Annealing temperature influence on electrical properties of ion beam sputtered Bi2Te3 thin films

Ion beam sputtering process was used to deposit n-type fine-grained Bi₂Te₃ thin films on BK7 glass substrates at room temperature. In order to enhance the thermoelectric properties, thin films are annealed at the temperatures ranging from 100 to 400 °C. X-ray diffraction (XRD) shows that the films have preferred orientations in the c-axis direction. It is confirmed that grain growth and crystallization along the c-axis are enhanced as the annealing temperature increased. However, broad impurity peaks related to some oxygen traces increase when the annealing temperature reached 400 °C. Thermoelectric properties of Bi₂Te₃ thin films were investigated at room temperature. The Bi₂Te₃ thin films, including as-deposited, exhibit the Seebeck coefficients of −90 to −168 μV K⁻¹ and the electrical conductivities of 3.92×10²-7.20×10² S cm⁻¹ after annealing. The Bi₂Te₃ film with a maximum power factor of 1.10×10⁻³ Wm⁻¹ K⁻² is achieved when annealed at 300 °C. As a result, both structural and transport properties have been found to be strongly affected by annealing treatment. It was considered that the annealing conditions reduce the number of potential scattering sites at grain boundaries and defects, thus improving the thermoelectric properties.     

Electrodeposition of BixSb2−xTey thermoelectric thin films from nitric acid and hydrochloric acid systems

The electrochemical behaviors of Bi^III, Te^IV and Sb^III single ions and their mixtures were investigated in nitric acid and hydrochloric acid system separately. Based on which, Bi_xSb_2−xTe_y thermoelectric films were prepared by potentiostatic electrodeposition from the solutions with different concentrations of Bi^III, Te^IV and Sb^III in the two acid systems. The morphologies, compositions, structures, Seebeck coefficients and resistivities of the deposited thin films were characterized and compared by ESEM (or FESEM), EDS, XRD, Seebeck coefficient measurement system and four-probe resistivity measuring device respectively. The results show that although Bi_xSb_2−xTe_y thermoelectric thin film which structure is consistent with the standard pattern of Bi_0.5Sb_1.5Te₃ can be gained in both of the two acid solutions by adjusting the deposition potential, their morphologies and thermoelectric properties have big differences in different acid solutions.     

Optical and thermoelectric characterizations of electroplated n-Bi2(Te0.9Se0.1)3

Bismuth selenotelluride (Bi₂(Te_0.9Se_0.1)₃) films were electrodeposited at constant current density from acidic aqueous solutions with Arabic gum in order to produce thin films for miniaturized thermoelectric devices. X-ray fluorescence spectroscopy determined film compositions. X-ray diffraction pattern shows that the films as deposited are polycrystalline, isostructural to Bi₂Te₃ and covered by crystallites. Mueller-matrix analysis reveals that the electroplated layers are optically like an isotropic medium. Their pseudo-dielectric functions were determined using mid-infrared spectroscopic ellipsometry. Tauc-Lorentz combined with Drude dispersion relations were successfully used. The energy band gap E_g was found to be about 0.15 eV. Moreover, the fundamental absorption edge was described by an indirect optical band-to-band transition. From Seebeck coefficient measurement, films exhibit n-type charge carrier and the value of thermoelectric power is about −40 μV/K.     

Switching phenomenon and optical properties of Se85Te10Bi5 films

Se₈₅Te₁₀Bi₅ films of different thicknesses ranging from 126 to 512 nm have been prepared. Energy-dispersive X-ray (EDX) spectroscopy technique showed that films are nearly stoichiometric. X-ray diffraction (XRD) measurements have showed that the Se₈₅Te₁₀Bi₅ films were amorphous. Electrical conduction activation energy (ΔE_σ) for the obtained films is found to be 0.662 eV independent of thickness in the investigated range. Investigation of the current voltage (I-V) characteristics in amorphous Se₈₅Te₁₀Bi₅ films reveals that it is typical for a memory switch. The switching voltage V_th increases with the increase of the thickness and decreases exponentially with temperature in the range from 298 to 383 K. The switching voltage activation energy (ε) calculated from the temperature dependence of V_th is found to be 0.325 eV. The switching phenomenon in amorphous Se₈₅Te₁₀Bi₅ films is explained according to an electrothermal model for the switching process. The optical constants, the refractive index (n) and the absorption index (k) have been determined from transmittance (T) and reflectance (R) of Se₈₅Te₁₀Bi₅ films. Allowed non-direct transitions with an optical energy gap (E_g^opt) of 1.33 eV have been obtained. ΔE_σ is almost half the obtained value of E_g^opt, which suggested band to band conduction as indicated by Davis and Mott.     

