Optical Properties of Pb-Doped Bi2Te3 Single Crystals

The reflectance and the transmittance spectra in the IR region were measured on Pb-doped Bi₂Te₃ single crystal samples grown by a modified Bridgman technique. The plasma resonance frequency, the optical relaxation time, and the high-frequency permittivity were determined by fitting the Drude-Zener formulas to the reflectance spectra. It was found that Pb impurities in Bi₂Te₃ behave as acceptors. A part of incorporated Pb atoms behaves as electrically inactive. This effect is explained as due to the fact that electrically active Pb-atoms form substitutional defects, Pb′_Bi, and the others form inactive two-dimensional defects — seven-layer lamellae Te—Bi—Te—Pb—Te—Bi—Te. The transmittance spectra were used for the determination of the dependence of the absorption coefficient K on the energy of incident photons. The optical width of the energy gap increases with increasing Pb content. The values of the exponent α from the relation of K ∼ λ^α for the long-wavelength absorption edge range within the interval of 1.6 to 2.8, i.e. the dominant scattering mechanism of free current carriers in Pb-doped Bi₂Te₃ crystals is the scattering by acoustic phonons. By comparison of the effect of doping atoms of the IV.B group of the periodic table on the concentration of holes in Bi₂Te₃ crystal lattice was concluded that the tendency to form substitutional defects Me′_Bi (Me = Ge, Sn, Pb) in these crystals increases from Ge to Pb, whereas the tendency to the formation of seven-layer lamellae Te—Bi—Te—Me—Te—Bi—Te decreases.     

Hydrothermal synthesis of Bi2Te3 nanowires through the solid-state interdiffusion of Bi and Te atoms on the surface of Te nanowires

Polycrystalline Bi₂Te₃ nanowires were prepared by a hydrothermal method that involved inducing the nucleation of Bi atoms reduced from BiCl₃ on the surface of Te nanowires, which served as sacrificial templates. A Bi–Te alloy is formed by the interdiffusion of Bi and Te atoms at the boundary between the two metals. The Bi₂Te₃ nanowires synthesized in this study had a length of 3–5 μm, which is the same length as that of the Te nanowires, and a diameter of 300–500 nm, which is greater than that of the Te nanowires. The experimental results indicated that volume expansion of the Bi₂Te₃ nanowires was a result of the interdiffusion of Bi and Te atoms when Bi was alloyed on the surface of the Te nanowires. The morphologies of Bi₂Te₃ are strongly dependent on the reaction conditions such as the temperature and the type and concentration of the reducing agent. The morphologies, crystalline structure and physical properties of the product were analyzed by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED) and X-ray photoelectron spectroscopy (XPS).     

Investigation of the nature of point defects in in Te-doped gallium antimonide

Precision lattice constant and density measurements held on gallium antimonide single crystals grown from stoichiometric melts showed that doping of such crystals with Te lead to the intensification of Ga-supersaturated solid solution decomposition process with initial Frenkel defect (Ga_i + V_Ga) production. It is supposed that Te_sb — simple donors form complexes with V_Ga which are believed to be acceptors. Doping of GaSb with Te up to the levels above 2 · 10¹⁸ cm⁻³ leads to partial decomposition of GaSb(Te) solid solution supersaturated with Te.     

Transport Coefficient of Gallium-doped Bi2Te3 Single Crystals

Gallium-doped Bi₂Te₃ single crystals were prepared by means of a modified Bridgman method. Temperature dependences of the Hall constant R_H( B ∥ c ), electrical conductivity σ⊥c and Seebeck coefficient S(Δ T ⊥ c) were measured on the samples of these crystals in the temperature interval of 100–400 K. The variations of the investigated transport coefficients with increasing Ga content in the samples showed that Ga atoms in the Bi₂Te₃ crystal lattice behave as donors. This effect is qualitatively explained on the basis of a model of point defects in Bi₂Te₃(Ga) crystals; singly ionised gallium atoms in interstitial sites; Ga_i, are considered to be the most probable defects.     

Characterization of Ag-Doped Bi1.5Sb0.5Te3 Single Crystals

Single crystals of Bi_1.5Sb_0.5Te₃ doped with Ag atoms (c_Ag = 0 - 4.34x10¹⁹ atoms/cm³) were characterized by measurement of Hall coefficient, electrical conductivity, Seebeck coefficient and the figure of merit. It was found that Ag atoms in the crystal structure of Bi_1.5Sb_0.5Te₃ behave like donors. It is necessary to add more than one Ag atom to the Bi_1.5Sb_0.5Te₃ compound in order to suppress the hole concentration by one hole. Such a behaviour of the dopant is explained by the formation of various structural defects. Besides the dominant interstitial defects of Ag* silver atoms form also positively charged substitutional defects Ag″, Ag′, and a four-layer-lamellae of the type [Ag_0.5Sb_0.5]-Te-[Ag_0.5Sb_0.5]-Te. The incorporation of Ag atoms into the Bi_1.5Sb_0.5Te₃ lattice, besides the suppression of the hole concentration, leads to a decrease in the figure of merit Z.     

