Effect of hot-press treatment on electrochemically deposited antimony telluride film

Antimony telluride thin film electrochemically deposited in a triethanol based alkaline electrolyte features amorphous structure, high electrical resistance, as well as fine morphology, minor impurity incorporation and anti-corrosivity. To further improve film thermoelectric performance, this film was subjected to hot-uniaxial-press (HUP) treatment at 170-250 °C. HUP treated films revealed crystallized structures, and exhibited 2-3 orders of magnitude improvement of electrical conductance. The [TeO₃²⁻]/[SbO₂⁻] of the deposition electrolyte was utilized to fine tune film composition and thermal electrical performance. Ni diffusion from the substrate into the film was also studied, and it can be reduced by using lower temperature and shorter time of HUP treatment. Film Seebeck coefficient and power factor reached 138 μV/K and 337 μW/K²?m, respectively, at elaborated deposition and HUP conditions.     

Optimization in fabricating bismuth telluride thin films by ion beam sputtering deposition

N-type bismuth telluride (Bi₂Te₃) thermoelectric thin films were deposited on BK7 glass substrates by ion beam sputtering method. Various substrate temperatures were tried to obtain optimal thermoelectric performance. The influence of deposition temperature on microstructure, surface morphology and thermoelectric properties was investigated. X-ray diffraction shows that the films are rhombohedral with c-axis as the preferred crystal orientation when the deposition temperature is above 250 °C. All the films with single Bi₂Te₃ phase are obtained by comparing X-ray diffraction and Raman spectroscopy. Scanning electron microscopy result reveals that the average grain size of the film is larger than 500 nm when the deposition temperature is above 300 °C. Thermoelectric properties including Seebeck coefficient and electrical conductivities were measured at room temperature, respectively. It is found that Seebeck coefficients increase from − 28 μV k^− 1 to − 146 μV k^− 1 and the electrical conductivities increase from 1.87 × 10³ S cm^− 1 to 3.94 × 10³ S cm^− 1 when the deposition temperature rose to 250 °C and 300 °C, respectively. An optimal power factor of 6.45 × 10^− 3 Wm^− 1 K^− 2 is gained when the deposition temperature is 300 °C. The thermoelectric properties of bismuth telluride thin films have been found to be strongly enhanced by increasing the deposition temperature.     

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.     

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.     

Thermoelectric properties and thermoelectric devices of free-standing GaN and epitaxial GaN layer

We studied the thermoelectric properties of free-standing GaN (fr-GaN) and epitaxial GaN layer (epi-GaN), and furthermore, we have fabricated thermoelectric devices using these materials. For fr-GaN, the maximum power factor was 7.7 × 10^− 4 W/m K² at 373 K, and for epi-GaN layer, the maximum power factor was 9.4 × 10^− 4 W/m K² at 373 K. The devices fabricated are (a) fr-GaN and chromel of 4 pairs, and (b) epi-GaN and chromel of 3 pairs. The maximum output power and the open output voltage were (a) 3.35 × 10^− 6 W and 2.76 × 10^− 2 V at ΔT = 153 K, and (b) 1.21 × 10^− 7 W and 1.71 × 10^− 2 V at ΔT = 153 K, respectively.     

An investigation on palladium sulphide (PdS) thin films as a photovoltaic material

Polycrystalline PdS thin films with tetragonal structure have been grown by direct sulphuration of Pd layers. They are formed by crystallites of size ∼ 50 nm. As-grown PdS films show a Seebeck coefficient, S = − 250 ± 30 μV/K, which indicates an n-type conductivity. Electrical resistivity of the samples, measured by the four contact probe, is (6.0 ± 0.6) × 10^− 2 Ω·cm. Hall effect measurements, confirms n-type conductivity with a negative carrier density n = (8.0 ± 2.0) × 10¹⁸ cm^− 3 and electron mobility μ of (20 ± 2) cm²/V s. Band gap energy (E_g) and absorption coefficient (α) are determined from the optical transmission and reflectance of the films. A direct transition with energy gap E_g = (1.60 ± 0.01) eV is obtained. Optical absorption coefficient in the range of photon energies hν > 2.0 eV is higher than 10⁵ cm^− 1. All these properties make PdS thin films a good alternative material for solar applications.     

