Preparation and characterization of single crystalline In2O3 films deposited on MgO (110) substrates by MOCVD

Epitaxial indium oxide (In₂O₃) films have been prepared on MgO (110) substrates by metal-organic chemical vapor deposition (MOCVD). The deposition temperature varies from 500 °C to 700 °C. The films deposited at each temperature display a cube-on-cube orientation relation with respect to the substrate. The In₂O₃ film deposited at 600 °C exhibits the best crystalline quality. A clear epitaxial relationship of In₂O₃ (110)|MgO (110) with In₂O₃ [001]|MgO [001] has been observed from the interface area between the film and the substrate. The average transmittance of the prepared films in the visible range is over 95%. The band gap of the obtained In₂O₃ films is about 3.55–3.70 eV.     

Synthesis, microstructure, and photocatalysis of In2O3 hollow particles

Indium oxide (In₂O₃) microspheres with hollow interiors have been prepared by a facile implantation route which enables indium ions released from indium-chloride precursors to implant into nonporous polymeric templates in C₂Cl₄ solvent. The templates are then removed upon calcination at 500 °C in air atmosphere, forming hollow In₂O₃ particles. Specific surface area (0.5-260 m² g⁻¹) and differential pore volume (7 × 10⁻⁹ to 3.8 × 10⁻⁴ m³ g⁻¹ Å⁻¹) of the hollow particles can be tailored by adjusting the precursor concentration. For the hollow In₂O₃ particles with high surface area (260 m² g⁻¹), an enhanced photocatalytic efficiency (up to ∼one-fold increase) against methylene blue (MB) dye is obtained under UV exposure for the aqueous In₂O₃ colloids with a dilute solids concentration of 0.02 wt.%.     

Electrochromic property of nano-composite Prussian Blue based thin film

In this paper, we present fabrication of a nano-composite Prussian Blue (NPB) film to synchronously improve the contrast and switching time of regular Prussian Blue (PB) film by applying the concept of nano-technology. The NPB consists of indium tin oxide (ITO) nano-particles (3.0 ± 1.0 Ω, 40 ± 5 nm) as a medium layer for PB to gain larger operative reaction surface area in Li⁺ based electrolyte (1 M LiClO₄/PC) system. The procedures for preparation of NPB are: first, a well-dispersed ITO nano-particle solution is sprayed onto ITO glass (30 Ω/sq) at 200 °C; the PB film is then electroplated onto the pre-sprayed ITO nano-particles. Since ITO nano-particles can be well covered with PB, the NPB film forms a nano-porous electrochromic layer. The switching speed and contrast of NPB exhibit much better performances than traditional PB thin films. The structure, morphology, and electrochromic properties were characterized by scanning electron microscopy (SEM), cyclic voltammograms (CV), and UV-vis spectroscopy.     

Enhanced solid-state electrogenerated chemiluminescence of Au/CdS nanocomposite and its sensing to H2O2

Au nanoparticles (AuNPs) are good quenchers once they closely contact with luminophore. Here we reported a simple approach to obtain enhanced electrogenerated chemiluminescence (ECL) behavior based on Au/CdS nanocomposite films by adjusting the amount of AuNPs in the nanocomposite. The maximum enhancement factor of about 4 was obtained at an indium tin oxide (ITO) electrode in the presence of co-reactant H₂O₂. The mechanism of this enhancement was discussed in detail. The strong ECL emission from Au/CdS nanocomposites film was exploited to determine H₂O₂. The resulting ECL biosensors showed a linear response to the concentration of H₂O₂ ranging from 1.0 × 10⁻⁸ to 6.6 × 10⁻⁴ mol L⁻¹ with a detection limit of 5 nmol L⁻¹ (S/N = 3) and good stability and reproducibility.     

