Structure and magnetic properties of cobalt-intercalated layered InSe crystals

We study the structure and magnetic properties of Co _x InSe layered crystals electrochemically intercalated by cobalt in a constant magnetic field. It is found that impurity clusters consisting of cobalt nano-particles with the fcc structure are formed in the intercalates under investigation on the Van der Waals planes in the space between the layers. Intercalates Co_0.1InSe obtained by implantation in a magnetic field exhibit a change in their magnetic properties (dependence of the magnetic moment in the magnetic field strength has the form of a hysteresis loop, which is typical of ferromagnetic materials).     

Auger electron spectroscopy studies of In4Se3 layered crystals

In₄Se₃ pure and silver intercalated layered semiconductor crystals’ surfaces have been studied with application of Auger electron spectroscopy (AES). It was found that peculiarities of their adsorptial activity appear as the result of atomic and electron-energetic structure of the crystals’ cleavage surfaces. Silver intercalation (2.5–3 at.%) of In₄Se₃ leads to a rise in the CO sticking coefficient and simultaneous appearance of adsorption activity relative to oxygen. It was established that In₄Se₃ crystal heating leads to active interaction of cleavage surfaces with oxygen and its chemisorption.     

两步化学气相沉积法制备In2Se3/MoSe2范德华尔斯异质结

Two-dimensional transition metal dichalcogenides heterostructures have stimulated wide interest not only for the fundamental research,but also for the application of next generation electronic and optoelectronic devices.Herein,we report a successful two-step chemical vapor deposition strategy to construct vertically stacked van der Waals epitaxial In₂Se₃/MoSe₂ heterostructures.Transmission electron microscopy characterization reveals clearly that the In₂Se₃ has well-aligned lattice orientation with the substrate of monolayer MoSe₂.Due to the interaction between the In₂Se₃ and MoSe₂ layers,the heterostructure shows the quenching and red-shift of photoluminescence.Moreover,the current rectification behavior and photovoltaic effect can be observed from the heterostructure,which is attributed to the unique band structure alignment of the heterostructure,and is further confirmed by Kevin probe force microscopy measurement.The synthesis approach via van der Waals epitaxy in this work can expand the way to fabricate a variety of two-dimensional heterostructures for potential applications in electronic and optoelectronic devices.     

Investigation of the morphology of the van der Waals surface of the InSe single crystal

The morphology of the (0001) van der Waals surfaces of the layered single crystal In_1.03Se_0.97, which were prepared using different techniques, has been investigated by scanning probe microscopy methods. It has been assumed that the van der Waals surface prepared with the use of an adhesive tape oxidizes in air due to the chemisorption of acid agents on dangling bonds of the metal and selenium. An analysis of the current-voltage characteristics of the tunneling current has shown that the composition of natural oxides represents a mixture of phases of the In₂O₃ oxide and wide-band-gap selenium oxides. In the InSe surface prepared by cleavage with subsequent exposure in air for approximately 2 min, the scanning with a tunneling microscope has revealed a surface ordering in the form of a corrugation of a complex profile with a fine structure. The last fact reflects the charge density redistribution after the chemisorption of gas molecules from air on this surface and its relaxation to the state with a minimum energy. Atoms of the basal plane are observed on the InSe(0001) van der Waals surface prepared by cleavage in an oxygen-free medium. The surface corrugation is absent. Point defects cause a disturbance of the periodic potential of the single crystal, which extends over a distance equal to four lattice spacings and appears as a shadowing. A technique has been proposed for producing In₂O₃ oxide nanostructures on the surface of the single crystal of the layered semiconductor InSe with the use of an atomic-force microscope probe as a nanoindenter. The ability of the probe to operate in gaseous and liquid media significantly extends the capabilities of the method.     

