Microstructure and thermoelectric properties of Sn-doped Bi2Te2.7Se0.3 thin films deposited by flash evaporation method

(Bi_1 − xSn_x)₂Te_2.7Se_0.3 thermoelectric thin films with thickness of 800 nm have been deposited on glass substrates by flash evaporation method at 473 K. The structures, morphology of the thin films were analyzed by X-ray diffraction and field emission scanning electron microscopy respectively. Effects of Sn-doping concentration on thermoelectric properties of the annealed thin films were investigated by room-temperature measurement of Seebeck coefficient and electrical resistivity. The thermoelectric power factor was enhanced to 12.8 μW/cmK² (x = 0.003). From x = 0.004 to 0.01 Sn doping concentration, the Seebeck coefficients are positive and show p-type conduction. The Seebeck coefficient and electrical resistivity gradually decrease with increasing Sn doping concentration.     

Optimization of thermoelectric properties on Bi2Te3 thin films deposited by thermal co-evaporation

The optimization of the thermal co-evaporation deposition process for n-type bismuth telluride (Bi₂Te₃) thin films deposited onto polyimide substrates and intended for thermoelectric applications is reported. The influence of deposition parameters (evaporation rate and substrate temperature) on film composition and thermoelectric properties was studied for optimal thermoelectric performance. Energy-dispersive X-ray spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy and Raman spectroscopy confirmed the formation of Bi₂Te₃ thin films. Seebeck coefficient (up to 250 μV K^− 1), in-plane electrical resistivity (≈10 μΩ m), carrier concentration (3×10¹⁹-20×10¹⁹ cm^− 3) and Hall mobility (80-170 cm² V⁻¹ s^− 1) were measured at room temperature for selected Bi₂Te₃ samples.     

Thermal co-evaporation of Sb2Te3 thin-films optimized for thermoelectric applications

Antimony telluride (Sb₂Te₃) is a chalcogenide material used in thermoelectric applications. The deposition of thin films of Sb₂Te₃ requires a precisely controlled process to achieve a desirable high thermoelectric figure-of-merit. The optimization of the thermal co-evaporation process for p-type Sb₂Te₃ thin-film onto plastic substrates (Kapton© polyimide) for thermoelectric applications is reported. The influence of deposition parameters and composition on thermoelectric properties was studied, seeking optimal thermoelectric performance. Energy-dispersive X-ray spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy and Raman spectroscopy all confirmed the formation of Sb₂Te₃ thin films. Seebeck coefficient (up to 190 μVK⁻¹), in-plane electrical resistivity (8-15 μΩm), carrier concentration (1 × 10¹⁹-7 × 10¹⁹ cm⁻³) and Hall mobility (120-180 cm²V⁻¹s⁻¹) were measured at room temperature for the best Sb₂Te₃ thin-films.     

Crystallization behavior and thermoelectric characteristics of the electrodeposited Sb2Te3 thin films

Crystallization behavior of the electrodeposited Sb₂Te₃ film was characterized and the effect of the amorphous-crystalline transition on the Seebeck coefficient was evaluated. The as-electrodeposited Sb₂Te₃ film was amorphous and exhibited the Seebeck coefficient of 268-322 μV/K, which was much larger than the value of the crystalline Sb₂Te₃ film. When annealed at temperatures above 100 °C, the Seebeck coefficient of the Sb₂Te₃ film dropped significantly to 78-107 μV/K due to the amorphous-crystalline transition at 94 °C. The thermal stability of the electrodeposited Sb₂Te₃ film was improved by the addition of Cu, and the crystallization temperature of the CuSbTe film increased up to 149.5 °C.     