Effect of potassium hydrogen phthalate (C8H5KO4) on the one-step electrodeposition of single-phase CuInS2 thin films from acidic solution

The effect of potassium hydrogen phthalate (C₈H₅KO₄) as a special additive on the one-step electrodeposition of single-phase CuInS₂ thin films from acidic solution (pH 2.5) was investigated in detail. The XRD, SEM and UV-vis-NIR characterization confirms that the addition of an adequate concentration of C₈H₅KO₄ (23 mM) to the electrolytic bath containing 12.5 mM Cu²⁺, 10 mM In³⁺, 40 mM S₂O₃²⁻ and 100 mM LiCl can contribute greatly to the controllable growth of pure chalcopyrite CuInS₂ films with uniform surfaces and an ideal band gap of approximately 1.54 eV. Complexation studies of C₈H₅KO₄ with Cu²⁺ and In³⁺ in electrolytic solutions indicated that C₈H₅KO₄ can complex Cu²⁺ more strongly than In³⁺ and move the electrode potentials of Cu²⁺ and In³⁺ near each other as determined by polarization analysis. Furthermore, the potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) analysis performed in a series of solution systems revealed a three-step reaction mechanism for CuInS₂ deposition and considerable adsorption of C₈H₅O₄⁻ and Cu(C₈H₅O₄)⁺ to the cathode surface. This deposition shows that the synergetic effects of complexation and adsorption originated from the additive on the Cu²⁺ electro-reduction, thus promoting the co-deposition of copper, indium and sulfur in the form of single-phase CuInS₂.     

Polarization properties of La0.6Sr0.4Co0.2Fe0.8O3-based double layer-type oxygen electrodes for reversible SOFCs

We have developed double layer-type (catalyst layer/current collecting layer) oxygen electrodes (DLE) for reversible SOFCs. As the catalyst layer (cathode for SOFC and anode for steam electrolysis) interfaced with a samaria-doped ceria [(CeO₂)_0.8(SmO_1.5)_0.2, SDC] interlayer/YSZ solid electrolyte, mixed conducting La_0.6Sr_0.4Co_0.2Fe_0.8O₃ (LSCF) and SDC particles were employed. The current collecting porous LSCF layer was formed on the catalyst layer. By controlling the SDC content, as well as the thickness and porosity of the catalyst layer, the gas diffusion rate and the conduction networks for electrons and oxide ions were optimized, resulting in a marked reduction of the overpotential. The LSCF + SDC/LSCF DLE exhibited higher performance than single-layer electrodes of LSCF + SDC or LSCF; the IR-free anode potential vs. an air reference electrode was 0.12 V (corresponding to an overpotential of 0.08 V) at 0.5 A cm⁻² and 900 °C under an atmosphere of O₂ (1 atm).     

A bi-layer cathode based on lanthanum based cobalt- and iron-containing perovskite and gadolinium doped ceria for thin yttria stabilized zirconia electrolyte solid oxide fuel cells

Composite cathodes based on La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ (LSCF) are investigated for lower operating temperature (<750 °C) applications of a solid oxide fuel cell (SOFC). To enhance a charge transfer, a bi-layer SOFC cathode is proposed, which has a LSCF–Ce_0.9Gd_0.1O_1.95 (GDC) composite layer and a pure LSCF layer. The bi-layer cathode SOFC shows a current density of 0.65 A cm⁻² at 0.8 V and 660 °C, which is higher than a LSCF–GDC composite single-layer cathode SOFC cell of 0.35 A cm⁻². The charge transfer polarizations in the bi-layer cathode SOFC are 0.14 Ω cm² and 0.35 Ω cm² at 760 °C and 660 °C, respectively, which are lower than those in the single-layer cathode cell of 0.23 Ω cm² and 0.66 Ω cm². The impedances characterized with a fitting model show that the lowered charge transfer polarization in the bi-layer cathode is a dominant factor in reducing the total polarization of SOFC.     