Surface-induced structural modification in ZnO nanoparticles

Cobalt?Ccobalt carbide [Co _x C (x?=?2 or 3)] and cobalt (FCC-Co) microwires have been synthesized using a polyol method in the presence of a high external magnetic field of 4.3?kOe. It was reported before that the synthesis of these particles in the absence of magnetic field leads to the formation of spherical particles. Analysis of the X-ray diffraction (XRD) scans indicates that the synthesized Co _x C wires consist of four phases?? ??-Co, ??-Co, Co₃C, and Co₂C. The percent composition of these phases was 53.3?% Co₃C, 26.8?% Co₂C, 12.5?% ??-Co, and 7.4?% ??-Co. XRD analysis of the as-synthesized cobalt wires shows that it consists of single-phase FCC-Co. Based on Scherrer analysis of the XRD data, the average crystallite sizes of the cobalt carbide and the cobalt particles are 18.5 and 16.3?nm, respectively. Scanning electron microscopy (SEM) studies show that the diameter of Co _x C wires is in the range of 1.6(±0.2)???m with their length varying between 18 and 30???m while the diameter of the cobalt wires is 1.65(±0.1). The SEM results infer that the morphology of the growing particles was controlled by the magnetic field with the applied field directs the growth of the particles into wires. The magnetic measurements indicate a superparamagnetic character of the cobalt wires and a soft ferromagnetic nature of the synthesized Co _x C chains. The degree and field range of the interactions between magnetic domains have been investigated using a Henkel plot.     

Octahedral vs tetrahedral coordination of the co(II) ion in layer compounds: CoxZn1−xIn2S4(O⩽x⩽0.46) solid solution

Large crystals of Co_xZn_1−xIn₂S₄ (0.00 ⩽ x ⩽ 0.46) solid solution were grown from the vapour phase by chemical transport modified by the time variation of the temperature profile procedure. Co²⁺ ions were found, by XPS analysis, to occupy tetrahedral as well as octahedral sites of the ZnIn₂S₄-type structure. The magnetic properties of Co_0.46Zn_0.54In₂S₄, crystallizing in space group R 3m, were explained in terms of the short-range magnetic order arising from the presence of isolated clusters of magnetic ions.     

Studies of metal-insulator transition in TiSxSe2-x single crystals

A temperature induced metal-insulator transition has been found in TiS_xSe_2-x single crystals. The M-I transition is found to occur over the temperature range 250° to 300°C for 1.0 ≤ x ≤ 1.7. The present observation of the M-I transition has been compared and contrasted with the earlier reported M-I transition in TiS_1.7 single crystals. Evidence is presented and arguments are put forward in support of the occurrence of the M-I transition in terms of the variation in disorder of the extra Ti atoms in the van der Waals gap. The possible reason for the suppression of the M-I transition in TiS_xSe_2-x for x ≤ 1 is outlined.     

Optical properties of TlGaxIn1-xSe2-layered mixed crystals (0.5 ≤ x ≤ 1) by spectroscopic ellipsometry,transmission, and reflection measurements

The layered semiconducting TlGa_xIn_1-xSe₂-mixed crystals (0.5?≤?x?≤?1) were studied for the first time by spectroscopic ellipsometry measurements in the 1.2–6.2?eV spectral range at room temperature. The spectral dependence of the components of the complex dielectric function, refractive index, and extinction coefficient were revealed using an optical model. The interband transition energies in the studied samples were found from the analysis of the second-energy derivative spectra of the complex dielectric function. The effect of the isomorphic cation substitution (indium for gallium) on critical point energies in TlGa_xIn_1-xSe₂ crystals was established. Moreover, the absorption edge of TlGa_xIn_1-xSe₂ crystals have been studied through the transmission and reflection measurements in the wavelength range of 500–1100?nm. The analysis of absorption data revealed the presence of both optical indirect and direct transitions. It was found that the energy band gaps decrease with the increase of indium content in the studied crystals.     

Nano-scaled top-down of bismuth chalcogenides based on electrochemical lithium intercalation

A two-step method has been used to fabricate nano-particles of layer-structured bismuth chalcogenide compounds, including Bi₂Te₃, Bi₂Se₃, and Bi₂Se_0.3Te_2.7, through a nano-scaled top-down route. In the first step, lithium (Li) atoms are intercalated between the van der Waals bonded quintuple layers of bismuth chalcogenide compounds by controllable electrochemical process inside self-designed lithium ion batteries. And in the second step, the Li intercalated bismuth chalcogenides are subsequently exposed to ethanol, in which process the intercalated Li atoms would explode like atom-scaled bombs to exfoliate original microscaled powder into nano-scaled particles with size around 10 nm. The influence of lithium intercalation speed and amount to three types of bismuth chalcogenide compounds are compared and the optimized intercalation conditions are explored. As to maintain the phase purity of the final nano-particle product, the intercalation lithium amount should be well controlled in Se contained bismuth chalcogenide compounds. Besides, compared with binary bismuth chalcogenide compound, lower lithium intercalation speed should be applied in ternary bismuth chalcogenide compound.     

