The improvement of pyroelectric properties of PZT thick films on Si substrate by TiOx barrier layer

The effects of TiO_x diffusion barrier layer thickness on the microstructure and pyroelectric characteristics of PZT thick films were studied in this paper. The TiO_x layer was prepared by thermal oxidation of Ti thin film in air and the PZT thick films were fabricated by electrophoresis deposition method (EPD). To demonstrate the barrier effect of TiO_x layer, the electrode/substrate interface and Si content in PZT thick films were characterized by scanning electron microscope (SEM) and X-ray energy dispersive spectroscopy (EDS), respectively. The TiO_x barrier thickness shows significant influence on the bottom electrode and the pyroelectric performance of the PZT thick films. The average pyroelectric coefficient of PZT films deposited on 400 nm TiO_x layer was about 8.94 × 10⁻⁹ C/(cm² K), which was improved by 70% than those without diffusion barrier layer. The results showed in this study indicate that TiO_x barrier layer has great potential in fabrication of PZT pyroelectric device.     

Quick response PZT/P(VDF-TrFE) composite film pyroelectric infrared sensor with patterned polyimide thermal isolation layer

The fabrication method and the pyroelectric response of a single element infrared sensor based lead zirconate titanate (PZT) particles and polyvinylidene fluoride P(VDF-TrFE) copolymer composite thick film is reported in this paper. A special thermal insulation structure, including polyimide (PI) thermal insulation layer and thermal insulation tanks, was used in this device. The thermal insulation tanks were fabricated by laser micro-etching technique. Voltage responsivity (R_V), noise voltage (V_noise), noise equivalent power (NEP), and detectivity (D^*) of the PZT/P(VDF-TrFE) based infrared sensor are 1.2 × 10³ V/W, 1.25 × 10⁻⁶ V Hz^1/2, 1.1 × 10⁻⁹ W and 1.9 × 10⁸ cm Hz^1/2 W⁻¹ at 137.3 Hz modulation frequency, respectively. The thermal time constant of the infrared sensor τ_T was about 15 ms. The results demonstrate that the composite infrared sensor show a high detectivity at high chopper frequency, which is an essential advantage in infrared detectors and some other devices.     

Lead free KNN/P(VDF-TrFE) 0–3 pyroelectric composite films and its infrared sensor

(K_0.5Na_0.5)NbO₃ (KNN)/[P(VDF-TrFE)70:30] composite thick films with different KNN weight ratios have been fabricated and the effect of KNN mass content on the material structure and properties have been studied in this paper. Properties of the infrared sensor based KNN/[P(VDF-TrFE)70:30] composite thick film were also systematically studied. It was found that the sample containing 30 wt.% KNN show optimal properties for pyroelectric appliance and the highest pyroelectric coefficient was 63 μCm⁻² K⁻¹. Infrared sensors using 30 wt.% KNN-70 wt.%[P(VDF-TrFE)70:30] show highest detectivity (D¹ = 3.21 × 10⁸ cm Hz^1/2 W⁻¹) at 137.3 Hz, indicating it is an promising candidate in lead-free quick response infrared detectors.     

An infrared pyroelectric detector improved by cool isostatic pressing with cup-shaped PZT thick film on silicon substrate

In this paper, we presented a new pyroelectric detector with back to back silicon cups and micro-bridge structure. The PZT thick film shaped in the front cup was directly deposited with designed pattern by electrophoresis deposition (EPD). Pt/Ti Metal film, which was fabricated by standard photolithography and lift-off technology, was sputtered to connect the top electrode and the bonding pad. The cold isostatic press (CIP) treatment could be applied to improve the pyroelectric properties of PZT thick film. The infrared (IR) properties the CIP-optimized detector were measured. The voltage responsivity (R_V) was 4.5 × 10² V/W at 5.3 Hz, the specific detectivity (D^*) was greater than 6.34 × 10⁸ cm Hz^1/2 W⁻¹ (frequency > 110 Hz), and the thermal time constant was 51 ms, respectively.     