Sb2Te3 Single Crystals Doped with Chromium Atoms

Chromium-doped Sb₂Te₃ single crystals were prepared from elements of semiconductor purity using a modified Bridgman method. The samples of these crystals were characterized by means of X-ray diffraction analysis, measurements of the reflectivity in the plasma resonance frequency range ω_p, of the Hall constant R_H and electrical conductivity σ. It was found that the incorporation of Cr atoms into the Sb₂Te₃ crystal lattice reduces the volume of the unit cell, whereas the values of ω_p and R_H (i.e. the concentration of holes) remain unaltered and the values of σ decrease with increasing chromium content. This effect is qualitatively explained by an interaction of incorporated Cr atoms with antisite defects of Sb₂Te₃ crystal lattice. The In (R_Hσ) vs. In T dependences show that the dominant mechanism of scattering of free charge carriers in the studied crystals is the scattering by acoustic phonons; the presence of chromium atoms increases the scattering rate by ionized impurities.     

Te NMR chemical shifts and tellurium coordination environments in crystals and glasses in the Ge-As-Sb-Te system

The local coordination environments of Te atoms have been investigated in crystalline and glassy binary and ternary tellurides in the system Ge-As-Sb-Te using ¹²⁵Te solid-state wideline nuclear magnetic resonance (NMR) spectroscopy. The average ¹²⁵Te NMR chemical shifts in these materials range from 300 to 1050, 90 to 700 and − 2000 to − 4100 ppm for 2, 3 and 6-coordinated environments, respectively. Te atoms are predominantly 2-coordinated in binary Ge-Te, As-Te and ternary Ge-As-Te glasses. The ¹²⁵Te NMR spectrum of the cubic Ge₁Sb₂Te₄ phase with rock salt structure is consistent with a random distribution of Ge/Sb vacancies in the lattice. Besides the coordination number, the ¹²⁵Te chemical shifts in these materials are also found to be sensitive to the chemical identity of the nearest neighbors. ¹²⁵Te NMR spectroscopy shows significant future promise in its application as a technique complementary to diffraction and EXAFS in understanding the short-range structure of amorphous Ge-As-Sb tellurides.     

Optical Properties of Bi2Se3‐xAsx Single Crystals

Bi₂Se_3‐xAs_x single crystals with the As content of c_As = 0 to 2.0x10¹⁹ atoms/cm³ prepared from the elements of 5N purity by means of a modified Bridgman method were characterized by measurements of infrared reflectance and transmittance. Values of the plasma resonance frequency omega_p, optical relaxation time tau, and high‐frequency permittivity were determined by fitting the Drude‐Zener formulas to the reflectance spectra. It was found that the substitution of As atoms for Se atoms in the Bi₂Se₃ crystal lattice leads to a decrease in the omega_p values. This effect is accounted for by a model of point defects in the crystal lattice of Bi₂Se_3‐xAs_x. The dependences of the absorption coefficient K on the energy of incident photons were determined from the transmittance spectra. The optical width of the energy gap is found to decrease with increasing As content. The values of the exponent b from the relation of K ∼ lamda^b for the long‐wavelength absorption edge range within the interval 2.0 to 2.3, i.e. the dominant scattering mechanism of free current carriers in Bi₂Se_3‐xAs_x crystals is the scattering by acoustic phonons.     

Electrical switching and thermal studies on bulk Ge-Te-Bi glasses

Bulk, melt quenched Ge₁₈Te_82-xBi_x glasses (1 ≤ x ≤ 4) have been found to exhibit memory type electrical switching behavior, which is in agreement with the lower thermal diffusivity values of Ge-Te-Bi samples. A linear variation in switching voltages (V_th) has been found in these samples with increase in thickness which is consistent with the memory type electrical switching. Also, the switching voltages have been found to decrease with an increase in temperature which happens due to the decrease in the activation energy for crystallization at higher temperatures. Further, V_th of Ge₁₈Te_82-xBi_x glasses have been found to decrease with the increase in Bi content, indicating that in the Ge-Te-Bi system, the resistivity of the additive has a stronger role to play in the composition dependence of V_th, in comparison with the network connectivity and rigidity factors. In addition, the composition dependence of crystallization activation energy has been found to show a decrease with an increase in Bi content, which is consistent with the observed decrease in the switching voltages. X-ray diffraction studies on thermally crystallized samples reveal the presence of hexagonal Te, GeTe, Bi₂Te₃ phases, suggesting that bismuth is not taking part in network formation to a greater extent, as reflected in the variation of switching voltages with the addition of Bi. SEM studies on switched and un-switched regions of Ge-Te-Bi samples indicate that there are morphological changes in the switched region, which can be attributed to the formation of the crystalline channel between two electrodes during switching.     