Characterization of PbSe1−xTex thin films

The lead salts and their alloys are extremely interesting semiconductors due to their technological importance. The fabrication of devices with alloys of these compounds possessing detecting and lasing capabilities has been an important recent technological development. The high quality polycrystalline thin films of PbSe_1−xTe_x with variable composition (0≤x≤1) have been deposited onto ultra clean glass substrates by vacuum evaporation technique. As deposited films were annealed in vacuum at 350 K. The optical, electrical and structural properties of PbSe_1−xTe_x thin films have been examined. The optical constants (absorption coefficient and bandgap) of the films were determined by absorbance measurements in the wavelength range 2500-5000 nm using Fourier transform infrared spectrophotometer. The dc conductivity and activation energy of the films were measured in the temperature range 300-380 K. The X-ray diffraction patterns were used to determine the sample quality, crystal structure and lattice parameter of the films.     

Annealing effects on the structural and electrical transport properties of n-type Bi2Te2.7Se0.3 thin films deposited by flash evaporation

N-type Bi₂Te_2.7Se_0.3 thermoelectric thin films with thickness 800 nm have been deposited on glass substrates by flash evaporation method at 473 K. Annealing effects on the thermoelectric properties of Bi₂Te_2.7Se_0.3 thin films were examined in the temperature range 373-573 K. The structures, morphology and chemical composition of the thin films were characterized by X-ray diffraction, field emission scanning electron microscope and energy dispersive X-ray spectroscopy, respectively. Thermoelectric properties of the thin films have been evaluated by measurements of the electrical resistivity and Seebeck coefficient at 300 K. The Hall coefficients were measured at room temperature by the Van der Pauw method. The carrier concentration and mobility were calculated from the Hall coefficient. The films thickness of the annealed samples was measured by ellipsometer. When annealed at 473 K, the electrical resistivity and Seebeck coefficient are 2.7 mΩ cm and −180 μV/K, respectively. The maximum of thermoelectric power factor is enhanced to 12 μW/cm K².     

Electrochemical deposition of Bi2Te3-based thin films

The electrochemical reduction processes on stainless-steel substrates from an aqueous electrolyte composed of nitric acid, Bi³⁺, HTeO₂⁺, SbO⁺ and H₂SeO₃ systems were investigated using cyclic voltammetry. The thin films with a stoichiometry of Bi₂Te₃, Bi_0.5Sb_1.5Te₃ and Bi₂Te_2.7Se_0.3 have been prepared by electrochemical deposition at selected potentials. The structure, composition, and morphology of the films were studied by X-ray diffraction (XRD), environmental scanning electron microscopy (ESEM) and electron microprobe analysis (EMPA). The results showed that the films were single phase with the rhombohedral Bi₂Te₃ structure. The morphology and growth orientation of the films were dependent on the deposition potentials.     

Structural and optical properties of In35Sb45Se20−xTex phase-change thin films

Physical properties of In₃₅Sb₄₅Se_20−xTe_x thin films with different compositions (x=2.5, 5, 7.5, 10, 12.5 and 15 at %) prepared by electron beam evaporation method are studied. X-ray diffraction results indicate that the as-evaporated films depend on the Te content and the crystallized compounds consist mainly of Sb₂Se₃ with small amount of Sb₂SeTe₂. Transmittance and reflectance of the films are found to be thickness dependent. Optical-absorption data indicate that the absorption mechanism is direct transition. Optical band gap values decrease with increase in Te content as well as with increase in film thickness.     

Activation energies of the acceptor-bound excitons and the donor-acceptor pairs in nitrogen-doped p-type ZnSe, p-type ZnSySe1−y, and p-type Zn1−xMgxSySe1−y epitaxial films grown on GaAs (1 0 0) substrates

Nitrogen-doped p-type ZnSe, p-type ZnS_ySe_1−y, and p-type Zn_1−xMg_xS_ySe_1−y epilayers were grown on n-type GaAs (1 0 0) substrates by molecular beam epitaxy. Photoluminescence (PL) spectra for the p-type ZnSe and the lattice-matched p-type ZnS_0.06Se_0.94, and p-type Zn_0.92Mg_0.08S_0.12Se_0.88 epilayers showed a deep acceptor bound exciton emission and a donor-acceptor pair emission. Temperature-dependent PL measurements were carried out to determine the activation energies of these states. The activation energies of the acceptor-bound excitons and the donor-acceptor pairs were determined to be 40 and 65 meV in the p-type ZnSe epilayer, 20 and 45 meV in the p-type ZnS_0.06Se_0.94, and 45 and 43 meV in the p-type Zn_0.92Mg_0.08S_0.12Se_0.88 epilayers.     