Quantum oscillations in heavily doped bismuth chalcogenides

The observation of Shubnikov-de Haas and Hall oscillations in high-quality Bi_{2 ? x} Cu _x Se₃ single crystals is reported. Measurements carried out upon rotating the samples with respect to the magnetic field demonstrate that the oscillations originate from two-dimensional surface states in three-dimensional single crystals and are determined only by the perpendicular component of the magnetic field.     

Superconductivity and non-metallicity induced by doping the topological insulators Bi2Se3 and Bi2Te3

We show that by Ca doping the Bi₂Se₃ topological insulator, the Fermi level can be fine tuned to fall inside the band gap and therefore suppresses the bulk conductivity. Non-metallic Bi₂Se₃ crystals are obtained. On the other hand, the Bi₂Se₃ topological insulator can also be induced to become a bulk superconductor, with T_c∼3.8 K, by copper intercalation in the van der Waals gaps between the Bi₂Se₃ layers. Likewise, an as-grown crystal of metallic Bi₂Te₃ can be turned into a non-metallic crystal by slight variation in the Te content. The Bi₂Te₃ topological insulator shows small amounts of superconductivity with T_c∼5.5 K when reacted with Pd to form materials of the type Pd_zBi₂Te₃.     

Thickness dependence of antiferromagnetic phase transition in Heisenberg-type MnPS3

The behavior of 2-dimensional (2D) van der Waals (vdW) layered magnetic materials in the 2D limit of the few-layer thickness is an important fundamental issue for the understanding of the magnetic ordering in lower dimensions. The antiferromagnetic transition temperature T_N of the Heisenberg-type 2D magnetic vdW material MnPS₃ was estimated as a function of the number of layers. The antiferromagnetic transition was identified by temperature-dependent Raman spectroscopy, from the broadening of a phonon peak at 155 cm⁻¹, accompanied by an abrupt redshift and an increase of its spectral weight. T_N is found to decrease only slightly from ~78 K for bulk to ~66 K for 3L. The small reduction of T_N in thin MnPS₃ approaching the 2D limit implies that the interlayer vdW interaction is playing an important role in stabilizing magnetic ordering in layered magnetic materials.     

Surface morphology and Raman spectroscopy of thin layers of antimony and bismuth chalcogenides

The phonon spectra in thin layers of bismuth telluride and solid solutions of Bi_2–xSb_xTe_3–ySe_y of different composition, belonging to three-dimensional topological insulators, have been investigated by micro-Raman spectroscopy, and the morphology of an interlayer van der Waals (0001) surface in them has been studied by semicontact atomic force microscopy at room temperature. The analysis of the Raman spectra and the intensity ratio of active and inactive longitudinal optical modes depending on the composition, morphology of the interlayer surface, and thickness of the layers enabled the estimation of the effect of topological surface states of Dirac fermions, associated with the strengthening of the electron–phonon interaction as a result of resonance Raman scattering, and the identification of the compositions, in which the contribution of topological surface states becomes dominant.     

Rigid layer modes and van der Waals interactions in Cdi2−CdBr2 mixed layer compounds

Rigid layer modes in the (CdI₂)_1?x(CdBr₂)_x, mixed system have been observed in the concentration range 0 ? x ? 0.5. The frequency of the mode decreases with increasing x. In order to analyze the result, a van der Waals potential with an exponential-type repulsive term is employed for the interatomic potential between halogen ions of opposite layers. Two parameters ρ and B in the potential are determined so as to fit the result by use of the van der Waals constant estimated for halogen-halogen ions in alkali halides. The values of the parameter thus determined are comparable to the values obtained for other materials. This procedure is applied to other layer compounds, PbI₂ and HgI₂. The validity of the present method is discussed.     

Local atomic structure of Cu(In x Ga1−x )Se2 (x = 0.25, 0.5, and 0.75) systems for solar cells

The local atomic structure of thin surface layers of crystalline quasi-binary Cu(In _x Ga_1?x )Se₂ solid solutions was studied by SIMS and EXAFS techniques. The SIMS method showed that the elemental composition of the sample changes most significantly in thin layers at a depth of 5–10 nm; in deeper layers, the component concentrations correspond to the bulk values. The EXAFS method in the x-ray fluorescence mode showed that the results obtained are in agreement with the assumption that quaternary crystalline quasi-binary Cu(In _x Ga_1?x )Se₂ solid solutions exhibit local disorder while average long-range order is detected from x-ray diffraction data.     

