Iridium Oxide Thin Films Research Articles

Determination of solid phase chemical diffusion coefficient and density of states by electrochemical methods: Application to iridium oxide-based thin films

Potentiostatic intermittent titration technique (PITT) and electrochemical impedance spectroscopy (EIS) were investigated as methods to determine solid phase chemical diffusion coefficient (D) and electronic density of states (DOS). These techniques were then applied to iridium oxide (IrOx) and iridium-tantalum oxide (IrTaOx) thin films prepared by sputter deposition. The experiments, performed in 1M propionic acid between −0.2 and 0.8V vs Ag∕AgCl, showed effects of interfacial side reactions, whose contribution to the electrochemical response could be identified and corrected for in the case of PITT as well as EIS. It was found that D is strongly underestimated when using PITT with the common Cottrell formalism, which follows from non-negligible interfacial charge transfer and Ohmic resistances. EIS indicated an anomalous diffusion mechanism, and D was determined to be in the 10−11–10−10cm2∕s range for IrOx and IrTaOx. Both PITT and EIS showed that the intercalated charge as a function of potential exhibits a shape that resembles the theoretical DOS of crystalline iridium oxide, especially for IrTaOx.

Iridium Oxide Film‐Enhanced Impedance Immunosensor for Rapid Detection of Carcinoembyronic Antigen

AbstractA simple, rapid and sensitive impedance immunosensor based on iridium oxide (IrOx) thin film for the detection of carcinoembyronic antigen (CEA) in human sera has been proposed. Gold electrode was electrochemically modified with IrOx thin film and simultaneously functionalized with protein A (PA) to bind anti‐CEA antibodies in an orientated way. It has been found that the antibody loading amount was dependent on the PA concentration and the deposition time of IrOx matrix. Under the optimized experimental conditions, the electron transfer resistances obtained were linearly related to the CEA concentration ranging from 36.2 to 460.0 ng/mL, with a detection limit of 28.0 ng/mL. Analytical results of clinical samples from cancer patients show that the proposed immunoassay is reasonably comparable with the chemiluminescence immunoassay (CLIA), indicating the feasibility of using the proposed method for CEA immunoassay in clinical laboratory.

Microstructure and Resistivity of Iridium Oxide Thin Films by Pulsed Laser Deposition Technique

Highly conductive IrO2 thin films were prepared on Si (100) substrates by pulsed laser deposition technique from an iridium metal target in an oxygen ambient atmosphere. The effect of substrate temperature on the structure and electrical properties of IrO2 films was investigated. The deposited films at substrate temperatures ranging from 250 to 500°C under an oxygen pressure of 20Pa were pure polycrystalline tetragonal IrO2 and the preferential growth orientation changed with the substrate temperature. IrO2 films were well solidified with the fairly homogeneous thickness and exhibited a good adhesion with the substrate. The room-temperature resistivity of IrO2 films decreased with the increase of substrate temperature and the minimum resistivity of (42±6) μ-·cm was deposited at 500°C.

Characterization of iridium oxide thin films deposited by pulsed-direct-current reactive sputtering

Thin films of iridium oxide were deposited on silicon and borosilicate glass substrates by pulsed-direct-current (pulsed-DC) reactive sputtering of iridium metal in an oxygen-containing atmosphere. Optimum deposition conditions were identified in terms of plasma pulsing conditions, oxygen partial pressures, and substrate temperature. The films were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy, and Rutherford backscattering spectroscopy. According to the results, it was possible to obtain films that are near-stoichiometric, smooth and uniform in texture. The films deposited without substrate heating were amorphous, and those deposited at substrate temperatures above 300 °C were found to have a homogeneous polycrystalline structure. The results also showed that pulsed-DC sputtered iridium oxide films were smoother and had lower micro-inclusions density than DC-sputtered films obtained under otherwise similar deposition conditions. This improvement in the film quality is at the expense of a tolerable decrease in the deposition rate.