Effect of composition and thermal annealing on the absorption and electrical conduction of Se85−xTe15Sbx glasses

The optical absorption of the as-prepared and thermally annealed Se_85−xTe₁₅Sb_x (0≤x≤9) thin films was measured. The mechanism of the optical absorption follows the rule of non-direct transition. The optical energy gap (E₀) decreased from 1.12 to 0.84 eV with increasing Sb content of the as-prepared films from 0 to 9 at.%. The as-prepared Se₇₆Te₁₅Sb₉ films showed an increase in (E₀) with increasing the temperature of annealing in the range above T_g (363 K). The electrical conductivity of the as-prepared and annealed films was found to be of Arrhenius type with temperature in the range 300-360 K. The activation energy for conduction was found to decrease with increasing both the Sb content and temperature of annealing. The results were discussed on the basis of the lone-pair electron effect and of amorphous crystalline transformation.     

Fabrication of multilayered Ge nanocrystals embedded in SiOxGeNy films

Multilayered Ge nanocrystals embedded in SiO_xGeN_y films have been fabricated on Si substrate by a (Ge + SiO₂)/SiO_xGeN_y superlattice approach, using a rf magnetron sputtering technique with a Ge + SiO₂ composite target and subsequent thermal annealing in N₂ ambient at 750 °C for 30 min. X-ray diffraction (XRD) measurement indicated the formation of Ge nanocrystals with an average size estimated to be 5.4 nm. Raman scattering spectra showed a peak of the Ge-Ge vibrational mode downward shifted to 299.4 cm⁻¹, which was caused by quantum confinement of phonons in the Ge nanocrystals. Transmission electron microscopy (TEM) revealed that Ge nanocrystals were confined in (Ge + SiO₂) layers. This superlattice approach significantly improved both the size uniformity of Ge nanocrystals and their uniformity of spacing on the ‘Z’ growth direction.     

Surface morphology of DyxOy films grown on Si

The crystalline structure and surface morphology of Dy_xO_y dielectric films grown on Si substrates were studied by grazing incidence diffraction and absorption with use of synchrotron radiation and by atomic force microscopy. The crystalline structure and the roughness of Dy_xO_y films were found to be strongly dependent on the deposition rate. The dielectric-silicon interface depends on the type of gas used in the annealing process. Moreover, results from the near edge X-ray absorption studies, have revealed that none of the examined films has a stoichiometry close to the Dy₂O₃. The level of stoichiometry is determined by the technological conditions. Nevertheless, MOS structures with Dy_xO_y films (EOT ∼ 23 Å) have shown a rather good Dy_xO_y-Si interface properties, which can be further improve by thermal annealing, and introducing of several additives, therefore Dy_xO_y films can be considered as suitable candidates for gate dielectric in MOS devices.     

Stress induced preferred orientation and phase transition for ternary WCxNy thin films

We deposit ternary WC_xN_y thin films on Si (1 0 0) substrates at 500 °C using direct current (DC) reactive magnetron sputtering in a mixture of CH₄/N₂/Ar discharge, and explore the effects of substrate bias (V_b) on the intrinsic stress, preferred orientation and phase transition for the obtained films by virtue of X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and selective area electron diffraction (SAED). We find that with increasing the absolute value of V_b up to 200 V the carbon (x) and nitrogen (y) atom concentrations of WC_xN_y films keep almost constant with the values of 0.75 and 0.25, respectively. The XPS and SAED results, combined with the density-functional theory (DFT) calculations on the electronic structure of WC_0.75N_0.25, show our obtained WC_xN_y films are single-phase of carbonitrides. Furthermore, we find that the compressive stress sharply increases with increasing the absolute value of V_b, which leads to a pronounced change in the preferred orientation and phase structure for the film, in which a phase transition from cubic β-WC_xN_y to hexagonal α-WC_xN_y occurs as V_b is in the range of −40 to −120 V. In order to reveal the relationship between the stress and phase transition as well as preferred orientation, the DFT calculations are used to obtain the elastic constants for β-WC_xN_y and α-WC_xN_y. The calculated results show that the preferred orientation is dependent on the competition between strain energy and surface energy, and the phase transition can be attributed to a decrease in the strain energy.     

Low-temperature thermoelectric properties of Bi85Sb15−xNbx alloys prepared by high-press sintering

The nanocrystalline materials with the general formula Bi₈₅Sb_15−xNb_x (x=0, 0.5, 1, 2, 3) were prepared by mechanical alloying and subsequent high-pressure sintering. Their transport properties involving electrical conductivity, Seebeck coefficient and thermal conductivity have been investigated in the temperature range of 80-300 K. The absolute value of Seebeck coefficient of Bi₈₅Sb₁₃Nb₂ reaches a maximum of 161 μV/K at 105 K, which is 69% larger than that of Bi₈₅Sb₁₅ at the same temperature. The power factor and figure-of-merit are 4.45×10⁻³ WK⁻²m⁻¹ at 220 K and 1.79×10⁻³ K⁻¹ at 196 K, respectively. These results suggest that thermoelectric properties of Bi₈₅Sb₁₅ based material can be improved by Nb doping.     