Catalyst-free growth of Sb2Te3 nanowires

In this study, a catalyst-free growth method was discovered to prepare the high-quality single crystal Sb₂Te₃ nanowires from the Al:Ge:Sb:Te thin films. The diameters of Sb₂Te₃ nanowires were found to be ~ 100 nm and their lengths were as great as tens of micrometers. The Al content and the annealing temperature play an important role in the growth of Sb₂Te₃ nanowires. When the Al content (> 12.4 at.%) was sufficiently contained in Al:Ge:Sb:Te film, Sb₂Te₃ nanowires were extruded spontaneously on the surface of thin film with increase in annealing temperatures. Compared with the vapor-liquid-solid method, our method has advantages of low temperature (~ 300 °C) and no impurities, such as a metal catalyst.     

Microstructure and thermoelectric properties of n-type 95%Bi2Te3-5%Bi2Se3 alloy produced by rapid solidification and hot extrusion

n-type SbI₃-doped 95%Bi₂Te₃+5%Bi₂Se₃ compounds were prepared by a rapid solidification and extrusion at the temperature range 420-480 °C using an extrusion ratio of 25:1. The microstructure and thermoelectric properties of the compounds were investigated as a function of extrusion temperature. The fabricated powder consists of homogeneous Bi₂Te₃+Bi₂Se₃ solid solution and the relative density of over 99% was obtained by hot extrusion. The values of Seebeck coefficient for the compounds hot extruded at 420, 450, and 480 °C were −160.8, −170.2, and −165.7 μV K⁻¹, respectively. The values of electrical resistivity (ρ) for the compounds hot extruded at 420, 450, and 480 °C were 0.49, 0.57, and 0.51×10⁻⁵ Ω m, respectively. The maximum power factor value of the compounds hot extruded at 480 °C was 53.8×10⁶ μW cm⁻¹ K⁻².     

Crystallization behavior and resistance change in eutectic Si15Te85 amorphous films

Crystallization process and the corresponding electrical resistance change were investigated in eutectic Si₁₅Te₈₅ amorphous thin films. The Si₁₅Te₈₅ amorphous film showed two-stage crystallization process upon heating. In the first stage, the Si₁₅Te₈₅ amorphous crystallized into Te crystals at 175 °C. In the second stage, the residual amorphous phase crystallized into Si₂Te₃ crystals at above 300 °C accompanying the resistance drop. Before the second crystallization, the electrical resistance once increased in the temperature range of about 250-295 °C. This phenomenon can be explained by considering the formation of amorphous phase with a high electrical resistivity.     

Effect of the substrate on the electrodeposition of Bi2Te3−ySey thin films

The potentiostatic electrodeposition of n-type Bi₂Te_3−ySe_y thermoelectric films onto stainless steel and gold substrates from nitric acid aqueous solutions has been carried out at room temperature. The cathodic process during the electrodeposition of Bi₂Te_3−ySe_y films was investigated by cyclic voltammetric experiments. The structure and surface morphology of Bi₂Te_3−ySe_y films deposited on both substrates were characterized by X-ray diffraction (XRD) and environment scanning electron microscopy (ESEM) coupled with energy dispersive spectroscopy (EDS). Electrical and thermoelectric properties of as-deposited films were also measured at room temperature. The results show that the reduction process under the same depositing conditions on gold and stainless steel substrates is very different. On gold substrates, H₂SeO₃ in the electrolyte is firstly reduced to elemental Se, and then the deposited Se reacts with HTeO₂⁺ and Bi³⁺ to form Bi₂Te_3−ySe_y alloy. On stainless steel substrates, HTeO₂⁺ in the electrolyte is firstly replaced by elemental Fe to produce elemental Te, and subsequently the generated Te reacts with H₂SeO₃ and Bi³⁺ to form Bi₂Te_3−ySe_y alloy. Analysis of ESEM show that the surface morphology of the films electrodeposited on gold substrates is more compact than that on stainless steel substrates. The XRD patterns indicate that the films electrodeposited on both substrates exhibit preferential orientation along (1 1 0) plane, but the relative peak intensity of (0 1 5) and (2 0 5) planes on stainless steel substrates is stronger than that on gold substrates. The Seebeck coefficient and electrical resistivity of the films deposited on stainless steel substrates are higher than that on gold substrates.     