ESR study of Mn2+ in GeTe and GeTeSi glasses

The electron spin resonance spectra of Mn²⁺ ions have been studied in Ge_xTe_100?x with x = 15, 17.5 and 20, and Ge_20?xTe₈₀Si_x with 0 ?x? 20. All samples are found to exhibit six hyperfine lines centered at g = 4.3 with hyperfine interaction constant A = 56 × 10^?4cm^?1. The g = 4.3 line is interpreted as being caused by Mn²⁺ ions incorporated in the amorphous network and surrounded by four Te atoms in an arrangement of orthorhombic symmetry. Some of the samples of GeTe show a g = 2.0 line. This line also appears after heat treatment in air at temperatures above the glass transition temperature. It is concluded that the g = 2.0 line is caused by Mn²⁺ ions in phase separated microcrystalline or concentrated regions of MnO in the glass.     

Czochralski-growth of germanium crystals containing high concentrations of oxygen impurities

Oxygen-containing germanium (Ge) single crystals with low density of grown-in dislocations were grown by the Czochralski (CZ) technique from a Ge melt, both with and without a covering by boron oxide (B₂O₃) liquid. Interstitially dissolved oxygen concentrations in the crystals were determined by the absorption peak at 855 cm⁻¹ in the infrared absorption spectra at room temperature. It was found that oxygen concentration in a Ge crystal grown from melt partially or fully covered with B₂O₃ liquid was about 10¹⁶ cm⁻³ and was almost the same as that in a Ge crystal grown without B₂O₃. Oxygen concentration in a Ge crystal was enhanced to be greater than 10¹⁷ cm⁻³ by growing a crystal from a melt fully covered with B₂O₃; with the addition of germanium oxide powder, the maximum oxygen concentration achieved was 5.5×10¹⁷ cm⁻³. The effective segregation coefficients of oxygen in the present Ge crystal growth were roughly estimated to be between 1.0 and 1.4.     

Radial distribution studies of glassy tellurium-silicon alloys

X-ray investigations of glassy tellurium-silicon alloys (Si content 10–40 at%) are described. Alloys with 13 to 27 at% Si were obtained in bulk form, non-crystalline samples with 10, 30, 33, 36 and 40 at% Si were obtained by rapid quenching from the melt by the splat-cooling technique. The interference functions and the radial distribution functions of all alloys show a great similarity. However, the positions of the maxima of the pair distribution function decrease continuously with growing Si content and lead to values which are similar to atomic distances in crystalline Te and Si₂Te₃. The areas of the first two peaks of the RDF, F₁ (rougnly 2) and F₂ (roughly 12), are compared with calculated areas derived from different structural models which are based on the short-range order in crystalline Te with a chain structure and in Si₂Te₃ with a tetrahedron configuration. An interstitial model with Si atoms in holes of Te chains and a random substitution model, where the Te atoms and the Si atoms have the same short-range order, both show a concentration dependence of the areas F₁ contrary to the experimental values. A structural model which assumes the tetrahedron configuration of Si₂Te₃ for Si atoms (coordination number N_Si = 4) and a coordination number N_Te = 2 for Te atoms can describe the short-range order of glassy TeSi alloys in the whole investigated concentration range with 10–40 at% Si.     

On the structure of amorphous GexTe1−x systems

Calculations have been made for the quadrupole splitting of a $\text{3}\text{2}$ spin state of Te¹²⁵ in an amorphous Ge_xTe_1?x system. The results favour the existence of a threefold coordinated black phosphorus structure with an excess of TeTe chains for x-values between o and 0.5; beyond 0.5, threefold coordinated GeTe and an excess of amorphous Ge coexist.     