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.     

The dependence of the structural and optical properties on the Te mole fraction in ZnS1−xTex/GaAs heterostructures

Lattice-mismatched ZnS_1−xTe_x epilayers with various Te mole fractions on GaAs (100) substrates were grown by double well temperature gradient vapor deposition. X-ray diffraction patterns showed that the grown ZnS_1−xTe_x layers were epitaxial films. The photoluminescence spectra showed that the peak position of the acceptor-bound exciton (A⁰, X) varied dramatically with changing the Te mole fraction and that the behavior of the (A⁰, X) peak position of the ZnS_1−xTe_x epilayers with a small amount of the Te mole fraction was attributed to a bowing effect. The reflectivity and ellipsometry spectra showed that the absorption energy peak was significantly affected due to the Stoke's effect. These results provide important information on the structural and optical properties of ZnS_1−xTe_x/GaAs heterostructures for improving optoelectronic device efficiencies operating in the spectral range between near ultraviolet and visible regions.     

Field electron emission from HfNxOy thin films deposited by direct current sputtering

HfN_xO_y thin films were deposited on Si substrates by direct current sputtering at room temperature. The samples were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD). SEM indicates that the film is composed of nanoparticles. AFM indicates that there are no sharp protrusions on the surface of the film. XRD pattern shows that the films are amorphous. The field electron emission properties of the film were also characterized. The turn-on electric field is about 14 V/μm at the current density of 10 μA/cm², and at the electric field of 24 V/μm, the current density is up to 1 mA/cm². The field electron emission mechanism of the HfN_xO_y thin film is also discussed.     

Third-order optical nonlinearities of lead-free (Na1−xKx)0.5Bi0.5TiO3 thin films

(Na_1−xK_x)_0.5Bi_0.5TiO₃ (NKBT) (x = 0.1, 0.2, and 0.3) thin films with good surface morphology and rhombohedral perovskite structure were fabricated on quartz substrates by a sol-gel process. The fundamental optical constants (the band gaps, linear refractive indices and absorption coefficients) of the films were obtained through optical transmittance measurements. The nonlinear optical properties were investigated by Z-scan technique performed at 532 nm with a picosecond laser. A two-photon absorption effect closely related with potassium-doping content was found in thin films, and the nonlinear refractive index n₂ increases evidently with potassium-doping. The real part of the third-order nonlinear susceptibility χ⁽³⁾ is much larger than its imaginary part, indicating that the third-order optical nonlinear response of the NKBT films is dominated by the optical nonlinear refractive behavior. These results show that NKBT thin films have potential applications in nonlinear optics.     

Structural characterization of thermally evaporated Bi2Te3 thin films

Thermally evaporated Bi₂Te₃ thin films were deposited on glass substrates. X-ray diffraction study confirmed that the growned films are polycrystalline in nature having hexagonal structure. The film exhibits preferential orientation along the [0 1 5] direction for the films of all thickness together with other abundant planes [0 1 1 1] and [1 1 0]. Various structural parameters such as lattice constants, crystallite size, strain, and dislocation density have been calculated and they are found to be thickness dependent. The lattice parameters are found to be a=4.38 Å and c=30.40 Å. The grain size of the films increases with thickness as the dislocation density and the microstrain decreases with thickness. The mean bond energy and the average coordination number of Bi₂Te₃ thin film are found to be 1.72 eV and 2.4, respectively.     

Laser-induced voltage characteristics of Bi2Sr2Co2Oy thin films on LaAlO3 substrates

We report the laser-induced voltage (LIV) effects in c-axis oriented Bi₂Sr₂Co₂O_y thin films grown on (0 0 1) LaAlO₃ substrates with the title angle α of 0°, 3°, 5° and 10° by a simple chemical solution deposition method. A large open-circuit voltage with the sensitivity of 300 mV/mJ is observed for the film on 10° tilting LaAlO₃ under a 308 nm irradiation with the pulse duration of 25 ns. When the film surface is irradiated by a 355 nm pulsed laser of 25 ps duration, a fast response with the rise time of 700 ps and the full width at half maximum of 1.5 ns is achieved. In addition, the experimental results reveal that the amplitude of the voltage signal is approximately proportional to sin 2α and the signal polarity is reversed when the film is irradiated from the substrate side rather than the film side, which suggests the LIV effects in Bi₂Sr₂Co₂O_y thin films originate from the anisotropic Seebeck coefficient of this material.