Transparent p-AgCoO2/n-ZnO diode heterojunction fabricated by pulsed laser deposition

Transparent diode heterojunction on ITO coated glass substrates was fabricated using p-type AgCoO₂ and n-type ZnO films by pulsed laser deposition (PLD). The PLD of AgCoO₂ thin films was carried out using the pelletized sintered target of AgCoO₂ powder, which was synthesized in-house by the hydrothermal process. The band gap of these thin films was found to be ∼ 3.89 eV and they had transmission of ∼ 55% in the visible spectral region. Although Hall measurements could only indicate mixed carrier type conduction but thermoelectric power measurements of Seebeck coefficient confirmed the p-type conductivity of the grown AgCoO₂ films. The PLD grown ZnO films showed a band gap of ∼ 3.28 eV, an average optical transmission of ∼ 85% and n-type carrier density of ∼ 4.6 × 10¹⁹ cm^− 3. The junction between p-AgCoO₂ and n-ZnO was found to be rectifying. The ratio of forward current to the reverse current was about 7 at 1.5 V. The diode ideality factor was much greater than 2.     

Fabrication and characterization of n-CdSe0.7Te0.3/p-CdSe0.15Te0.85 solar cell

Hot wall deposited CdSe_xTe_1−x where 0 ≤ x ≤ 1 thin films for solar cell applications have been prepared from a compound synthesized by direct reaction of high purity Cd, Se and Te elements. Crystal structure and composition of the films were analyzed by X-ray diffraction, scanning electron microscope and EDAX. X-ray diffraction studies carried out on pseudo-binary system revealed that the films are polycrystalline in nature with CdSe_0.7Te_0.3 film exhibiting hexagonal structure and CdSe_0.15Te_0.85 film exhibiting cubic zinc blende structure. The type of conduction was determined by Hall studies. A novel solar cell with structure n-CdSe_0.7Te_0.3/p-CdSe_0.15Te_0.85 has been fabricated and the efficiency was found to be 3.13%.     

Growth and characterization of Bi2Se3 thin films by pulsed laser deposition using alloy target

Bi₂Se₃ thin films were deposited on the (100) oriented Si substrates by pulsed laser deposition technique at different substrate temperatures (room temperature −400 °C). The effects of the substrate temperature on the structural and electrical properties of the Bi₂Se₃ films were studied. The film prepared at room temperature showed a very poor polycrystalline structure with the mainly orthorhombic phase. The crystallinity of the films was improved by heating the substrate during the deposition and the crystal phase of the film changed to the rhombohedral phase as the substrate temperature was higher than 200 °C. The stoichiometry of the films and the chemical state of Bi and Se elements in the films were studied by fitting the Se 3d and the Bi 4d5/2 peaks of the X-ray photoelectron spectra. The hexagonal structure was seen clearly for the film prepared at the substrate temperature of 400 °C. The surface roughness of the film increased as the substrate temperature was increased. The electrical resistivity of the film decreased from 1 × 10⁻³ to 3 × 10⁻⁴ Ω cm as the substrate temperature was increased from room temperature to 400 °C.     

Effect of structural transformation on the electrical properties for Ge1Sb2Te4 thin film

Dependence of electrical properties of phase change Ge₁Sb₂Te₄ thin film on structural transformation was investigated. The electrical resistivity of the film decreases with increasing annealing temperature with a steep drop at ∼ 230 °C (the second crystallization temperature), at which the structure of Ge₁Sb₂Te₄ changes from face-centered cubic to trigonal state. The steep drop of resistivity at the second crystallization temperature is mainly due to the increase of hole density within the p-type film, according to Hall measurement. The crystallization process has been followed by in situ resistance measurement at various annealing temperatures. Transmission electron microscope and atomic force microscope were also employed to study the film.     