Differential pH measurements of metabolic cellular activity in nl culture volumes using microfabricated iridium oxide electrodes

In this paper we describe a new approach to measure pH differences in microfluidic devices and demonstrated acidification rate measurements in on-chip cell culture systems with nl wells. We use two miniaturized identical iridium oxide (IrOx) thin film electrodes (20 micromx400 microm), one as a quasi-reference electrode, the other as a sensing electrode, placed in two confluent compartments on chip. The IrOx electrodes were deposited onto microfabricated platinum (Pt) electrodes simultaneously using electrodeposition. Incorporating the electrodes into a microfluidic device allowed us to expose each electrode to a different solution with a pH difference of one pH unit maintaining a confluent connection between the electrodes. In this configuration, we obtained a reproducible voltage difference between the two IrOx thin film electrodes, which corresponds to the electrode sensitivities of -70 mV/pH at 22 degrees C. In order to measure the acidification rate of cells in nl cell culture volumes we placed one IrOx thin film electrode in the perfusion channel as a quasi-reference electrode and the other in the cell culture volume. We obtained an acidification rate of 0.19+/-0.02 pH/min for fibroblast cells using a stop flow protocol. These results show that we can use two identical miniaturized microfabricated IrOx electrodes to measure pH differences to monitor the metabolic activity of cell cultures on chip. Furthermore, our approach can also be applied in biosensor or bioanalytical applications.

Effect of film thickness on electrochromic activity of spray deposited iridium oxide thin films

Electrochromic iridium oxide thin films were deposited onto fluorine doped tin oxide (FTO) coated glass substrates from an aqueous iridium chloride solution using a spray pyrolysis process. The deposition temperature was 250 °C. The solution quantity was varied from 25 to 55 ml to obtain films with different thickness. The as-deposited samples were X-ray amorphous. The electrochromic properties were studied in proton containing electrolyte (0.5N, H 2SO 4) using cyclic voltammetry, chronoamperometry and spectrophotometry techniques. The films exhibit anodic electrochromism. The colouration efficiency at 630 nm was maximum for thicker sample, owing to its large charge storage capacity and hydration.

Development and characterization of an all-solid-state potentiometric biosensor array microfluidic device for multiple ion analysis

A microfluidic device with an all-solid-state potentiometric biosensor array was developed using microfabrication technology. The sensor array included a pH indicator, and potassium and calcium ion-selective microelectrodes. The pH indicator was an iridium oxide thin film modified platinum microelectrode and the iridium oxide was deposited by an electrochemical method. The potassium and calcium ion-selective microelectrodes were platinum coated with silicon rubber based ion-selective membranes with respectively potassium (valinomycin) and calcium (ETH 1001) ionophores. The detection system was integrated with a micro-pneumatic pump which can continuously drive fluids into the microchannel through sensors at flow rates ranging from 52.4 microl min(-1) to 7.67 microl min(-1). The sensor array microfluidic device showed near-Nernstian responses with slopes of 62.62 mV +/- 2.5 mV pH(-1), 53.76 mV +/- 3 mV -log[K+](-1) and 25.77 mV +/- 2 mV -log[Ca2+](-1) at 25 degrees C +/- 5 degrees C, and a linear response within the pH range of 2-10, with potassium and calcium concentrations between 0.1 M and 10(-6) M. In this study the device provided a convenient way to measure the concentration of hydrogen, potassium and calcium ions, which are important physiological parameters.

Properties of mixed molybdenum oxide–iridium oxide thin films synthesized by spray pyrolysis

Molybdenum-doped iridium oxide thin films have been deposited onto corning glass- and fluorine-doped tin oxide coated corning glass substrates at 350 °C by using a pneumatic spray pyrolysis technique. An aqueous solution of 0.01 M ammonium molybdate was mixed with 0.01 M iridium trichloride solution in different volume proportions and the resultant solution was used as a precursor solution for spraying. The as-deposited samples were annealed at 600 °C in air medium for 1 h. The structural, electrical and optical properties of as-deposited and annealed Mo-doped iridium oxide were studied and values of room temperature electrical resistivity, and thermoelectric power were estimated. The as-deposited samples with 2% Mo doping exhibit more pronounced electrochromism than other samples, including pristine Ir oxide.