Phase composition and properties of solid solutions of GdFeO3–GdInO3 bulks

Solid solutions of the GdFeO₃–GdInO₃ system were prepared at 1550 °C by ceramic powder processing. The formulated composition was Gd(Fe_1−xIn_x)O₃ (GFI) with the indium contents at x = 0, 0.25, 0.5, 0.75, and 1.0. A stable phase of Gd(Fe_1/3In_2/3)O₃ in our system was identified by X-ray diffraction and phase composition analysis. Multi-phase morphologies were observed for GFI bulks with x = 0.5 and 0.75. Dielectric and electrical properties of the GFI bulks were investigated. The addition of 25% In³⁺ in GdFeO₃ had an obvious enhancement in polarization and led to an elevated resonance frequency. Dielectric properties of GFI bulks except GdInO₃ were strongly dependent upon the test frequency, which corresponded to the response of polarization mechanism. GdInO₃ displayed as a stable dielectric, which was frequency- and temperature-insensitive. GdInO₃ was thermally activated and became leaky until above 600 °C.     

Li diffusion in LiNi0.5Mn0.5O2 thin film electrodes prepared by pulsed laser deposition

Kinetic and transport parameters of Li ion during its extraction/insertion into thin film LiNi_0.5Mn_0.5O₂ free of binder and conductive additive were provided in this work. LiNi_0.5Mn_0.5O₂ thin film electrodes were grown on Au substrates by pulsed laser deposition (PLD) and post-annealed. The annealed films exhibit a pure layered phase with a high degree of crystallinity. Surface morphology and thin film thickness were investigated by field emission scanning electron microscopy (FESEM). The charge/discharge behavior and rate capability of the thin film electrodes were investigated on Li/LiNi_0.5Mn_0.5O₂ cells at different current densities. The kinetics of Li diffusion in these thin film electrodes were investigated by cyclic voltammetry (CV) and galvanostatic intermittent titration technique (GITT). CV was measured between 2.5 and 4.5 V at different scan rates from 0.1 to 2 mV/s. The apparent chemical diffusion coefficients of Li in the thin film electrode were calculated to be 3.13 × 10⁻¹³ cm²/s for Li intercalation and 7.44 × 10⁻¹⁴ cm²/s for Li deintercalation. The chemical diffusion coefficients of Li in the thin film electrode were determined to be in the range of 10⁻¹²-10⁻¹⁶ cm²/s at different cell potentials by GITT. It is found that the Li diffusivity is highly dependent on the cell potential.     

Enhanced electrochromic performance of macroporous WO3 films formed by anodic oxidation of DC-sputtered tungsten layers

Self-organized macroporous tungsten trioxide (WO₃) films are obtained by anodic oxidation of DC-sputtered tungsten (W) layers on 10 mm × 25 mm indium tin oxide (ITO)-coated glass. Under optimized experimental conditions, uniformly macroporous WO₃ films with a thickness of ca. 350 nm are formed. The film shows a connected network with average pore size of 100 nm and a pore wall thickness of approximately 30 nm. The anodized film becomes transparent after annealing without significant change in macroporous structure. In 0.1 M H₂SO₄, the macroporous WO₃ films show enhanced electrochromic properties with a coloration efficiency of 58 cm² C⁻¹. Large modulation of transmittance (∼50% at 632.8 nm) and a switching speed of about 8 s are also achieved with this macroporous film.     

Nanocrystalline In2O3-SnO2 thick films for low-temperature hydrogen sulfide detection

Nanocrystalline In₂O₃-SnO₂ thick films were fabricated using the screen-printing technique and their responses toward low concentrations of H₂S in air (2-150 ppm) were tested at 28-150 °C. The amount of In₂O₃-loading was varied from 0 to 9 wt.% of SnO₂ and superb sensing performance was observed for the sensor loaded with 7 wt.% In₂O₃, which might be attributed to the decreased crystallite size as well as porous microstructure caused by the addition of In₂O₃ to SnO₂ without structural modification. The interfacial barriers between In₂O₃ and SnO₂ might be another major factor. Typically, the response of 7 wt.% In₂O₃-loaded SnO₂ sensor toward 100 ppm of H₂S was 1481 at room temperature and 1921 at optimal operating temperature (40 °C) respectively, and showed fast and recoverable response with good reproducibility when operated at 70 °C, which are highly attractive for the practical application in low-temperature H₂S detection.     