High room-temperature pyroelectric response of MgO-modified Pb0.99(Zr0.95Ti0.05)0.98Nb0.02O3 ceramics

The dielectric and pyroelectric responses of MgO-modified Pb_0.99(Zr_0.95Ti_0.05)_0.98Nb_0.02O₃ ceramics were investigated near F_R(LT)–F_R(HT) phase transition. It was found that MgO additive reduced the F_R(LT)–F_R(HT) phase transition temperature from 41 °C to room temperature (24 °C). Superior room-temperature pyroelectric properties were obtained in the composition of 0.10 wt% MgO addition without DC bias. The largest pyroelectric coefficient, 65 × 10⁻⁸ C cm⁻² K⁻¹, was detected. Accordingly, the detectivity figures of merit F_d had maximum values of 20 × 10⁻⁵ Pa^−1/2, and especially the voltage responsivity F_v = 0.91 m²C⁻¹ is the highest value reported so far among all pyroelectric materials. It shows promising potential for application in uncooled pyroelectric infrared detector.     

Characterization of LSGM films obtained by electrophoretic deposition (EPD)

The application of the electrophoretic deposition (EPD) technique to the preparation of high quality electrolyte films for intermediate temperature solid oxide fuel cells (IT-SOFCs) was investigated. Films of La_0.83Sr_0.17Ga_0.83Mg_0.17O_2.83 (LSGM) were deposited on Pt and La_0.8Sr_0.2MnO₃ (LSM) substrates from suspensions in acetone/ethanol (3:1 by volume) mixture solvent and sintered at 1300 °C. Pt supported LSGM films, 10–20 μm thick, exhibited good adhesion to the Pt substrate, well-distributed microporosity and some surface roughness. LSM supported films exhibited cracking after sintering at 1300 °C for 3 h. Up to 900 °C the bulk conductivity of the Pt supported LSGM film showed the same behaviour of LSGM pellet (E_a = 0.93 eV and 0.99 eV, respectively). The LSGM film exhibited lower bulk electrical conductivity than the latter (4.1 × 10^− 3 and 4.4 × 10^− 2 Ω^− 1 cm^− 1, respectively, at 700 °C). This difference should be ascribed to the slight Ga depletion in the LSGM film. An important issue remains the selection of adequate electrode for LSGM electrolyte films.     

Densification and microstructure of lead zirconate titanate ceramics fabricated from a triol sol–gel powder

Lead zirconate titanate (PZT) nano-powder was prepared by a triol sol–gel process. X-ray diffraction and transmission electron microscopy results showed that as-synthesized amorphous powder started to crystallize at the calcination temperature above 500 °C. The crystalline powder was formed into pellets and sintered at temperatures between 900 and 1300 °C. Co-existence of tetragonal and rhombohedral phase was observed in all ceramics. Microstructural investigation of PZT ceramics showed that uniform grain size distribution with average grain size of ∼0.8–2.5 μm were received with sintering temperature up to 1200 °C. Further increasing the temperature caused abnormal grain growth with the grain as large as 13.5 μm. An attempt to optimize densification with uniform grain size distribution was also performed by varying heating rate and holding time during sintering. It was found that dense (∼97%) sol–gel derived PZT ceramic with uniform microstructure was achieved at 1100 °C with a heating rate of 5 °C min⁻¹ and 6 h dwell time.     

Growth and characterization of indium oxide films

In₂O₃ films have been deposited using chemical spray pyrolysis technique at different substrate temperatures that varied in the range, 250–450 °C. The structural and morphological properties of the as-deposited films were studied using X-ray diffractometer and scanning electron microscope as well as atomic force microscope, respectively. The films formed at a temperature of 400 °C showed body-centered cubic structure with a strong (2 2 2) orientation. The structural parameters such as the crystallite size, lattice strain and texture coefficient of the films were also calculated. The films deposited at a temperature of 400 °C showed an optical transmittance of >85% in the visible region. The change of resistivity, mobility, carrier concentration and activation energies with the deposition temperature was studied. The highest figure of merit for the layers grown at 400 °C was 1.09 × 10⁻³ Ω⁻¹.     