Promotion of electrochromism in spray-deposited molybdenum oxide-doped iridium oxide thin films

Electrochromic molybdenum oxide-doped iridium oxide thin films were prepared by using a pneumatic spray pyrolysis technique onto fluorine-doped tin oxide (FTO) coated conducting glass substrates. An aqueous solution of 0.01 M ammonium molybdate was mixed with 0.01 M iridium trichloride in different volume proportions and the resultant solution was used as a precursor for spraying. An aqueous electrolyte (0.5 N H2SO4) was used to study electrochromic properties of thin films using cyclic voltammetry (CV), chronoamperometry (CA) and spectrophotometry. During the potential scan the iridium oxide electrode switches between coloured and bleached state due to Ir+4–Ir+3 intervalency charge transfers. The optical density difference (ΔOD)λ=630 nm and colouration efficiency was maximum for 2% molybdenum oxide-doped sample. Moreover, loss in charge density during extended cycling is less than undoped and other doped (>2%) samples.

Substrate temperature dependent morphology and resistivity of pulsed laser deposited iridium oxide thin films

Iridium oxide (IrO 2) thin films were deposited on Si (100) substrates by means of pulsed laser deposition technique at various substrate (deposition) temperatures ranging from 250 to 500 °C. Effects of substrate temperature on the crystalline nature, morphology and electrical properties of the deposited films were analyzed by using X-ray diffraction, Raman spectroscopy, Scanning electron microscopy and four-point probe method. It was found that the above properties were strongly dependent on the substrate temperature. The as-deposited films at all substrate temperatures were polycrystalline tetragonal IrO 2 and the preferential growth orientation changed with the substrate temperature. IrO 2 films exhibited fairly homogeneous thickness and good adhesion with the substrate, the average feature size increases with the substrate temperature. The room-temperature resistivity of IrO 2 films decreased with the increase of substrate temperature and the minimum resistivity of (42 ± 6) μΩ cm was obtained at 500 °C. The resistivity of IrO 2 films correlated well with the corresponding film morphology changes.

Investigation of the electrical and optical properties of iridium oxide by reflectance FTIR spectroscopy and density functional theory calculations

Variable angle reflectance FTIR spectroscopy was used to investigate the optical properties of iridium oxide thin films deposited on glass substrates in the near-IR spectral region. The reflectance was studied as a function of incident angle and wavenumber for p-polarized radiation. The Drude free-electron model along with the Fresnel equations of reflection were utilized to fit the experimental reflectance FTIR data to determine the plasma frequency and electronic scattering time of this conducting metal oxide thin film. These experimental studies were complemented by density functional theory (DFT) calculations of the electronic and optical properties of iridium oxide. The calculations used the crystal structure of iridium oxide with periodic boundary conditions. These theoretical studies yielded the optical band gap, Fermi energy, charge carrier concentration, effective electron mass, plasma frequency and the conduction band orbital character of iridium oxide. The computed dependence of the optical band gap, Fermi energy, charge carrier concentration and the plasma frequency on compression or expansion of the iridium oxide unit cell was investigated.

Effect of substrate temperature on electrochromic properties of spray-deposited Ir-oxide thin films

Electrochromic iridium oxide thin films were prepared by using a simple and inexpensive spray pyrolysis technique onto fluorine doped tin oxide (FTO)-coated glass substrates, from iridium chloride solution. The substrate temperature was varied between 250 and 400 °C. The as-deposited samples were amorphous. The electrochromic properties of thin films were studied in aqueous electrolyte (0.5N H 2SO 4) using cyclic voltammetry (CV), chronoamperometry (CA) and spectroelectrochemical techniques. The films exhibit anodic electrochromism upon intercalation and deintercalation of H + ions. The colouration efficiency at 630 nm was calculated and found maximum for I 250 sample, owing its hydration.

Electrochromism in spray deposited iridium oxide thin films

Electrochromic iridium oxide thin films were deposited onto fluorine doped tin oxide coated glass substrates from an aqueous iridium chloride solution by pneumatic spray pyrolysis technique. The as-deposited samples were X-ray amorphous. The electrochromic properties of thin films were studied in an aqueous electrolyte (0.5N H 2SO 4) using cyclic voltammetry (CV), chronoamperometry (CA) and spectrophotometry. Iridium oxide films show pronounced anodic electrochromism owing to Ir +4 ↔ Ir +3 intervalency charge transition. The reversibility of cyclic process in Ir oxide films is found to be higher, which increases with increasing number of colour–bleach cycles.