Relationship between glass network structure and conductivity of Li2O-B2O3-P2O5 solid electrolyte

Solid state glass electrolyte, xLi₂O-(1 − x)(yB₂O₃-(1 − y)P₂O₅) glasses were prepared with wide range of composition, i.e. x = 0.35 - 0.5 and y = 0.17 - 0.67. This material system is one of the parent compositions for chemically and electrochemically stable solid-state electrolyte applicable to thin film battery. Lithium ion conductivity of Li₂O-B₂O₃-P₂O₅ glasses was studied in the correlation to the structural variation of glass network by using FTIR and Raman spectroscopy. The measured ionic conductivity of the electrolyte at room temperature increased with x and y. The maximum conductivity of this glass system was 1.6 × 10⁻⁷ Ω⁻¹ cm⁻¹ for 0.45Li₂O-0.275B₂O₃-0.275P₂O₅ at room temperature. It was shown that the addition of P₂O₅ reduces the tendency of devitrification and increases the maximum amount of Li₂O added into glass former without devitrification. As Li₂O and B₂O₃ contents increased, the conductivity of glass electrolyte increased due to the increase of three-coordinated [BO₃] with a non-bridging oxygen (NBO).     

Comparative study on the microstructure and properties of 10 wt%- and 35 wt%- tin doped indium oxide materials

Due to the resource shortage of indium, the application of 10 wt%- tin doped indium oxide (10 wt%- ITO) with 74.4 wt% of indium is restricted in the field of flat panel display. A new ternary compound TCO material with 53.8 wt% of indium (35 wt%- ITO) was prepared by In₂O₃-35 wt% SnO₂ powders, whose microstructure and properties were studied in comparison to 10 wt%- ITO. The research findings show that: (1) The phase composition of 35 wt%- ITO target is mainly In₄Sn₃O₁₂ and In₂SnO₅, without In₂O₃: Sn phase for 10 wt%- ITO; (2) When films possess the strong crystalline structure, the photoelectric properties of 35 wt%- ITO films are superior to 10 wt%- ITO. In addition, the crystalline structure of 35 wt%- ITO films could be changed from In₄Sn₃O₁₂ + amorphous to In₄Sn₃O₁₂ + In₂O₃ by annealing, but for 10 wt%- ITO, only the crystallinity is changed.     

Electrodeposition of indium onto Mo/Cu for the deposition of Cu(In,Ga)Se2 thin films

A study of the electrodeposition and the oxidation process of indium on Mo/Cu substrates from a bath containing 0.008 M InCl₃, 0.7 M LiCl at pH 3 is described in this work. The voltamperometric study showed a reduction process which corresponds to the conversion of In³⁺ to In⁰ and an oxidation process which takes place in different steps. Utilizing the chronoamperometric technique the total efficiency of process, the number of monolayers, the film thickness and the diffusion coefficient were evaluated. The analysis of current transients, using theoretical growth model, showed that the electrodeposition of indium adjusts to a three-dimensional growth under instantaneous nucleation limited by diffusion. The kinetic growth parameters were evaluated through a non-linear fit. The films were characterized by X-ray diffraction and scanning electron microscopy techniques. These studies showed that the films were of crystalline in nature with compact and uniform surface, even for the film with a deposition time of 1 min.     