Structural and thermoelectric properties of HfNiSn half-Heusler thin films

The bulk thermoelectric properties of half-Heusler alloys have recently been extensively studied due to their potential as thermoelectric materials. However, only a few publications have been addressed on thin film systems. The present study investigated the structural and thermoelectric properties of HfNiSn half-Heusler alloy thin films grown at different substrate temperatures: 25 °C, 200 °C, and 400 °C. The crystalline phase and structural variation of the films were determined by X-ray diffraction and scanning electron microscopy. Polycrystalline thin films were obtained for utilizing lower substrate temperatures. The HfNiSn thin films exhibited preferred (111) orientation when substrate temperature was higher than 400 °C. The in-plane Seebeck coefficient and resistivity of HfNiSn thin films with preferred orientation were much lower than those of films without orientation. This implies the thermoelectric properties of HfNiSn alloy may exhibit anisotropic characteristics. The best Seebeck coefficient and power factor of HfNiSn thin films obtained in this work are −68 μV/K and 1.3 μW/K²cm, respectively, measured at room temperature. The effects of partial substitution of Sn by Sb on thermoelectric properties of HfNiSn thin films were also studied with a “pseudo-combinatorial” approach.     

Novel thermoelectric materials based on boron-doped silicon microchannel plates

The thermoelectric properties of boron-doped silicon microchannel plates (MCPs) were investigated. The samples were prepared by photo-assisted electrochemical etching (PAECE). The Seebeck coefficient and electrical resistivity at room temperature (25 °C) were measured to determine the thermoelectric properties of the samples. In order to decrease the very high resistivity, boron doping was introduced and by modulating the doping time, a series of samples with different resistivity as well as Seebeck coefficient were obtained. Boron doping changed the electrical resistivity of the samples from 1.5 × 10⁵ Ω cm to 5.8 × 10⁻³ Ω cm, and the absolute Seebeck coefficient deteriorated relatively slightly from 674 μV/K to 159 μV/K. According to the Seebeck coefficient and electrical conductivity, the power factor was calculated and a peak value of 4.7 × 10⁻¹ mW m⁻¹ K⁻² was obtained. The results indicate that silicon MCPs doped with boron are promising silicon-based thermoelectric materials.     

Electrical and thermal transport properties of electrically stressed Bi-Sb-Te nanocrystalline thin films

Nanoscale size effect is beneficial for enhancing thermoelectric figure-of-merit of Bi-Sb-Te compounds due to the decrease of thermal conductivity. Bi-Sb-Te nanocrystalline thin films prepared by sputtering at room temperature, in general, require a post-deposition treatment to improve their electrical transport properties by eliminating residual crystal defects. In this study we present an electric current stressing treatment to effectively eliminate crystal defects in sputtered Bi-Sb-Te films at low temperature. By maintaining a low thermal conductivity of 0.6-0.7 W/mK, the electrically stressed Bi-Sb-Te nanocrystalline films possess highly enhanced Hall mobility and moderately reduced carrier concentration as compared to the films thermally treated at the same temperature. Carrier concentration, mobility and Seebeck measurement results suggest that the change of electrical transport properties involves the elimination of Sb_Te antisite defects as supported by the observation of some Sb-rich precipitates in the thermally/electrically treated Bi-Sb-Te films. Besides, crystal defects are also suggested to be preferentially removed in the (00l)-oriented grains due to anisotropic diffusion and electrical transport properties in the electrically stressed Bi-Sb-Te films.     

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.     

Microstructure and thermoelectric properties of p-type Bi-Sb-Te-Se thin films prepared by electrodeposition method

P-type Bi-Sb-Te-Se thermoelectric thin films with thickness of 8 μm have been prepared by cathodic electrodeposition technique on Au substrate from nitric acid solution system at room temperature. Cyclic voltammetry was used for determination of the deposition potentials of the thin films. In order to enhance the crystallinity, as well as the thermoelectric properties of the deposited films, they were annealed at 523 K for 2 h under nitrogen atmospheric pressure condition. X-ray diffraction (XRD), environmental scanning electron microscopy, and energy-dispersive spectroscopy (EDS) were employed to characterize the thin films. Seebeck coefficients and resistivities of the films were also evaluated. The results revealed that Bi, Sb, Te and Se could be co-deposited to form Bi-Sb-Te-Se semiconductor compound in the solution containing Bi^III, Sb^III, Te^IV and Se^IV and the compositions of the films were sensitive to the electrodepositing potentials. The XRD results suggested that the crystal structure of the thin films were changed from amorphous state to polycrystalline after annealing. The EDS data indicated that the composition of the films was consistent with XRD results. The annealed Bi-Sb-Te-Se thin films exhibited the Seebeck coefficients of 116-133 μV/K and a maximum power factor of 0.62 mW·K^− 2·m^− 1.     