Single-step sputtered Cu2SnSe3 films using the targets composed of Cu2Se and SnSe2

Cu₂SnSe₃ thin films were prepared by single-step D.C. sputtering at 100-400 °C for 3 h using targets composed of Cu₂Se and SnSe₂ in three different ratios of 2/1 (target A), 1.8/1 (target B), and 1.6/1 (target C). The advantages of self-synthesized SnSe₂ instead of commercially available SnSe for depositing Cu₂SnSe₃ thin films were demonstrated. Effects of target composition and substrate temperature on the properties of Cu₂SnSe₃ thin films were investigated. Structure, surface morphology, composition, electrical and optical properties at different process conditions were measured. The 400 °C-sputtered films obtained from target B display with direct band gap of 0.76 eV, electrical resistivity of 0.12 Ω cm, absorption coefficient of 10⁴-10⁵ cm^− 1, carrier concentration of ∼ 1.8 × 10¹⁹ cm^− 3, and electrical mobility of 2.9 cm²/V s.     

Medium-term thermal stability of amorphous Ge2Sb2Te5 flash-evaporated thin films with regards to change in structure and optical properties

The stability of flash-evaporated amorphous Ge₂Sb₂Te₅ thin films has been studied under medium-term temperature treatment (30 - 80 °C, with a step of 10 °C) in ten subsequent heating and cooling cycles. The significant changes in structure and optical properties are reported. The temperature cycling of the films resulted in formation of an isolated 5 - 7 nm nano-crystalline phase in the amorphous phase. The corresponding increase in refractive index and change in optical bandgap energy and sheet resistance are also presented. The formation of Ge₂Sb₂Te₅ nano-crystals (~ 5 - 7 nm) even under temperature below 80 °C could contribute to the explanation of mechanism of resistivity fluctuation (drift) of the “amorphous phase” films. We also show that the optical and electrical properties of flash evaporated Ge₂Sb₂Te₅ thin films are very similar to those reported for sputtered films.     

Crystallization and electrical characteristics of Ge1Cu2Te3 films for phase change random access memory

Phase change random access memory (PCRAM) requires an advanced phase change material to lower its power consumption and to enhance its data retention and endurance abilities. The present work investigated the crystallization behaviors and electrical properties of Ge₁Cu₂Te₃ compound films with a low melting point of about 500 °C for PCRAM application. Sputter-deposited Ge₁Cu₂Te₃ amorphous films showed a high crystallization temperature of about 250 °C. The Ge₁Cu₂Te₃ amorphous film showed an electrical resistance decrease of over 10²-fold and exhibited a small increase in thickness of 2.0% upon crystallization. The Ge₁Cu₂Te₃ memory devices showed reversible switching behaviors and exhibited a 10% lower power consumption for the reset operation than the conventional Ge₂Sb₂Te₅ memory devices. Therefore, the Ge₁Cu₂Te₃ compound is a promising phase change material for PCRAM application.     

The thermoelectric properties of Co4Sb12-xTex synthesized at different pressure

Skutterudite compounds Co₄Sb_12-xTe_x (0.1 ≤ ×≤0.8) was synthesized successfully by high temperature and high pressure (HTHP) method and characterized with X-ray diffractometry and thermoelectric properties measurements. The samples prepared by HTHP are nearly with the single phase CoSb₃. The electrical resistivity, Seebeck coefficient and thermal conductivity were all depending on synthetic pressure and the Te content of the Skutterudite compounds were performed at room temperature. As our expected, the Seebeck coefficient increased with an increase of the synthetic pressure and the thermal conductivity decreased with an increase of the synthetic pressure. These results indicated that HTHP technique may be helpful to prepare thermoelectric materials with enhanced thermoelectric properties.     