Oxygen diffusion and surface exchange studies on (La0.75Sr0.25)0.95Cr0.5Mn0.5O3−δ

Oxygen tracer diffusion coefficient (D^⁎) and surface exchange coefficient (k^⁎) have been measured for (La_0.75Sr_0.25)_0.95Cr_0.5Mn_0.5O_3−δ using isotopic exchange and depth profiling by secondary ion mass spectrometry technique as a function of temperature (700–1000 °C) in dry oxygen and in a water vapour-forming gas mixture. The typical values of D^⁎ under oxidising and reducing conditions at ∼ 1000 °C are 4 × 10^− 10 cm² s^− 1 and 3 × 10^− 8 cm² s^− 1 respectively, whereas the values of k^⁎ under oxidising and reducing conditions at ∼ 1000 °C are 5 × 10^− 8 cm s^− 1 and 4 × 10^− 8 cm s^− 1 respectively. The apparent activation energies for D^⁎ in oxidising and reducing conditions are 0.8 eV and 1.9 eV respectively.     

Effect of GZO thickness and annealing temperature on the structural,electrical and optical properties of GZO/Ag/GZO sandwich films

The GZO/Ag/GZO sandwich films were deposited on glass substrates by RF magnetron sputtering of Ga-doped ZnO (GZO) and ion-beam sputtering of Ag at room temperature. The effect of GZO thickness and annealing temperature on the structural, electrical and optical properties of these sandwich films was investigated. The microstructures of the films were studied by X-ray diffraction (XRD). X-ray diffraction measurements indicate that the GZO layers in the sandwich films are polycrystalline with the ZnO hexagonal structure and have a preferred orientation with the c-axis perpendicular to the substrates. For the sandwich film with upper and under GZO thickness of 40 and 30 nm, respectively, it owns the maximum figure of merit of 5.3 × 10⁻² Ω⁻¹ with a resistivity of 5.6 × 10⁻⁵ Ω cm and an average transmittance of 90.7%. The electrical property of the sandwich films is improved by post annealing in vacuum. Comparing with the as-deposited sandwich film, the film annealed in vacuum has a remarkable 42.8% decrease in resistivity. The sandwich film annealed at the temperature of 350 °C in vacuum shows a sheet resistance of 5 Ω/sq and a transmittance of 92.7%, and the figure of merit achieved is 9.3 × 10⁻² Ω⁻¹.     

Synthesis and investigations on the stability of La0.8Sr0.2CuO2.4+δ at high temperatures

For application in solid oxide fuel cells La_0.8Sr_0.2CuO_2.4+δ was synthesized and the phase evolution was characterized after quenching from different temperatures and after slow cooling. A single phase perovskite was found after quenching from 950 °C. The electrical conductivity of the La_0.8Sr_0.2CuO_2.4+δ perovskite exhibited metallic behavior reaching values of about 270 S/cm at 800 °C in air. The thermal expansion between 30 and 800 °C gave a thermal expansion coefficient of 11.1 × 10^− 6 K^− 1.At higher temperatures, the perovskite was transformed to the K₂NiF₄-type structure via an intermediate stage that can be best described as a LaSrCuO₄ phase with preferential growing of {020} lattice planes. After sintering at 1100 °C and slow cooling in the furnace a phase mixture of (La,Sr)CuO_4+δ and (La,Sr)CuO_2.4+δ perovskite was obtained. This phase mixture showed higher electrical conductivity (400 S/cm at 800 °C) and smaller thermal expansion coefficient (9.6 × 10^− 6 K^− 1) than the single phase La_0.8Sr_0.2CuO_2.4+δ perovskite.     

Preparation of cadmium stannate films by spray pyrolysis technique

Cadmium stannate thin films were prepared by spray pyrolysis technique using cadmium acetate and tin(II) chloride precursors at substrate temperatures 450 °C and 500 °C. XRD pattern confirms the formation of orthorhombic (1 1 1) cadmium stannate phase for the film prepared at substrate temperature of 500 °C, whereas, films prepared at 450 °C are amorphous. Film formation does not occur at substrate temperature from 300 to 375 °C. SEM images reveal that the surface of the prepared Cd₂SnO₄ film is smooth. The average optical transmittance of ∼86% is obtained for the film prepared at substrate temperature of 500 °C with the film thickness of 400 nm. The optical band gap value of the films varies from 2.7 to 2.94 eV. The film prepared at 500 °C shows a minimum resistivity of 35.6 × 10⁻⁴ Ω cm.     

