Flexible thermoelectric generator for ambient assisted living wearable biometric sensors

In this work we proposed design, fabrication and functional characterization of a very low cost energy autonomous, maintenance free, flexible and wearable micro thermoelectric generator (μTEG), finalized to power very low consumption electronics ambient assisted living (AAL) applications. The prototype, integrating an array of 100 thin films thermocouples of Sb₂Te₃ and Bi₂Te₃, generates, at 40 °C, an open circuit output voltage of 430 mV and an electrical output power up to 32 nW with matched load. In real operation conditions of prototype, which are believed to be very close to a thermal gradient of 15 °C, the device generates an open circuit output voltage of about 160 mV, with an electrical output power up to 4.18 nW.In the first part of work, deposition investigation Sb₂Te₃ and Bi₂Te₃ thin films alloys on Kapton HN polyimide foil by RF magnetron co-sputtering technique is discussed. Deposition parameters have been optimized to gain perfect stoichiometric ratio and high thermoelectric power factor; fabricated thermogenerator has been tested at low gradient conditioned to evaluate applications like human skin wearable power generator for ambient assisted living applications.     

Micro thermoelectric cooler: Planar multistage

A suspended, planar multistage micro thermoelectric (TE) cooler is designed using thermal network model to cool MEMS devices. Though the planar (two-dimensional) design is compatible with MEMS fabrication, its cooling performance is reduced compared to that of a pyramid (three-dimensional) design, due to a mechanically indispensable thin dielectric substrate (SiO₂) and technical limit on TE film thickness. We optimize the planar, six-stage TE cooler for maximum cooling, and predict ΔT_max = 51 K with power consumption of 68 mW using undoped, patterned 4–10 μm thick co-evaporated Bi₂Te₃ and Sb₂Te₃ films. Improvement steps of the planar design for achieving cooling performance of the ideal pyramid design are discussed. The predicted performance of a fabricated prototype is compared with experimental results with good agreements.     

On the role of ultra-thin oxide cathode synthesis on the functionality of micro-solid oxide fuel cells: Structure, stress engineering and in situ observation of fuel cell membranes during operation

Microstructure and stresses in dense La_0.6Sr_0.4Co_0.8Fe_0.2O₃ (LSCF) ultra-thin films have been investigated to increase the physical thickness of crack-free cathodes and active area of thermo-mechanically robust micro-solid oxide fuel cell (μSOFC) membranes. Processing protocols employ low deposition rates to create a highly granular nanocrystalline microstructure in LSCF thin films and high substrate temperatures to produce linear temperature-dependent stress evolution that is dominated by compressive stresses in μSOFC membranes. Insight and trade-off on the synthesis are revealed by probing microstructure evolution and electrical conductivity in LSCF thin films, in addition to in situ monitoring of membrane deformation while measuring μSOFC performance at varying temperatures. From these studies, we were able to successfully fabricate failure-resistant square μSOFC (LSCF/YSZ/Pt) membranes with width of 250 μm and crack-free cathodes with thickness of ∼70 nm. Peak power density of ∼120 mW cm⁻² and open circuit voltage of ∼0.6 V at 560 °C were achieved on a μSOFC array chip containing ten such membranes. Mechanisms affecting fuel cell performance are discussed. Our results provide fundamental insight to pathways of microstructure and stress engineering of ultra-thin, dense oxide cathodes and μSOFC membranes.     

Photoelectrochemical properties of spray deposited n-CdSe thin films

Polycrystalline cadmium selenide (CdSe) thin films have been prepared by spraying a mixture of an equimolar aqueous solutions of cadmium chloride and selenourea on preheated fluorine doped tin oxide (FTO) coated glass substrates at different substrate temperatures. The cell configuration n-CdSe/1 M (NaOH + Na₂S + S)/C is used for studying the capacitance-voltage (C-V) characteristics in dark, current-voltage (I-V) characteristics in dark and under illumination, photovoltaic power output and spectral response characteristics of the as deposited films. Photoelectrochemical study shows that as deposited CdSe thin films exhibits n-type of conductivity. The spectral response characteristics of the films at room temperature show a prominent sharp peak at 725 nm. The measured values of efficiency (η) and fill factor (FF) are found to be 0.50% and 0.44 respectively for film deposited at 300 °C. Electrochemical impedance spectroscopy studies show that the CdSe film deposited at 300 °C shows better performance in PEC cell.     