Temperature-dependent high-resolution X-ray photoelectron spectroscopic study on Ge1Sb2Te4

Oxygen-free and amorphous Ge₁Sb₂Te₄ thin film was obtained in an ultra-high vacuum and then annealed in situ to the stable-phase temperature. High-resolution X-ray photoelectron spectroscopy using synchrotron radiation was performed on the film at the different annealing temperatures of 100, 130, 150, 180, and 250 °C. The Te 4d, Sb 4d, and Ge 3d shallow core levels as well as the valence-band spectra were acquired. In the shallow core-level spectra, we observed distinguishable changes in the Sb 4d and Ge 3d levels as the film phase changed. As the temperature increased, a higher binding-energy (BE) component appeared at the Sb 4d level, the intensity of the component increased, and the spin-orbit split feature was enhanced at the Ge 3d level. In the valence-band spectra, a slight increase was observed at 0-1, ~ 3, ~ 9, and ~ 12 eV BE, and a decrease, at ~ 1.5 and ~ 4.5 eV BE. The energy resolution employed in this study was about 150 meV.     

Thermoelectric properties of Sb2Te3 thin films by electron beam evaporation

This study applies the thermoelectric grains of Sb2Te3 on conductive glass to evaporate Sb2Te3 thin films by the electron beam evaporation method. Through experimental tests with different evaporation process parameters and film annealing conditions, thin films with better Seebeck coefficient, resistivity (p) and power fact (PF) can be obtained. Experimental results show that when thin films are annealed, their defects can be decreased accordingly, and carrier mobility can be enhanced to further elevate the conductivity of thin films. When the substrate temperature is set at 200 degrees C to fabricate Sb2Te3 thin films by the evaporation process and by annealing at 220 degrees C for 60 minutes, the Seebeck coefficient of Sb2Te3 thin films increase from 87.6 microV/K to 177.7 microV/K; resistivity falls from 6.21 m ohms-cm to 2.53 m ohms-cm and PF can achieve the maximum value of 1.24 10(-3) W/K2 m. Finally, this study attempts to add indium (In) to Sb2Te3 thin films. Indium has been successfully fabricated In3SbTe, thin films. This study also analyzes the effects of In on the thermoelectric properties of In3SbTe2 thin films.     

Microstructure evolution and thermoelectric properties of Te-poor and Te-rich (Bi,Sb)<Subscript>2</Subscript>Te<Subscript>3</Subscript> prepared via solidification

This paper explores in detail, the microstructures and thermoelectric properties of Te-rich and Te-poor (Bi,Sb)₂Te₃ alloys. We show that tuning the composition of ternary Bi–Sb–Te type alloys allows us to synthesize a range of microstructures containing a primary solid solution of (Bi,Sb)₂Te₃ with varying amounts of Te solid solution or a (Bi,Sb)Te compound. Te exists as a constituent of the multilayer domain while (Bi,Sb)Te appears in the thin intercellular regions of the (Bi,Sb)₂Te₃ dendritic cells. The presence of Te imparts an n-type behavior to the composite while the (Bi,Sb)₂Te₃ with a small amount of (Bi,Sb)Te exhibits p-type properties. A maximum ZT value of ≈0.4 at 425 K was achieved, opening up the possibility of using these alloys for thermoelectric device applications.     

Enhancement of thermoelectric figure of merit by doping Dy in La0.1Sr0.9TiO3 ceramic

Ceramic samples of La_0.1Sr_0.9−xDy_xTiO₃ (x = 0.01, 0.03, 0.07, 0.10) have been prepared by the solid-state reaction method. Characterization from the powder X-ray diffraction indicates that their crystal structure changes from cubic to tetragonal phase. Their electrical and thermal transport properties are measured in the temperature range of 300-1100 K. n-Type thermoelectric is obtained with large Seebeck coefficient. The figure of merit is markedly improved, due to relatively lower electrical resistivity and thermal conductivity by Dy doping effect. A much lower electrical resistivity of 0.8 mΩ cm at room temperature is obtained in La_0.1Sr_0.8Dy_0.1TiO₃, and with a relatively lower thermal conductivity of 2.5 W/m K at 1075 K. The maximum figure of merit reaches ∼0.36 at 1045 K for La_0.1Sr_0.83Dy_0.07TiO₃, which is the largest value among n-type oxide thermoelectric ceramics.