Effect of the Iridium Oxide Thin Film on the Electrochemical Activity of Platinum Nanoparticles

The influence of the iridium oxide thin film on the electrocatalytic properties of platinum nanoparticles was investigated using the electro-oxidation of methanol and CO as a probe. The presence of the IrO(2) thin film leads to the homogeneous dispersion of Pt nanoparticles. For comparison, polycrystalline platinum and Pt nanoparticles dispersed on a Ti substrate in the absence of an IrO(2) layer (Ti/Pt) were also investigated in this study. Inverted and enhanced CO bipolar peaks were observed using an in situ electrochemical Fourier transform infrared technique during the methanol oxidation on the Pt nanoparticles dispersed on a Ti substrate. Electrochemical impedance studies showed that the charge transfer resistance was significantly lower for the Ti/IrO(2)/Pt electrode compared with that of the massive Pt and Ti/Pt nanoparticles. The presence of the IrO(2) thin film not only greatly increases the active surface area but also promotes CO oxidation at a much lower electrode potential, thus, significantly enhancing the electrocatalytic activity of Pt nanoparticles toward methanol electro-oxidation.

Sputtered Iridium Oxide Films as Charge Injection Material for Functional Electrostimulation

The paper reports on the deposition of iridium oxide thin films by dc reactive magnetron sputtering and their characterization by surface analysis methods (X-ray diffraction, scanning electron microscopy, atomic force microscopy, and X-ray photoelectron spectroscopy) and electrochemical techniques (cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic square waves). The sputtering process was investigated by applying the method of generic curves. An optimal combination of sputtering parameters has been established [40 standard cubic centimeters per minute (sccm) argon/8-12 sccm oxygen/40% effective pump power/100 W dc power/“cold” sputtering] that yields stable microporous amorphous films with a highly extended surface. These films have shown an excellent electrochemical reversibility in physiological saline solution with a “safe” potential range of −1.2 to 1.3 V vs. Ag/AgCl reference electrode, a charge delivery capacity of 90-95 mC/cm2, a constant impedance of 70-80 Ω in the frequency range of 100 kHz down to 0.5-1.0 Hz, and a quick response to bipolar current pulses with a safe charge per phase of 2 mC/cm2/ph. The demonstrated remarkable electrochemical characteristics combined with their established long-term mechanical stability and corrosion resistance allow one to recommend the use of sputtered iridium oxide films as an ideal electrode material for neural stimulation. © 2004 The Electrochemical Society. All rights reserved.

Iridium Oxide as Low Temperature<tex>$hbox NO_2$</tex>-Sensitive Material for Work Function-Based Gas Sensors

This paper presents the results on work function-based NO/sub 2/-sensing properties of iridium-oxide thin films at 130/spl deg/C. Films of 20-nm and 100-nm thickness were deposited on silicon substrates using dc sputtering followed by annealing in oxygen ambient. Sensitivity of these films to different concentrations of NO/sub 2/, H/sub 2/, CO, Cl/sub 2/, and NH/sub 3/ in synthetic air was measured using a Kelvin probe. It was observed that work function of 20-nm-thick iridium-oxide film changed by /spl sim/100 mV on exposure to 5-ppm NO/sub 2/ (German safety limit). Cross sensitivity to other gases (except NH/sub 3/) and interference of humidity was found to be negligibly small. The film was incorporated as a gate electrode in a hybrid suspended gate field effect transistor (HSGFET) structure to examine its suitability in FET-type sensors. The films were characterized using Rutherford backscattering spectroscopy, X-ray diffraction analysis, and scanning electron microscopy to determine their composition, phase, and surface morphology. The results suggest that iridium-oxide film is a promising material for the realization of a FET-based NO/sub 2/ sensor.