Preparation and properties of thin Pt-Ir films deposited by dc magnetron co-sputtering

A series of Pt-Ir thin films envisaged for application as fuel cell cathodic catalysts are deposited by dc co-sputtering from pure metal targets. To achieve different metal ratios, the sputtering power applied on the iridium target (P_Ir) is varied in the range 0-100 W at constant power of the Pt target (P_Pt). The influence of the sputtering power on the film composition, morphology, and surface structure is analysed by energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The catalytic activity towards oxygen reduction reaction (ORR) is evaluated in sulphuric acid solutions applying the methods of cyclic voltammetry and potentiodynamic polarization curves. The performed morphological and electrochemical investigations reveal that catalytic efficiency of the co-sputtered Pt-Ir films is superior compared to pure Pt. The ORR is most intensive on the sample deposited at power ratio P_Pt:P_Ir = 100:30 W containing 11 at.% Ir that has also the most developed active surface. The ORR current density for this film achieved at 0.825 V in acid solution (4.1 mA cm⁻²) is about 6 times higher than for pure Pt (0.67 mA cm⁻²). The improved activity of the thin co-sputtered Pt-Ir over Pt allows for essential reduction of the catalyst loading at preserved performance.     

Improving power density and efficiency of miniature radioisotopic thermoelectric generators

We have built and tested a prototype miniaturized thermoelectric power source that generates 450 μW of electrical power in a system volume of 4.3 cm³. The measured power density of 104 μW cm⁻³ exceeds that of any previously reported thermoelectric power system of equivalent size. This improvement was achieved by implementing a novel thermopile design in which wagon wheel-shaped thermoelectric elements contact the entire circumference of the heat source whereas traditional approaches utilize only one heat source surface. The thermopile consists of 22 wagon wheel-shaped elements (11 P–N thermocouples) fabricated from 215-μm thick bismuth–telluride wafers having ZT = 0.97 at 30 °C. The power source operates on a 150 mW thermal input provided by an electrical resistance heater that simulates a capsule containing 0.4 g of ²³⁸PuO₂ located at the center of the device. Our primary research objective was to develop and demonstrate a prototype thermopile and radioisotopic thermoelectric generator (RTG) architecture with improved power density at small scales. Output power from this device, while optimized for efficiency, was not optimized for output voltage, and the maximum power was delivered at 41 mV. We also discuss modifications to our prototype design that result in significantly improved voltage and power. Numerical predictions show that a power output of 1.4 mW, power density of 329 μW cm⁻³, and voltage of 362 mV, is possible in the same package size.     

Photoelectrochemical performances of n-CdS1−xSex thin films prepared by spray pyrolysis technique

The CdS_1−xSe_x (0.0 ? x ? 1.0) thin films of various compositions have been deposited onto the amorphous and FTO coated glass substrates using a spray pyrolysis technique. An electrode/electrolyte interface has been formed between an n-type CdS_1−xSe_x (0.0 ? x ? 1.0) alloyed/mixed type semiconductor and a sulphide/polysulphide redox electrolyte and investigated through the current-voltage, capacitance-voltage and photovoltaic power output characteristics. The dependence of the dark current through the junction and the junction capacitance on the voltage across the junction have been examined and analysed. Upon illumination of the interface with a light of 20 mW/cm², an open-circuit voltage of the order of 335 mV and a short-circuit current of 1.02 mA/cm² have been developed (for x = 0.8), which results in energy conversion efficiency and fill factor 0.79% and 0.46% respectively. The magnitudes of the barrier heights at the interfaces have been determined. The significant electrochemical properties have been observed for a cell with electrode composition x = 0.8.     