Optimization of Bi2Te3 and Sb2Te3 thin films deposited by co-evaporation on polyimide for thermoelectric applications

The optimization of the deposition process of n-type Bismuth Telluride and p-type Antimony Telluride thin films for thermoelectric applications is reported. The films were deposited on a 25 μm-thick flexible polyimide (kapton) substrate by co-evaporation of Bi and Te, for the n-type element, and Sb and Te, for the p-type element. The evaporation rate of each material was monitorized by an oscillating crystal sensor and the power supplied to each evaporation boat was controlled with a PID algorithm in order to achieve a precise user-defined constant evaporation rate.The influence of substrate temperature (in the range 240-300 °C) and evaporation rates of Bi, Te and Sb on the electronic properties of the films was studied and optimized to obtain the highest Seebeck coefficient. The best n-type Bi₂Te₃ films were deposited at 300 °C with a polycrystalline structure, a composition close to stoichiometry, electrical resistivity ∼20 μΩ m and Seebeck coefficient −195 μV/°C. The best p-type Sb₂Te₃ films were deposited at 240 °C, are slightly Te-rich, have electrical resistivity ∼20 μΩ m and Seebeck coefficient +153 μV/°C. These high Seebeck coefficients and low electrical resistivities make these materials suitable for fabrication of Peltier coolers and thermopile devices.     

Improved thermoelectric performance of highly-oriented nanocrystalline bismuth antimony telluride thin films

Improved thermoelectric performance of highly-oriented nanocrystalline bismuth antimony telluride thin films is described. The thin films are deposited by a flash evaporation method, followed by annealing in hydrogen. By optimizing the annealing conditions, the resulting thin films exhibit almost perfect orientation with the c-axis normal to the substrate, and are composed of nano-sized grains with an average grain size of 150 nm. The in-plane electrical conductivity and Seebeck coefficient were measured at room temperature. The cross-plane thermal conductivity of the thin films was measured by a 3ω method, and the in-plane thermal conductivity was evaluated by using an anisotropic factor of thermal conductivity based on a single crystal bulk alloy with almost the same composition and carrier concentration. The measured cross-plane thermal conductivity is 0.56 W/(m K), and the in-plane thermal conductivity is evaluated to be 1.05 W/(m K). Finally, the in-plane power factor and figure-of-merit, ZT, of the thin films are 35.6 μW/(cm K²) and 1.0 at 300 K, respectively.     

Characterization of thermoelectric properties of layers obtained by pulsed magnetron sputtering

The pulsed magnetron sputtering technique was applied for the preparation of layers of Bi₂Te₃ and Sb₂Te₃. Target materials were synthesized in evacuated quartz ampoules by melting elemental powders mixed in stoichiometric proportions. The structure and microstructure of targets and prepared films were characterized by X-ray diffraction, scanning electron microscopy and energy dispersive X-ray analysis. Thermoelectric properties were defined by the Seebeck coefficient and electrical conductivity measurements in the temperature range 320-430 K. The layers were deposited at various powers (0.09-0.20 kW) and currents (0.07-0.16 A) at an argon pressure of about 3.0 Pa. The efficiencies of thermoelectric power obtained for bismuth telluride and antimony telluride were 2-4×10⁻⁴ and 2-6×10⁻³ W K⁻² m⁻¹, respectively. The synthesized materials were used for the fabrication of thermoelectric couples with Bi₂Te₃ as the n-type material and Sb₂Te₃ as the p-type material. The thermocouples were annealed under vacuum to obtain optimum thermoelectric properties. The Seebeck coefficient of thermocouples was evaluated by a Seebeck scanning microprobe [Platzek D, Karpinski G, Stewie C, Muchilo D, Müller E. Proceedings of the second European conference on thermoelectrics, Poland, Cracow, September 15-17, 2004].     

Structural and optical properties of amorphous and crystalline antimony sulfide thin-films

Smooth and compact thin films of amorphous and crystalline antimony sulfide (Sb₂S₃) were prepared by radio frequency sputtering of an Sb₂S₃ target. As-deposited films are amorphous. Polycrystalline antimony sulfide films composed of ∼ 500 nm grains are obtained by annealing the as-deposited films at 400 °C in sulfur vapors. Both amorphous and crystalline antimony sulfide have strong absorption coefficients of 1.8 × 10⁵ cm^− 1 at 450 nm and 7.5 × 10⁴ cm^− 1 at 550 nm, and have direct bandgaps with band energies of 2.24 eV and 1.73 eV, respectively. These results suggest the potential use of both amorphous and crystalline antimony sulfide films in various solid state devices.     