In-situ construction of plasma-pretreated CNT networks endow the LPDS dual-layer coating with advanced thermal management and anti-static properties

Carbon nanotubes (CNTs) for temperature regulation have been proven to be promising for passive radiative heat dissipation. However, it remains a considerable challenge to assemble a CNTs layer in situ while simultaneously achieving horizontal electrical conductivity, vertical electrical insulation, and radiative heat dissipation. Herein, plasma pretreatment was employed to functionalize CNTs in an aqueous solution, thus improving their dispersion capability. Subsequently, a liquid-plasma-assisted particle deposition and sintering (LPDS) technology was proposed to prepare a dual-layer coating with an Al₂O₃-P₂O₅-SiO₂-In₂O₃ glass system embedded with crystalline indium tin oxide (ITO) as the porous bottom layer and ITO-CNTs as the top layer on the aluminum alloy surface. The results show that plasma pretreatment significantly increases the deposition amount of ITO nanoparticles and functionalized CNTs on the coating surface, resulting in the transition from a single-layer composite coating to a dual-layer coating. The surface micro-/nano hierarchical structure favors strong absorptance/emittance, exhibiting a high infrared emittance of 0.94 (3-20 μm) and high solar absorptance of 0.92 (0.2-2.5 μm). Meanwhile, the surface balance temperature of the dual-layer coating is about 392 K, which is 146 K lower than that of aluminum alloy. Furthermore, the top conductive ITO-CNTs layer contributes to the low surface resistivity of 3.46×10² Ω, while the glass phase of the bottom layer ensures vertical electrical insulation with a volume resistance of 4.20×10⁷ Ω. The process provides a new path for preparing thermal control coatings with anti-static function.     

Nano-sized Sm0.5Sr0.5CoO3−δ as the cathode for solid oxide fuel cells with proton-conducting electrolytes of BaCe0.8Sm0.2O2.9

Nano-sized Sm_0.5Sr_0.5CoO_3−δ (SSC) was fabricated onto the inner face of porous BaCe_0.8Sm_0.2O_2.9 (BCS) backbone by ion impregnation technique to form a composite cathode for solid oxide fuel cells (SOFCs) with BCS, a proton conductor, as electrolyte. The electro-performance of the composite cathodes was investigated as function of fabricating conditions, and the lowest polarization resistance, about 0.21 Ω cm² at 600 °C, was achieved with BCS backbone sintered at 1100 °C, SSC layer fired at 800 °C, and SSC loading of 55 wt.%. Impedance spectra of the composite cathodes consisted of two depressed arcs with peak frequency of 1 kHz and 30 Hz, respectively, which might correspond to the migration of proton and the dissociative adsorption and diffusion of oxygen, respectively. There was an additional arc peaking at 1 Hz in the Nyquist plots of a single cell, which should correspond to the anode reactions. With electrolyte about 70 μm in thickness, the simulated anode, cathode and bulk resistances of cells were 0.021, 0.055 and 0.68 Ω cm² at 700 °C, relatively, and the maximum power density was 307 mW cm⁻² at 700 °C.     

The distribution of lithium intercalated in V2O5 thin films studied by XPS and ToF-SIMS

The distribution of lithium in V₂O₅/V lower oxide duplex thin films prepared by thermal oxidation of V metal was analysed by XPS and ToF-SIMS after intercalation at 2.8 V versus Li/Li⁺ and de-intercalation at 3.8 V following cycling between 3.8 and 2.8 V in 1 M LiClO₄-PC. XPS analysis of the intercalated thin film evidenced a partial reduction (43 at.% V⁴⁺) of the V₂O₅ surface, the modification of its electronic structure and the presence of Li, consistent with the formation of the δ-Li_xV₂O₅ (0.9 ≤ x ≤ 1) phase. The Li in-depth distribution measured by ToF-SIMS shows a maximum in the outer layer of V₂O₅, but Li is also found at the oxide film/metal substrate interface indicating its diffusion across the inner layer of V lower oxides. The analyses performed after de-intercalation on the samples cycled 12, 120 and 300 times reveal the effect of aging on the trapping of lithium. A significant reduction (17-22 at.% V⁴⁺) of the V₂O₅ surface was measured after 300 cycles. The Li in-depth distribution shows a maximum at the interface between the outer layer of V₂O₅ and the inner layer of lower oxides. Aging favours the accumulation of lithium at this interface with a resulting enlarged distribution enriching the sub-surface of the outer layer of V₂O₅ and the inner layer of lower oxides after 300 cycles. Lithium is also found, but in smaller quantities, at the oxide film/metal substrate interface. Measurements performed in the non-electrochemically treated surface areas of the de-intercalated samples revealed the same type of modifications, evidencing the diffusion of lithium along the interfaces where it is trapped.     