Brush electrodeposited CdSexTe1−x thin films and their properties

CdSe_xTe_1−x thin films were brush plated on titanium and conducting glass substrates from the precursors at different substrate temperatures in the range of 30-80 °C. X-ray diffraction studies indicated the films to possess hexagonal structure irrespective of composition. The strain and dislocation density decrease with increase of substrate temperature. The crystallite size increased from 30 to 100 nm as the substrate temperature increased. The resistivity of the films decreased with increase of substrate temperature. The carrier density and mobility increased with substrate temperature. Optical band gap of the films varied in the range of 1.45-1.72 eV. Higher photosensitivity was obtained compared to earlier reports.     

Analysis on the cooling performance of the thermoelectric micro-cooler

Numerical analysis has been carried out to figure out the performance of the thermoelectric micro-cooler with the three-dimensional model. A small-size and column-type thermoelectric cooler is considered and Bi₂Te₃ and Sb₂Te₃ are selected as the n- and p-type thermoelectric materials, respectively. The thickness of a thermoelectric element considered is 5–20 μm. The effect of parameters such as the temperature difference, the current, the thickness of a thermoelectric element, and the number of thermoelectric pairs on the performance of the cooler has been investigated. The predicted results show that the performance can be improved for the thick element with the large number of thermoelectric pairs or the small cross-sectional area of the element.     

Bimetallic (Ni–Fe) anode-supported solid oxide fuel cells with gadolinia-doped ceria electrolyte

Anode-supported solid oxide fuel cells (SOFC) comprising nickel + iron anode support and gadolinia-doped ceria (GDC) of composition Gd_0.1Ce_0.9O_2−δ thin film electrolyte were fabricated, and their performance was evaluated. The ratio of Fe₂O₃ to NiO in the anode support was 3 to 7 on a molar basis. Fe₂O₃ and NiO powders were mixed in the desired proportions and discs were die-pressed. All other layers were sequentially applied on the anode support. The cell structure consisted of five distinct layers: anode support – Ni + Fe; anode functional layer – Ni + GDC; electrolyte – GDC; cathode functional layer – LSC (La_0.6Sr_0.4CoO_3−δ) + GDC; and cathode current collector – LSC. Cells with three different variations of the electrolyte were made: (1) thin GDC electrolyte (∼15 μm); (2) thick GDC electrolyte (∼25 μm); and (3) tri-layer GDC/thin yttria-stabilized zirconia (YSZ)/GDC electrolyte (∼25 μm). Cells were tested with hydrogen as fuel and air as oxidant up to 650 °C. The maximum open circuit voltage measured at 650 °C was ∼0.83 V and maximum power density measured was ∼0.68 W cm⁻². The present work shows that cells with Fe + Ni containing anode support can be successfully made.     

Structure, composition and optical properties of Cu2ZnSnS4 thin films deposited by Pulsed Laser Deposition method

Polycrystalline Cu₂ZnSnS₄ (CZTS) thin films have been directly deposited on heating Mo-coated glass substrates by Pulsed Laser Deposition (PLD) method. The results of energy dispersive X-ray spectroscopy (EDX) indicate that these CZTS thin films are Cu-rich and S-poor. The combination of X-ray diffraction (XRD) results and Raman spectroscopy reveals that these thin films exhibit strong preferential orientation of grains along [1 1 2] direction and small Cu_2−xS phase easily exists in CZTS thin films. The lattice parameters and grain sizes have been examined based on XRD patterns and Atom Force Microscopy (AFM). The band gap (E_g) of CZTS thin films, which are determined by reflection spectroscopy varies from 1.53 to 1.98 eV, depending on substrate temperature (T_sub). The optical absorption coefficient of CZTS thin film (T_sub=450 °C) measured by spectroscopic ellipsometry (SE) is above 10⁴ cm⁻¹.     