Bulk crystal growth of Mg2Si by the vertical Bridgman method

Mg₂Si were grown by the vertical Bridgman (VB) method in crucibles made of chemical vapor deposition (CVD) pyrolytic graphite (PG) in order to minimize the reaction and sticking of molten Mg-Si during growth. Congruent crystallization was derived from a stoichiometric melt of Mg₂Si, and incongruent crystallization was derived from nonstoichiometric melts having Mg/Si ratios of 85:15, 70:30 and 60:40. Grown samples were characterized by X-ray diffraction and electron-probe microanalysis, and their power factors were calculated from the Seebeck coefficients and electrical conductivities measured from room temperature to 773 K. The grown crystals were single-crystal-like and had high Seebeck coefficients at the temperatures from 500 to 773 K. A sample derived from a stoichiometric melt had a Seebeck coefficient of −470 μV/K and the highest power factor, 7.8×10⁻⁶ W/cm K² at 373 K, was calculated for the sample derived from a melt with an Mg/Si ratio of 70:30.     

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.     

Transparent amorphous In-Ga-Zn-O thin film as function of various gas flows for TFT applications

The electrical and optical properties of amorphous indium gallium zinc oxide (a-IGZO) films, which can be used as a channel layer, deposited by radio frequency (rf) magnetron sputtering system at room temperature (RT), were investigated as function of various gas flows. The optical transmittance of films deposited under Ar, O₂ / Ar + O₂ and O₂ / Ar-4% H₂ + O₂ atmospheres in the visible wavelength was consistently above 90% at a wavelength of 550 nm at all gas flows, although the film deposited under Ar-4% H₂ atmosphere exhibited a transmittance of below 50%. The carrier concentration and mobility of the a-IGZO films fabricated under Ar and Ar-4% H₂ were observed slight decrease as a function of the flow, respectively. The thin film transistors (TFTs) with an a-IGZO channel deposited under Ar and Ar-4% H₂ atmosphere exhibited the following good characteristics: V_th of 0.34 V, µ_FE of 3.6 cm² V^− 1 s^− 1, on/off ratio of 10⁶, and S value of 0.04 V decade^− 1.     

Pulsed laser deposition of p-type α-AgGaO2 thin films

Polycrystalline α-AgGaO₂ powders were prepared by the hydrothermal conversion of β-AgGaO₂. The β-AgGaO₂ was synthesized by the ion exchange reaction between NaGaO₂ and molten AgNO₃ under nitrogen atmosphere. The α-AgGaO₂ thus synthesized was used as the target for pulsed laser ablation. The films grown on α-Al₂O₃ (0001) single crystal substrates are crystalline and are 50% transparent in the visible region. The temperature dependence of conductivity shows a semiconducting behaviour with room temperature conductivity 3 × 10^− 4 Scm^− 1. The positive sign of Seebeck coefficient (+ 70 μVK^− 1) demonstrated the p-type conduction in the films. Transparent p-n heterojunctions on a glass substrate were fabricated. The structure of the device was glass/ITO/n-ZnO/p-AgGaO₂. The ratio of forward to reverse current was more than 100 in the range of − 1.5 V to + 1.5 V.     

导电聚苯胺薄膜上Bi2Te3合金层的电沉积及其热电性能

在导电聚苯胺薄膜上电沉积n型Bi-Te合金薄膜,采用循环伏安、XRD、EDS和SEM等手段分别对电化学沉积过程和产物的结构、形貌及组成等进行了表征,研究了聚苯胺绝缘化处理前后Bi_2Te_3沉积层热电性能的变化,以及沉积电位对其结构和性能的影响.结果表明:在180℃保温3 h可大大降低聚苯胺薄膜的导电性;阴极电位在-125 mV与-340 mV之间变化时,Bi-Te合金中的Te含量呈近似抛物线变化,且在-125 mV达到最大值67.76%;Te含量不同也相应地改变了沉积层的组织结构和热电性能;基体的导电性影响聚苯胺薄膜的热电参数测试值,通过热处理消除基体的影响后,热电薄膜的塞贝克系数和导电率的测量值分别提高了47.6μV/K和6.86×10~4s/m,功率因子从热处理前的1.6×10~(-4)W/K~2m提高到处理后的14.3×10~(-4)W/K~2m.