Structural and optical properties of La-doped BaSnO3 thin films grown by PLD

In this study the structural and optical properties of lanthanum-doped BaSnO₃ powder samples and thin films deposited on fused silica were investigaed using laser ablation. Under an oxygen pressure of 5×10⁻⁴ mbar, phase pure BaSnO₃ films with a lattice constant of 0.417 nm and grain size of 21 nm were prepared at 630 °C. The band gap of BaSnO3 powder sample and thin films was calculated to be 3.36 eV and 3.67 eV, respectively. There was a progressive increase in conductivity for thin films of BaSnO₃ doped with 0~7 at% of La. The highest conductivity, 9 Scm⁻¹, was obtained for 7 at% La-doped BaSnO₃. Carrier concentration, obtained from Burstein-Moss (B-M) shift, nearly matches the measured values except for 3 at% and 10 at% La-doped BaSnO₃ thin films.     

Synthesis of ammonia at atmospheric pressure with Ce0.8M0.2O2−δ (M = La,Y, Gd,Sm) and their proton conduction at intermediate temperature

Ionic conduction in fluorite-type structure oxide ceramics Ce_0.8M_0.2O_2−δ (M = La, Y, Gd, Sm) at temperature 400–800 °C was systematically studied under wet hydrogen/dry nitrogen atmosphere. On the sintered complex oxides as solid electrolyte, ammonia was synthesized from nitrogen and hydrogen at atmospheric pressure in the solid states proton conducting cell reactor by electrochemical methods, which directly evidenced the protonic conduction in those oxides at intermediate temperature. The rate of evolution of ammonia in Ce_0.8M_0.2O_2−δ (M = La, Y, Gd, Sm) is up to 7.2 × 10^− 9, 7.5 × 10^− 9, 7.7 × 10^− 9, 8.2 × 10^− 9 mol s^− 1 cm^− 2, respectively.     

Sensor application-related defect chemistry and electromechanical properties of langasite

The operation of langasite (La₃Ga₅SiO₁₄) resonators as sensors at elevated temperature and controlled atmospheres is examined. This paper focuses on mapping the regimes of gas-insensitive operation of uncoated langasite resonators and the correlation to langasite's defect chemistry for temperatures up to 1000 °C. As a measure of sensitivity, the fundamental resonant mode at 5 MHz is estimated to be determined to within ± 4 Hz by network analysis for resonators operated in air at temperatures below 1000 °C. The calculated frequency shift induced by redox-related reactions in langasite only exceeds the limit of ± 4 Hz below p_O2 ≈ 10^− 17 bar at 1000 °C, below 10^− 24 bar at 800 °C and below 10^− 36 bar at 600 °C. Water vapor is found to shift the resonance frequency at higher oxygen partial pressures. In the hydrogen-containing atmospheres applied here, langasite can be regarded as a stable resonator material above oxygen partial pressures of about 10^− 13 and 10^− 20 bar at 800 and 600 °C, respectively.     

Ac and Dc conductivities of polyaniline/poly vinyl formal blend films

The synthesis and characterization of polyaniline (PANI)/poly vinyl formal (PVF) blend films were carried out in this work. Polyaniline base was doped using dodecylbenzene sulfonic acid (DBSA). These blend films were characterized by UV–Visible, FTIR spectra and scanning electron microscopy (SEM) to investigate their optical, structural and morphological properties. It was found that the percolation threshold of these blends is 4.4 wt% of PANI. The dc and ac conductivities of these blend films have been measured at a temperature range from 300 to 100 K in the frequency range of 10 kHz to 1 MHz. The electrical conductivity of the blend films enhanced with the increase of polyaniline amount up to a value of 2.5 × 10⁻⁴ S cm⁻¹ at 65 wt% of polyaniline. The dc conductivity of the PANI/PVF blend films follows the three-dimension variable range hopping. Temperature variation of frequency exponents in this blend suggests that ac conduction is attributed to be correlated barrier hopping.     