Methodological reviews and analyses on the emerging research trends and progresses of thermoelectric generators

Thermoelectric generator is among the earliest initiated electricity‐harvesting methods. It is a very potential power harvester that can convert wasteful thermal energy into electricity. However, it often suffers from low energy conversion rate due to its inconsistent heat source, inefficient thermoelectric material (or thermoelement) performance, and incompetent structural issues. Progressively for the first time, detailed methodological surveys and analyses are made for bulk, thick, and thin films in this review. This is in order to accommodate better insights and comprehensions on the emerging trends and progresses of thermoelectric generators from 1989 to 2017. The research interests in thermoelectric generators have started back in 1989, and have continuously experienced emerging progresses in the number of studies over the last years. The methodological reviews and analyses of thermoelectric generator showed that almost 46.6% of bulk and 46.1% of thick and thin film research works, respectively, are actively progressed in 2014 to 2017. Nearly 86.2% of bulk and 44.1% of thick and thin film thermoelectric generators are realizing in between 0.001 and 4 μW cm^?2 K^?2, while 43.1% of thick and thin films are earning among 10^?6 to 0.001 μW cm^?2 K^?2. The highest achievement made until now is 2.5 W cm^?2 at a temperature difference of 140 K and thermoelectric efficiency factor of 127.55 μW cm^?2 K^?2. This achievement remarked positive elevation for the field and interest in thermoelectric power generation. Consecutively, the research trends of fundamental devices' structure, thermoelement, fabrication, substrate, and heat source characteristics are analyzed too, along with the desired improvement highlights for the applications of thermoelectric generators.     

Impact of substrate material and annealing conditions on the microstructure and chemistry of yttria-stabilized-zirconia thin films

Si-diffusion from Si-based substrates into yttria-stabilized-zirconia (YSZ) thin films and its impact on their microstructure and chemistry is investigated. YSZ thin films used in electrochemical applications based on micro-electrochemical systems (MEMS) are deposited via spray pyrolysis onto silicon-based and silicon-free substrates, i.e. Si_xN_y-coated Si wafer, SiO₂ single crystals and Al₂O₃, sapphire. The samples are annealed at 600 °C and 1000 °C for 20 h in air. Transmission electron microscopy (TEM) showed that the Si_xN_y-coated Si wafer is oxidized to SiO_z at the interface to the YSZ thin film at temperatures as low as 600 °C. On all YSZ thin films, silica is detected by X-ray photoelectron spectroscopy (XPS). A particular large Si concentration of up to 11 at% is detected at the surface of the YSZ thin films when deposited on silicon-based substrates after annealing at 1000 °C. Their grain boundary mobility is reduced 2.5 times due to the incorporation of SiO₂. YSZ films on Si-based substrates annealed at 600 °C show a grain size gradient from the interface to the surface of 3 nm to 10 nm. For these films, the silicon content is about 1.5 at% at the thin film's surface.     

Effect of Ti sublayer on the ORR catalytic efficiency of dc magnetron sputtered thin Pt films

A series of thin Pt films were deposited by dc magnetron sputtering directly on a commercial hydrophobic carbon paper substrate having a thin microporous Vulcan-XC72 layer or upon a thin Ti sublayer sputtered on the top of the microporous carbon film. The electrocatalytic properties of the sputtered Pt films toward the oxygen reduction reaction were investigated in 0.5 M H₂SO₄ solution and in a hydrogen PEM fuel cell. The catalyst with ultralow Pt loading of 22 μg cm⁻² deposited on a 33 Å thick Ti sublayer is robust, mechanically stable, possesses highly developed surface area and improved catalytic efficiency. Its performance as a MEA cathode in a single hydrogen PEM fuel cell (577 mA cm⁻² at 0.4 V cell voltages and a maximum power of 0.954 W) proved to be much superior compared to that of MEA with the same cathode Pt loading but without Ti sublayer (173 mA cm⁻² at 0.4 V, 0.231 W, respectively).     