A neutron powder diffraction study of the helimagnetic structure of TlCo2Se2−xSx

The magnetic layer structure of TlCo₂Se_2−xS_x has been thoroughly re-investigated with neutron powder diffraction. The cobalt magnetic moments are ferromagnetically arranged within the layers, but the interlayer coupling differs profoundly with varying composition (x): the spins in TlCo₂Se₂ form a helix along the c-axis with a turning-angle of ∼119° at 1.4 K. This kind of helical structure prevails for 0≤x≤1.5 with a gradual decrease of the angle with increasing sulphur content, down to 34°, showing an almost linear relationship with the interlayer distance of Co-Co. For x≥1.75 the interlayer coupling changes to ferromagnetic. Unexpectedly, two helices were found to coexist at x=0.5 and x=1.0. The interaction between adjacent cobalt layers is there characterized by an incommensurate angle (106°, resp., 73°) together with a commensurate angle of 90°. The magnetic structures have been refined as two magnetic phases, each having a characteristic wave vector. A tentative model where the symmetry of the structure and the interlayer distance compete is considered for explaining the simultaneous occurrence of the two kinds of diffraction profile satellites.     

Morphology,chemical composition,and electrical characteristics of hybrid (Ni-C) nanocomposite structures grown on the van der Waals GaSe(0001) surface

The morphology and chemical composition of metal (Ni), carbon, and composite (Ni-C) nanostructures grown on oxidized and unoxidized (0001) surfaces of a layered GaSe crystal by electron beam vacuum evaporation of the material from a liquid ion source in an electric field have been investigated using atomic force microscopy and X-ray photoelectron spectroscopy. It has been demonstrated that this technology makes it possible to grow nanostructures with different morphologies depending on the growth mode and substrate surface state. Dense homogeneous arrays of nickel nanoparticles (Ni@C) (with geometrical sizes of ～1–15 nm and a lateral density of higher than 10¹⁰ cm^?2) encapsulated into carbon shells, as well as carbon layers (with a thickness of the order of several nanometers), are grown on the unoxidized van der Waals GaSe(0001) surface, whereas Ni-C composite nanostructures are grown on the oxidized surface. The formation of oxide nanostructures on the van der Waals surface and their chemical composition have been examined. Vertical hybrid Au/Ni/(Ni-C)/n-Ga₂O₃(Ni@C)/p-GaSe structures grown on the GaSe(0001) surface contain Ni@C nanoparticles embedded in the wide-band-gap n-Ga₂O₃ oxide. The current-voltage characteristics of these structures at temperatures close to T = 300 K exhibit specific features of the Coulomb blockade effect.     

Changes of the magnetic interactions in TlCo2Se2 upon metal substitution

Various solid solutions TlCo_2−xMe_xSe₂ (Me=Fe, Ni and Cu) have been investigated by neutron powder diffraction, supplemented by magnetometry. The incommensurate spin-helix running along the c-axis in tetragonal TlCo₂Se₂ prevails for low concentrations of copper and iron but changes pitch. In the copper case, only cobalt carries a magnetic moment. On nickel substitution, however, collinear antiferromagnetic coupling between the ferromagnetic layers occurs. The magnetic moment distribution between the two transition metals in the solid solution TlCo_2−xNi_xSe₂ was tentatively probed with first principle calculations on fictive ordered TlCoNiSe₂, modelled by two types of superstructures. Also the ternary mother compounds, Pauli paramagnetic TlNi₂Se₂ and antiferromagnetic TlCo₂Se₂, were investigated with the same LMTO method.     

Anomalous character of the interaction of C<Subscript>60</Subscript> molecules with the sulfur-saturated Ta(100) surface

It is shown that, contrary to all previously studied systems, heating to ～800 K in the C₆₀? TaS² monolayer-Ta(100) adsorption system leads to the complete removal of the deposited fullerene molecules. A model is proposed that explains the observed phenomenon by a very weak nonchemisorption interaction between the C₆₀ molecules and the valence-saturated surface of tantalum disulfide that forms layered crystals with van der Waals interaction between layers.     

Near infrared magneto-absorption in the laser material KZn1−xCoxF3

Infrared absorption (1.4–2μm) of KZn_1−xCo_xF₃ (0⩽ x<0.15) at 4.2 K has been studied in a magnetic field (B⩽7 T). Large field-induced splittings were observed for Co²⁺-ion lines. Details of the cobalt concentration dependence of the absorptivity at B = 0 and at field are given along with the dependences on field direction and strength. Assignments are made of the observed Co²⁺ single-ion and pair transitions. The data has enabled the determination of the infrared (IR) transition g values.