Infrared studies of Se-based polynary chalcogenide glasses (II): YxZxSe100−2x (Y = Ge,As; Z = As,Te)

The infrared (IR) absorption spectra for Y_xZ_xSe_100?2x glasses (Y = Ge, As;Z = As, Te), x = 2.5 and 5.0 are measured in the wavenumber region 700-60 cm^?1 at room temperature. These IR spectra are explained by comparing with the IR spectra already reported for the binary glasses such as Ge–Se, As–Se and Se–Te. In Ge_xAs_xSe_100-2x glasses (x ? 5.0), the main spectral features as well explained by both the spectra of Ge_xSe_100?x and As_xSe_100?x glasses. Main structural units in these glasses are considered to be GeSe₄ tetrahedra and AsSe₃ pyramids, and Se₈ rings and Se_n chains which are the units in pure glassy Se. In Ge_xTe_xSe_100?2x glasses (x ? 5.0) and IR band which cannot be explained by either the spectra of Ge_xSe_100?x or Se_100?xTe_x glasses appears at 210 cm^?1. This band is considered to be due to Ge–Te bonds. The IR spectra of As_xTe_x Se_100?2x glasses (x ? 5.0) are well explained by both the spectra of As_xSe_100?x and Se_100?xTe_x glasses. It is concluded that As and Te atoms combine with Se atoms in the forms of AsE₃ pyramids and Se₅Te₃ mixed rings, respectively.     

Glass formation and third-order optical nonlinear properties within TeO2–Bi2O3–BaO pseudo-ternary system

Tellurite glasses from TeO₂–Bi₂O₃–BaO pseudo-ternary system were prepared using a conventional melt-quenching method and its glass-forming region was determined. A series of glasses were selected and their third-order optical nonlinearities (TONL) were measured by employing the Z-scan method at a wavelength of 800 nm with femtosecond laser pulses. The results showed that glass former Te⁴⁺ ions exhibited positive influences on the TONL and glass modifiers Ba²⁺ ions behaved similarly; low concentrated Bi³⁺ ions as glass modifiers weakened the nonlinearities, but an excess amount of Bi³⁺ behaved oppositely. FTIR measurements demonstrated that chemical bonds especially Te–O_eq vibrated at a high energy level remarkably promoted the TONL susceptibility χ⁽³⁾, and the glass sample with the highest Bi₂O₃ content exhibited the largest χ⁽³⁾ value which was due to the presence of BiO₃ polyhedra.     

A novel mixed valence iodide bridged Te(II)-Te(IV) complex featuring diisopropyldithiocarbamate(L) and iodide: ILTeII(I)TeIVL2I

The title compound is a novel mixed ligand and mixed valence complex of tellurium, the crystal structure of which is reported here. The compound crystallizes in the orthorhombic space group, Pca2₁ with four molecules per unit cell, the dimensions of which area=15.209(1),b=20.159(2),c=12.453(1) Å. The structure was solved by the heavy-atom method and refined by fullmatrix least-squares method to a finalR=0.046 andR _w=0.046 for 3011 unique reflections. The structure could be considered as 11 adduct of Te^IVL₂I₂ and Te^IILI (L=diisopropyldithiocarbamate). The two tellurium atoms, Te^II[Te(1)] and Te^IV[Te(2)] display entirely different coordinations and are bridged through iodine I(1) in a symmetrical manner. There is a short Te(1)Te(2) contact distance of 3.542(1) Å.     

Thermally-induced structural and electrical effects in GeTe-based amorphous alloys

The thermal, structural electrical properties of bulk glasses based on GeTe compositions near the binary eutectic, Ge₁₅Te₈₅, are studied. Information regarding the non-crystalline state and the transformation from the non-crystalline to the crystalline state is reported. The particular alloys studied represent binary (Ge₁₇Te₈₃), ternary (Ge₁₅Te₈₀As₅) and quaternary (Ge₁₅Te₈₁Sb₂S₂) compositions. Structural information is obtained using X-ray diffraction techniques and density measurements. Thermal data are reported from differential scanning calorimetry (DSC), thermogravimetry (TGA) and mass spectrometry results. The electrical conductivity is measured as a function of temperature and, on the ‘as-prepared’ glasses, shows semi-conducting behavior with activation energies, E, of 0.43–0.48 eV. DSC, TGA and X-ray powder diffraction patterns indicate the samples crystallize as Te and GeTe in a two-step process, and melt at the binary eutectic temperature. The binary vaporizes as Te and GeTe in a two-step process. GeTeAs and GeTeSbS vaporize by essentially the same mechanism, with As evaporating (<300°C) before the Te, and Sb and S evaporating (420–480°C) after the Te but before GeTe. The results show that the properties of the bulk ‘as-prepared’ glasses are strikingly similar. Thermally-induced changes in the structural and electrical properties of bulk samples have been examined following a series of anneals (5 h, vacuum) at temperatures from 111°C to 190°C (glass transition temperature $\text{?125?133°}\text{C}$; crystallization temperature $\text{?206?228°}\text{C}$ as determined by DSC). DSC, TGA and mass spectrometry results have been correlated to electrical and structural changes. Results show that crystalline Te nucleates at the surface and forms a conductive surface layer. The conductivity of this surface layer is nearly temperature independent with E ≈ 10^?2 eV for all three alloys. Crystallization and the associated electrically conductive regions extend into the bulk material with further annealing. In these disordered alloys the additives As and Sb + S apparently do not act as electrical dopants in the sense of affecting the conductivity activation energy. The additives Sb + S however do retard crystallization of GeTe. The secondary crystallization product, GeTe, apparently changes the conduction mechanism to either a metallic or degenerate semiconductor type behavior.     