Novel amperometric immunosensors based on iridium oxide matrices

Novel immunosensors based on antibodies immobilized in electrochemically grown iridium oxide (IrOx) thin film matrices have been developed. Antibody loading in the oxide was evaluated using a non-competitive electrochemical immunoassay for IgG. Anti-IgG loading in the oxide was found to be dependent on the concentration of anti-IgG present in the oxide growth step, with 400 μg/ml anti-IgG producing maximum amperometric responses. To study the potential analytical properties of the matrix, the dose–response behavior of the sensors was determined using optimized alkaline phosphatase-linked IgG immunoassay. Hydroquinone diphosphate (HQDP) was used as enzyme substrate and the oxidation of hydroquinone was detected amperometrically at +420 mV. The sensors displayed a linear dose–response behavior for IgG concentrations between 10 and 200 ng/ml, saturating above 600 ng/ml, and had a low detection limit of 8 ng/ml. Finally, the method was used to produce sensors containing immobilized anti-transferrin. Using a non-optimized electrochemical immunoassay for human transferrin (HT), dose–response behavior was observed for HT concentrations between 100 and 600 ng/ml. The results presented in this paper show that IrOx matrices represent a new method for immunosensor fabrication. The oxide acts as a hydrophilic, highly porous, three-dimensional matrix that can immobilize antibodies and retain their activity. The method is attractive because it offers the potential for high antibody loadings and is suitable for mass production of sensors in an easy and economical manner.

Thickness-dependent properties of sprayed iridium oxide thin films

Iridium oxide thin films with variable thickness were deposited by spray pyrolysis technique (SPT), onto the amorphous glass substrates kept at 350 °C. The volume of iridium chloride solution was varied to obtain iridium oxide thin films with thickness ranging from 700 to 2250 Å. The effect of film thickness on structural and electrical properties was studied. The X-ray diffraction (XRD) studies revealed that the as-deposited samples were amorphous and those annealed at 600 °C for 3 h in milieu of air were polycrystalline IrO 2. The crystallinity of Ir-oxide films ameliorate with film thickness thereby preferred orientation along (1 1 0) remains unchanged. The infrared spectroscopic results show Ir–O and Ir–O 2 bands. The room temperature electrical resistivity ( ρ RT) of these films decreases with increase in film thickness. The p-type semiconductor to metallic transition was observed at 600 °C.

Substrate temperature dependent structural, optical and electrical properties of spray deposited iridium oxide thin films

Iridium oxide thin films were deposited onto the glass substrates by spray pyrolysis technique (SPT) using aqueous solution of IrCl 3·3H 2O at various substrate (deposition) temperatures ranging from 250 to 400 °C. Emission of both physisorbed and chemisorbed water takes place during thermal decomposition process and Ir 2O 3 forms below 600 °C, above which dehydrated IrO 2 formation takes place. The as-deposited samples at all substrate temperatures were X-ray amorphous and those annealed at 600 °C for 3 h in milieu of air were polycrystalline tetragonal IrO 2. The infrared (IR) and Raman spectroscopic results echo above findings. The optical and electrical characteristics reveal that optical transition takes place through d–d intraband excitation and p-type semiconductor to metallic transition at 600 °C. The semiconducting to metal transitions in iridium oxide thin films were discussed on the basis of Anderson’s theory.

A room temperature HSGFET ammonia sensor based on iridium oxide thin film

Gas-sensing properties of hybrid suspended gate FET (HSGFET) sensor containing iridium oxide as sensitive layer are reported in this paper. The sensor response to NH 3 and H 2 was measured. We obtained a non-amplified signal of 70 mV for 50 ppm of ammonia and no signal to hydrogen even for 10,000 ppm. Further, the gas-sensing properties of thin film of iridium oxide has been studied using Kelvin probe (KP) setup. Sensitivity of these films to gases like CO, H 2, SO 2, Cl 2, NO 2 under dry and humid conditions were examined by measuring contact potential difference (CPD) resulting from work function change of the film due to exposure to test gases. The results suggest that iridium oxide-based HSGFET is selectively sensitive to ammonia with negligible signal to all other gases. Iridium oxide films of 20 nm thickness used in this study were prepared by dc sputter deposition at 300 °C followed by sintering at 600 °C in oxygen. The films were characterized using Rutherford backscattering spectroscopy (RBS), X-ray diffraction (XRD) analysis, scanning electron microscopy (SEM), and atomic force microscopy (AFM) to determine their composition, phase and surface morphology.