Cd2+ ions are expelled from NCs upon aging, and the NCs phase evolves from cubic to orthorhombic and their emission color changes from blue to green. Instead, when NCs are coated with ammonium bromides, the loss of Cd2+ ions is suppressed and the NCs tend to retain their blue emission (both in colloidal dispersions and in electroluminescent devices), as well as their cubic phase, over time. The improved compositional and structural stability in the latter cases is ascribed to the saturation of surface vacancies, which may act as channels for the expulsion of Cd2+ ions from NCs

Indium Selenide/Indium Tin Oxide Hybrid Films for Solution‐Processed Photoelectrochemical‐Type Photodetectors in Aqueous Media

Abstract 2D metal monochalcogenides have recently attracted interest for photoelectrochemical (PEC) applications in aqueous electrolytes. Their optical bandgap in the visible and near‐infrared spectral region is adequate for energy conversion and photodetection/sensing. Their large surface‐to‐volume ratio guarantees that the charge carriers are photogenerated at the material/electrolyte interface, where redox reactions occur, minimizing recombination processes. However, solution‐processed photoelectrodes based on these materials exhibit energy conversion efficiencies that are far from the current state of the art expressed by established technologies. This work reports a systematic morphological, spectroscopic, and PEC characterization of solution‐processed films of photoactive InSe flakes for PEC‐type photodetectors. By optimizing the thickness and hybridizing InSe flakes with electrically conductive Sn:In2O3 (ITO) nanocrystals, photoanodes with a significant photoanodic response in both acidic and alkaline media are designed, reaching responsivity up to 60.0 mA W−1 (external quantum efficiency = 16.4%) at +0.4 V versus RHE under visible illumination. In addition, a strategy based on the use of sacrificial agents (i.e., 2‐propanol and Na2SO3) is proposed to improve the stability of the InSe and ITO/InSe photodetectors. Our data confirm the potential of 2D InSe for PEC energy conversion and sensing applications, remarking the challenges related to InSe stability during anodic operation