Growth mechanism in atomic layer epitaxy (III) reevaporation of Cd and Te from CdTe (111) surfaces and thick elemental deposits monitored by quadrupole-mass spectrometry

Quadrupole-mass spectroscopical (QMS) studies on isothermal reevaporation of Cd and Te species from the CdTe (111) surface have been performed in two extreme cases. The first concerns the reevaporation of thick, bulk-like non-crystalline Cd and Te films deposited in high vacuum at room temperature on the (111) surface, whereas in the second case evaporation of the constituent species from the bare single crystalline (111) surface has been investigated. The fluxes of the species desorbing in high vacuum (10⁻⁶ Pa) have been monitored with QMS and the desorption temperatures have been measured with a thermocouple mounted as near as possible to the sample surface. The following values E_a(Cd)_bulk = 1.13 ± 0.12 eV, E_a(Te)_bulk = 1.64 ± 0.18 eV and E_a(Cd)₍₁₁₁₎ = 1.13 ± 0.06 eV, E_a(Te)₍₁₁₁₎ = 1.92 ± 0.13 eV of the activation energies for these two cases have been determined from the slopes of the Arrhenius plots. Using these experimental values, the numbers of atomic bonds N_Cd and N_Te occurring in the atomic aggregates of quasi-gas molecules forming the near surface quasi-gas transition layers have been estimated. For Cd quasi-gas molecules 2 ≤ N_Cd ≤ 5, whereas for Te molecules 3 ≤ N_Te ≤ 10. However, no prediction concerning the number of atoms creating the quasi-gas molecules could be made on the basis of the QMS investigations. It has also been shown that Cd atoms evaporate from the bare single crystalline CdTe (111) surface with an activation energy that is equal (in the limits of the experimental error) to the activation energy for sublimation of Cd atoms from pure, non-crystalline, bulk Cd pieces. The analogous activation energy measured for Te atoms is about 20% larger than that of the relevant sublimation process. This result confirms the fact that Te atoms are bound much stronger in the CdTe crystal lattice than Cd atoms.     

On symmetry of sillenites

A precise X-ray diffraction study of a sillenite crystal with the initial composition Bi₂₄(Si _x Mn_1−x )₂O₄₀ grown by the hydrothermal method showed the presence of diffraction reflections that make it possible to assign this crystal to the sp. gr. P23, in contrast to the Bi₂₄Si₂O₄₀ crystal with the sp. gr. I23. The distribution of cations over the two positions of the crystal structure of the general composition Bi₂₄(Bi_0.130(3)Si_0.277(3)Mn_1.593(3))O₄₀ with three atoms (Bi, Si, Mn) in one position of the sp. gr. P 23 is established. The disymmetrization of the Bi₂₄(Bi, Si, Mn)₂O₄₀ crystal is explained by the kinetic order-disorder phase transition, which is caused by the presence of several atoms with different crystallochemical properties in one crystallographic position of the structure, in contrast to the Bi₂₄Si₂O₄₀ crystal, where this phenomenon is absent.     

Static and dynamic structures of liquid GeTe mixtures

Neutron diffraction measurements of the liquid Ge–Te system and quasi- and inelastic neutron scattering experiments of the eutectic liquid Ge₁₅Te₈₅ were performed in the temperature range from 400 to 560 °C. The large temperature dependence of the static structure for liquid Ge₁₅Te₈₅ is reconfirmed; however it is found that the compositional dependence obtained at around 80 °C above the liquidus curve is rather small. The dynamic structure factors of liquid Ge₁₅Te₈₅ in the Q-region from 0.2 to 2.6 Å⁻¹ show a normal temperature dependence. From the vibrational density of states, it is found that the Te–Te covalent bond persists in liquid Ge₁₅Te₈₅; however a bending mode was not assigned clearly.