Modulation of electrical transport in calcium cobaltite ceramics and thick films through microstructure control and doping

Ca₃Co₄O₉ is a promising p-type thermoelectric oxide material having intrinsically low thermal conductivity. With low cost and opportunities for automatic large scale production, thick film technologies offer considerable potential for a new generation of micro-sized thermoelectric coolers or generators. Here, based on the chemical composition optimized by traditional solid state reaction for bulk samples, we present a viable approach to modulating the electrical transport properties of screen-printed calcium cobaltite thick films through control of the microstructural evolution by optimized heat-treatment. XRD and TEM analysis confirmed the formation of high-quality calcium cobaltite grains. By creating 2.0 at% cobalt deficiency in Ca_2.7Bi_0.3Co₄O_9+δ, the pressureless sintered ceramics reached the highest power factor of 98.0 μWm^?1 K^-2 at 823 K, through enhancement of electrical conductivity by reduction of poorly conducting secondary phases. Subsequently, textured thick films of Ca_2.7Bi_0.3Co_3.92O_9+δ were efficiently tailored by controlling the sintering temperature and holding time. Optimized Ca_2.7Bi_0.3Co_3.92O_9+δ thick films sintered at 1203 K for 8 h exhibited the maximum power factor of 55.5 μWm^?1 K^-2 at 673 K through microstructure control.     

Investigation of La0.6Sr0.4Co1-xNixO3-δ (x=0, 0.2, 0.4, 0.6, 0.8) catalysts on solid oxide fuel cells anode for biogas dry reforming

The introduction of catalyst on anode of solid oxide fuel cell (SOFC) has been an effective way to alleviate the carbon deposition when utilizing biogas as the fuel. A series of La_0.6Sr_0.4Co_1-xNi_xO_3-δ (x = 0, 0.2, 0.4, 0.6, 0.8) oxides are synthesized by sol-gel method and used as catalysts precursors for biogas dry reforming. The phase structure of La_0.6Sr_0.4Co_1-xNi_xO_3-δ oxides before and after reduction are characterized by X-ray diffraction (XRD). The texture properties, carbon deposition, CH₄ and CO₂ conversion rate of La_0.6Sr_0.4Co_1-xNi_xO_3-δ catalysts are evaluated and compared. The peak power density of 739 mW cm^?2 is obtained by a commercial SOFC with La_0.6Sr_0.4Co_0.4Ni_0.6O_3-δ catalyst at 850 °C when using a mixture of CH₄: CO₂ = 2:1 as fuel. This shows a great improvement from the cell without catalyst for internal dry reforming, which is attributed to the formation of NiCo alloy active species after reduction in H₂ atmosphere. The results indicate the benefits of inhibiting the carbon deposition on Ni-based anode through introducing the La_0.6Sr_0.4Co_0.4Ni_0.6O_3-δ catalyst precursor. Additionally, the dry reforming technology will also help to convert part of the exhaust heat into chemical energy and improve the efficiency of SOFC system with biogas fuel.     

Diluted chemical bath deposition of CdZnS as prospective buffer layer in CIGS solar cell

In this study, dilute chemical bath deposition technique has been used to deposit CdZnS thin films on soda-lime glass substrates. The structural, morphological, optoelectronic properties of as-grown films have been investigated as a function of different Zn²⁺ precursor concentrations. The X-ray diffractogram of CdS thin-film reveals a peak corresponding to (002) plane with wurtzite structure, and the peak shift has been observed with the increase of the Zn²⁺ concentration upon formation of CdZnS thin film. From morphological studies, it has been revealed that the diluted chemical bath deposition technique provides homogeneous distribution of film on the substrate even at a lower concentration of Zn²⁺. Optical characterization has shown that the transparency of the film is influenced by Zn²⁺ concentration and when the Zn²⁺ concentration is varied from 0 M to 0.0256 M, bandgap values of resulting films range from 2.42 eV to 3.90 eV while. Furthermore, electrical properties have shown that with increasing zinc concentration the resistivity of the film increases. Finally, numerical simulation validates and suggests that CdZnS buffer layer with composition of 0.0032 M Zn²⁺ concentration would be a promising candidate in CIGS solar cell.     