Electrical resistivity of thermally evaporated bismuth telluride thin films

Semiconducting chalcogenide thin films have been receiving considerable attention in the recent years because of their wide applications in the various fields of science and technology. The studies of the electronic properties of semiconductors have been largely stimulated by attractive micro-electronic device applications. Among the various V–VI compounds, Bismuth Telluride (Bi₂Te₃) is an established low-temperature thermo electric material and is widely employed in thermoelectric generators and coolers. The present work deals with the structural and the electrical characterization of Bi₂Te₃ thin films vacuum deposited on well-cleaned glass substrates. A constant rate of deposition was maintained through out the process. To obtain uniform and homogeneous film thickness through out on all the substrates a rotary drive was employed. Quartz crystal thickness monitor was used to measure the thickness of the samples. From the X-ray diffractogram the Bi₂Te₃ films are found to be amorphous at lower thicknesses and posses hexagonal polycrystalline structure at higher thickness, having lattice parameters a=4.44 Å and c=29.40 Å. The grain size of the Bi₂Te₃ thin films before annealing and after annealing are found to be 100 and 160 Å, respectively. The micro-strain and the dislocation density are found to decrease after annealing. The thermogravimetry–differential thermal analysis (TG–DTA) studies revealed that the Bi₂Te₃ films are non-decomposable. Electrical resistivity, TCR measurements have been carried out as a function of varying temperatures in the range 303–453 K are found to show the size effect. Analyzing the size dependence of electrical resistivity it is found that the electrical resistivity is a linear function of the reciprocal of thickness of the film. The energy gap of Bi₂Te₃ thin film was calculated from the graph ln ρ vs. 1/T and it is found that the energy gap decreases with increasing thickness. From the negative values of TCR, it is inferred that Bi₂Te₃ films exhibit semiconducting behavior.     

Fabrication of bilayered YSZ/SDC electrolyte film by electrophoretic deposition for reduced-temperature operating anode-supported SOFC

Bilayered Y₂O₃-stabilized ZrO₂ (YSZ)/Sm₂O₃-doped CeO₂ (SDC) electrolyte films were successfully fabricated on porous NiO–YSZ composite substrates by electrophoretic deposition (EPD) based on electrophoretic filtration followed by co-firing with the substrates. In EPD, positively charged YSZ and SDC powders were deposited directly on the substrates, layer by layer from ethanol-based suspensions. Delamination between YSZ and SDC films was avoided by reducing the SDC films’ thickness to ca. 1 μm. A single cell was constructed on the bilayered electrolyte films composed of ca. 4 μm-thick YSZ and ca. 1 μm-thick SDC films. As a cathode in the cell, La_0.6Sr_0.4Co_0.2Fe_0.8O_3−x (LSCF) was used. Maximum output power densities greater than 0.6 W cm⁻² were obtained at 700 °C for the bilayered YSZ/SDC electrolyte cells thus constructed.     

Preparation and characterization of spray-deposited Cu2ZnSnS4 thin films

Thin films of Cu₂ZnSnS₄ (CZTS), a potential candidate for absorber layer in thin film heterojunction solar cell, have been successfully deposited by spray pyrolysis technique on soda-lime glass substrates. The effect of substrate temperature on the growth of CZTS films is investigated. X-ray diffraction studies reveal that polycrystalline CZTS films with better crystallinity could be obtained for substrate temperatures in the range 643-683 K. The lattice parameters are found to be a=0.542 and c=1.085 nm. The optical band gap of films deposited at various substrate temperatures is found to lie between 1.40 and 1.45 eV. The average optical absorption coefficient is found to be >10⁴ cm⁻¹.     

Fabrication, electrochemical characterization and thermal cycling of anode supported microtubular solid oxide fuel cells