Frequency, temperature and In dependent electrical conduction in NiFe2O4 powder

A series of polycrystalline spinel ferrites with the composition NiIn_xFe_2-xO₄ (0 ≤ x ≤ 0.3) were prepared by the solid state reaction to study the effect of In³⁺ ions substitution on their dc electrical resistivity and dielectric properties. The dc resistivity has been investigated as a function of temperature and composition. The indium ion increases the dc resistivity and activation energy of the system. A study of the dielectric properties of these mixed ferrites, as a function of composition, frequency and temperature, has been undertaken. The dielectric constant (ε′), dielectric loss (ε″) and dielectric loss tangent (tanδ) all decreases with frequency as well as with the composition. The dielectric constant (ε′) and dielectric loss tangent (tanδ) were increases with increasing temperature. AC conductivity increases with increase in applied frequency. The dielectric behavior of the present samples is attributed to the Maxwell-Wagner type interfacial polarization. The conduction mechanism in these ferrites is due to electron hopping between Fe²⁺ and Fe³⁺ ions on adjacent octahedral sites.     

Direct electron-transfer and electrochemical catalysis of hemoglobin immobilized on mesoporous Al2O3

The direct electrochemistry of hemoglobin (Hb) has been achieved by immobilizing Hb on mesoporous Al₂O₃ (meso-Al₂O₃) film modified glassy carbon (GC) electrode. Meso-Al₂O₃ shows significant promotion to the direct electron-transfer of Hb, thus it exhibits a pair of well defined and quasi-reversible peaks with a formal potential of −0.345 V (vs. SCE). The electron-transfer rate constant (k_s) is estimated to be 3.17 s⁻¹. The immobilized Hb retains its biological activity well and shows high catalytic activity to the reduction of hydrogen peroxide (H₂O₂) and nitrite (NO₂⁻). Under the optimized experimental conditions, the catalytic currents are linear to the concentrations of H₂O₂ and NO₂⁻ in the ranges of 0.195-20.5 μM and 0.2-10 mM, respectively. The corresponding detection limits are 1.95 × 10⁻⁸ M and 3 × 10⁻⁵ M (S/N = 3). The resulting protein electrode has high thermal stability and good reproducibility due to the protection effect of meso-Al₂O₃. Ultraviolet visible (UV-vis) absorption spectra and reflection-absorption infrared (RAIR) spectra display that Hb keeps almost natural structure in the meso-Al₂O₃ film. The N₂ adsorption-desorption experiments show that the pore size of meso-Al₂O₃ is about 14.4 nm, suiting for the encapsulation of Hb (average size: 5.5 nm) well. Therefore, meso-Al₂O₃ is an alternative matrix for protein immobilization and biosensor preparation.     

V-doped In2O3 nanofibers for H2S detection at low temperature

Pristine and vanadium-doped In₂O₃ nanofibers were fabricated by electrospinning and their sensing properties to H₂S gas were studied. X-ray diffractometry (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to investigate the inner structure and the surface morphology. The H₂S-sensing performances were characterized at different temperatures ranging from 50 to 170 °C. The sensor based on 6 mol% V-doped In₂O₃ nanofibers exhibit the highest response, i.e. 13.9–50 ppm H₂S at the relatively low temperature of 90 °C. In addition, the fast response (15 s) and recovery (18 s) time, and good selectivity were observed.