Induced slim ferroelectric hysteresis loops and enhanced energy-storage properties of Mn-doped (Pb0·93La0.07)(Zr0·82Ti0.18)O3 anti-ferroelectric thick films by aerosol deposition

In this study, the high ferroelectric hysteresis loss of (Pb_0·93La_0.07)(Zr_0·82Ti_0.18)O₃ (PLZT 7/82/18) antiferroelectric (AFE) ceramics was reduced by employing a combinatorial approach of Mn acceptor doping followed by thick film fabrication via an aerosol deposition (AD) process. The grains of the as-deposited PLZT 7/82/18 AFE AD thick films were grown by thermal annealing at 550 °C to enhance their electrical properties. Investigation of the electrical properties revealed that Mn-doping results in improved dielectric and ferroelectric properties, increased dielectric breakdown strength (DBS), and energy-storage properties. The Mn-doped PLZT AFE AD films possess a frequency-independent high dielectric constant (ε_r ≈ 660) with low dielectric loss (tan δ ≈ 0.0146), making them suitable candidates for storage capacitor applications. The bipolar and unipolar polarization vs. electric field (P-E) hysteresis loops of PLZT 7/82/18 AFE AD thick films were found to be slimmer than those of their bulk form (double hysteresis) with significantly reduced ferroelectric hysteresis loss, which is attributed to the AD-induced mixed grain structure. The Mn-doped PLZT 7/82/18 AFE AD thick films exhibited a low remnant polarization (P_r ≈ 9.22 μC/cm²) at a high applied electric field (~2750 kV/cm). The energy-storage density and energy efficiency of the Mn-doped PLZT AFE AD thick films were calculated from unipolar P-E hysteresis loops and found to be ~38.33 J/cm³ and ~74%, respectively.     

Nano-Al doped-MoO3 high-energy composite films with excellent hydrophobicity and thermal stability

Developing the thermal stability of metal-based ceramic composites or their films has always been challenging and bottlenecks for the utilization of energy. In this paper, the novel mesh-like functional Al doped-MoO₃ nanocomposite film with even distribution and high purity was firstly fabricated by the high-efficiency electrophoretic deposition and surface modification. The optimal suspension turned out to be the mixture of isopropanol and the additives of polyethyleneimine and benzoic acid. The microtopography, crystalline structure, environmental resistance and thermal stability were analyzed by field emission scanning electron microscope (FESEM), energy dispersive X-ray (EDX), X-ray diffractometer (XRD), exposure and droplet-impacting test, DSC analysis and ignition test, respectively. The water contact angle and sliding angle of product can reach ~170° and <1°, indicating the excellent anti-wetting property. In addition, the high heat-release (~3180 J/g) of product all kept almost unchangeable after six months exposure experiments, demonstrating the outstanding thermostability. The exquisite design idea here can perfectly match microelectromechanical system (MEMS), providing the valuable reference for fabricating other metal-based high-energy composites with long lifespan for real industrial applications.     

Large domain-wall currents in epitaxial Au/BiFeO3/SrRuO3 thin-film capacitors with modulated oxygen vacancy and wall densities

Large domain wall (DW) conductivity in an insulating ferroelectric plays an important role in the future nanosensors and nonvolatile memories. However, the wall current was usually too small to drive high-speed memory circuits and other agile nanodevices requiring high output-powers. Here, a large domain-wall current of 67.8 μA in a high on/off ratio of ~4460 was observed in an epitaxial Au/BiFeO₃/SrRuO₃ thin-film capacitor with the minimized oxygen vacancy concentration. The studies from read current-write voltage hysteresis loops and piezo-response force microscope images consistently showed remaining of partially unswitched domains after application of an opposite poling voltage that increased domain wall density and wall current greatly. A theoretical model was proposed to explain the large wall current. According to this model, the domain reversal occurs with the appearance of head-to-head and tail-to-tail 180° domain walls (DWs), resulting in the formation of highly conductive wall paths. As the applied voltage increased, the domain-wall number increased to enhance the on-state current, in agreement with the measurements of current-voltage curves. This work paves a way to modulate DW currents within epitaxial Au/BiFeO₃/SrRuO₃ thin-film capacitors through the optimization of both oxygen vacancy and domain wall densities to achieve large output powers of modern domain-wall nanodevices.     