This work describes the manufacture and electrochemical characterization of anode supported microtubular SOFC's (solid oxide fuel cells). The cells consist of a Ni-YSZ anode tube of 400 μm wall-thickness and 2.4 mm inner diameter, a YSZ electrolyte of 15-20 μm thickness and a LSM-YSZ cathode. The microtubular anode supporting tubes were prepared by cold isostatic pressing. The deposition of thin layers of electrolyte and cathode are made by spray coating and dip coating respectively. The cells were electrochemically characterized with polarization curves and complex impedance measurements using 5% H₂/95% Ar and 100% of H₂, humidified at 3% as reactant gas in the anodic compartment and air in the cathodic one at temperatures between 750 and 900 °C. The complex impedance measurements show an overall resistance from 1 to 0.42 Ω cm² at temperatures between 750 and 900 °C with polarization of 200 mA cm⁻². The I-V measurements show maximum power densities of 0.3-0.7 W cm⁻² in the same temperature interval, using pure H₂ humidified at 3%. Deterioration in the cathode performance for thin cathodes and high sintering temperatures was observed. They were associated to manganese losses. The cell performance did not present considerable degradation at least after 20 fast shut-down and heating thermal cycles.     

Reactive Spray Deposition Technology - An one-step deposition technique for Solid Oxide Fuel Cell barrier layers

In order to reduce the cost of the manufacturing of Solid Oxide Fuel Cells (SOFC), and to enable metal supported cell fabrication, a new fabrication method called Reactive Spray Deposition Technology (RSDT) for direct deposition of the material onto ceramic or metal support for low temperature SOFC is currently being developed. The present work describes the effect on the performance of a SOFC when a Gd_0.2Ce_0.8O_1.9 (GDC) layer has been introduced as diffusion barrier layer between the yttria stabilized zirconia (YSZ) electrolyte and the La_0.6Sr_0.4CoO_3−δ (LSC) cathode. The dense, thin and fully crystalline GDC films were directly applied by RSDT, without any post-deposition heating or sintering step. The quality of the film and performance of the cell prepared by RSDT was compared to a GDC blocking layer deposited by screen printing (SP) and then sintered. The observed ohmic resistance of the ASC with a GDC layer deposited by RSDT is 0.24 Ω cm², which is close to the expected theoretical value of 0.17 Ω cm² for a 5-μm thick 8 mol% yttria YSZ (8YSZ) electrolyte at 873 K.     

Structural and electrical properties of magnetron sputtered Ti(ON) thin films: The case of TiN doped in situ with oxygen

Incorporation of oxygen into TiN lattice results in formation of titanium oxynitrides, TiO_xN_y that have become particularly interesting for photocatalytic applications. Elaboration as well as characterization of TiN and in situ oxygen-doped thin films is the subject of this paper. Thin films, 250-320 nm in thickness, have been deposited by dc-pulsed magnetron reactive sputtering from Ti target under controllable gas flows of Ar, N₂ and O₂. Optical monitoring of Ti plasma emission line at λ = 500 nm has been implemented in order to stabilize the sputtering rate. Scanning electron microscopy (SEM), X-ray diffraction in grazing incidence (GIXRD), micro-Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), optical spectrophotometry and four-point probe electrical resistivity measurements have been performed in order to follow evolution of film physical parameters as a function of the oxygen flow rate ηO₂ at which the films were deposited. The relationship between ηO₂ expressed in standard cubic centimetres per minute, sccm and the nitrogen/oxygen content in thin films has been established by means of the analysis of the XPS spectra. GIXRD studies indicate that incorporation of oxygen results in a progressive loss of preferential orientation in 〈1 1 1〉 direction, a change in the grain size from 16 nm for TiN to about 3 nm for films deposited at ηO₂=1.32 sccm and a decrease in the lattice constant. A systematic shift of all X-ray diffraction (XRD) lines towards higher diffraction angles is consistent with substitution of oxygen for nitrogen. Micro-Raman investigations indicate amorphisation of thin films upon oxidation. Binding energies determined from fitting of the XPS results concerning the N1s and Ti2p lines give evidence of the presence of TiO_xN_y compound. Red-shift of the plasma reflectance edge upon TiN oxidation is correlated with a decreased carrier concentration. Metal-semiconductor transition can be expected on the basis of the electrical conductivity decrease and development of the fundamental absorption across the forbidden band of TiO₂ upon increase in the oxygen flow rate. Additional absorption feature in the visible range, being a consequence of coexistence of free-electron and interband absorption within almost the same spectral range (λ = 400-600 nm) seems to be very promising for photocatalytic applications of titanium oxynitride thin films.