Preparation and characterization of F doped SnO2 films and electrochromic properties of FTO/NiO films

The dependence of structural and electrical properties of SnO₂ films, prepared using spray pyrolysis technique, on the concentration of fluorine is reported. X-ray diffraction, FTIR and scanning electron microscope (SEM) studies have been performed on SnO₂:F (FTO) films coated on glass substrates. Measured values of Hall coefficient and resistivity are reported. The 7.5 m% of F doped film had a resistivity of 15 × 10⁻⁴ Ω cm, carrier density of 18.7 × 10¹⁹ cm⁻³ and mobility of 21.86 cm² V⁻¹ S⁻¹. The NiO film was coated on an FTO substrate and its electrochromic (EC) behavior was studied and the results are reported and discussed in this paper.     

Ionic conductivity of polymer electrolyte membranes based on polyphosphazene with oligo(propylene oxide) side chains

A polyphosphazene [NP(NHR)₂]_n with oligo[propylene oxide] side chains − R = –[CH(CH₃)–CH₂O]_m–CH₃ (m = 6 – 10) was synthesized by living cationic polymerisation and polymer-analogue substitution of chlorine from the intermediate precursor [NPCl₂]_n using the corresponding primary amine RNH₂. The polymer had an average molecular weight of 3.3 × 10⁵ D. Polymer electrolytes with different concentrations of dissolved lithium triflate (LiCF₃SO₃) were prepared. Mechanically stable polymer electrolyte membranes were formed using UV radiation induced crosslinking of the polymer salt mixture in the presence of benzophenone as photoinitiator. The glass transition temperature of the parent polymer was found to be − 75 °C before cross linking. It increases after crosslinking and with increasing amounts of salt to a maximum of − 55 °C for 20 wt.% LiCF₃SO₃. The ionic conductivity was determined by impedance spectroscopy in the temperature range 0–80 °C. The highest conductivity was found for a salt concentration of 20 wt.% LiCF₃SO₃: 6.5 × 10^− 6 S·cm^− 1 at 20 °C and 2.8 × 10^− 4 S cm^− 1 at 80 °C. The temperature dependence of the conductivities was well described by the MIGRATION concept.     

A Boubaker polynomials expansion scheme (BPES)-related protocol for measuring sprayed thin films thermal characteristics

Measurements of In₂S₃ and ZnIn₂S₄ sprayed thin films thermal characteristics have been carried out using the photodetection technique. The thermal conductivity k and diffusivity D were obtained using a new protocol based on photothermal signal parameters analysis. Measured values of k and D were respectively, (15.2 ± 0.85) W m⁻¹K⁻¹ and (69.8 ± 7.1) × 10⁻⁶ m²s⁻¹ for In₂S₃, (7.2 ± 0.7) W m⁻¹K⁻¹ and (32.7 ± 4.3) × 10⁻⁶ m²s⁻¹ for ZnIn₂S₄. These values are extremely important since similar compounds are more and more proposed as Cd-free alternative materials for solar cells buffer layers.     

3 MeV electron irradiation-induced defects in CuInSe2 thin films

3 MeV electron irradiation induced-defects in CuInSe₂ (CIS) thin films have been investigated. Both of the carrier concentration and Hall mobility were decreased as the electron fluence exceeded 1×10¹⁷ cm⁻². The carrier removal rate was estimated to be about 1 cm⁻¹. To evaluate electron irradiation-induced defect, the electrical properties of CIS thin films before and after irradiation were investigated between 80 and 300 K. From the temperature dependence of the carrier concentration in non-irradiated thin films, we obtained N_D=1.8×10¹⁷ cm⁻³, N_A=1.7×10¹⁶ cm⁻³ and E_D=18 meV from the SALS fitting to the experimental data on the basis of the charge balance equation. After irradiation, a new defect level was formed, and N_T0=1.4×10¹⁷ cm⁻³ and E_T=54 meV were also obtained from the same procedure. From the temperature dependence of Hall mobility, the ionized impurity density was discussed before and after the irradiation.