Photophysical investigation of the formation of defect levels in P doped ZnO thin films

Zinc oxide (ZnO) offers a major disadvantage of asymmetry doping in terms of reliability, stability, and reproducibility of p-type doping, which is the main hindrance in realization of optoelectronic devices. The problem is even more complicated due to formation of various native defects in unintentionally doped n-type ZnO. The realization of p-type conductivity in doped ZnO requires an in-depth understanding of the formation of an effective shallow acceptor, as well as donor-acceptor compensation. Photophysical properties such as photoconductivity along with photoluminescence (PL) studies have unprecedentedly and effectively been utilized in this work to monitor the evolution of various in-gap defects. Phosphorus (P) doped ZnO thin films have been grown by RF magnetron sputtering under various Ar to O₂ gas ratios to investigate the effect of O₂ on the donor-acceptor compensation by comprehensive photoconductivity measurements supported by the PL studies. Initial elemental analyses indicate presence of abundant zinc vacancies (V_Zn) in O-rich ambience. The results predict that P sits in the zinc (Zn) site rather than the oxygen (O) site causing the formation of P_Zn–2V_Zn acceptor-like defects, which compensates the donor defects in P doped ZnO films. Photocurrent spectra uniquely reveal presence of more oxygen vacancies (V_O) defects states in lower O₂ flow, which gets compensated with an increase in the O₂ flow. Successive photocurrent transients indicate probable presence of more V_O in the films grown with lower O₂ flow and more V_Zn in higher O₂ flow. Overall the photosensitivity measurements clearly present that O-rich ambience expedites the formation of acceptor defects which are compensated, thereby lowering the dark current and enhancing the ultraviolet photosensitivity.     

Wear and corrosion properties of wollastonite and boron nitride doped,hydroxyapatite-based HAp-Wo-BN composite coatings prepared by pulsed laser deposition

In this study, hydroxyapatite-based hydroxyapatite-wollastonite-boron nitride (HAp-Wo-BN) composite film was formed on the surface of Ti6Al4V by pulsed laser deposition (PLD). Based on a survey in scientific literature, it is presumed that this is the first time such a process is being undertaken. The wear and corrosion resistance of this film were analyzed comparatively in simulated body fluid (SBF) to simulate the human body environment. In the coating, HAp was used to form a bone-like layer, wollastonite was to enhance bone-tissue regeneration and BN was used for its bone-tissue healing and anti-bacterial properties. The results showed that the wear as well as the corrosion resistance of all samples after PLD treatment increased. Relatively the best wear resistance was achieved from boron nitride and wollastonite doped hydroxyapatite layers, where the best corrosion resistance was from the ones that consisted of only hydroxyapatite.     

Agronomic performance of high oleic,low linolenic soybean in Tennessee

Soybean oil hydrogenation alters the linolenic acid molecule to prevent the oil from becoming rancid, however, health reports have indicated trans-fat caused by hydrogenation, is not generally regarded as safe. Typical soybeans contain approximately 80 g kg⁻¹ to 120 g kg⁻¹ linolenic acid and 240 g kg⁻¹ of oleic acid. In an effort to accommodate the need for high-quality oil, the United Soybean Board introduced an industry standard for a high oleic acid greater than 750 g kg⁻¹ and linolenic acid less than 30 g kg⁻¹ oil. By combing mutations in the soybean plant at four loci, FAD2-1A and FAD2-1B, oleate desaturase genes and FAD3A and FAD3C, linoleate desaturase genes, and seed oil will not require hydrogenation to prevent oxidation and produce high-quality oil. In 2017 and 2018, a study comparing four near-isogenic lines across multiple Tennessee locations was performed to identify agronomic traits associated with mutations in FAD3A and FAD3C loci, while holding FAD2-1A and FAD2-1B constant in the mutant (high oleic) state. Soybean lines were assessed for yield and oil quality based on mutations at FAD2-1 and FAD3 loci. Variations of wild-type and mutant genotypes were compared at FAD3A and FAD3C loci. Analysis using a generalized linear mixed model in SAS 9.4, indicated no yield drag or other negative agronomic traits associated with the high oleic and low linolenic acid genotype. All four mutations of fad2-1A, fad2-1B, fad3A, and fad3C were determined as necessary to produce a soybean with the new industry standard (>750 g kg⁻¹ oleic and <30 g kg⁻¹ linolenic acid) in a maturity group-IV-Late cultivar for Tennessee growers.