Visible light photoelectrochemical responsiveness of self-organized nanoporous WO3 films

Visible light-responsive WO₃ nanoporous films with preferential orientation of the (0 0 2) planes were prepared by anodization in neutral F⁻-containing strong electrolytes. The pore diameter of the self-organized structure was estimated to be in the region of 70-90 nm. Voltages were applied by stepping, which positively influenced passivity breakdown and played a significant role in the formation of self-organized nanoporous films. Under visible light irradiation, the photocurrent density (at 1.6 V vs. Ag/AgCl) and maximum photoconversion efficiency generated by the annealed nanoporous film were 3.45 mA/cm² and 0.91%, respectively. The annealed nanoporous WO₃ films show maximum incident photon-to-current conversion efficiency of 92% at 340 nm at 1.2 V vs. Ag/AgCl. These values are higher than that of annealed compact WO₃ film due to the large interfacial heterojunction area. The photoelectrochemical activities and electronic conductivities were also enhanced by annealing crystallization, which removed the recombination centers.     

Anodic formation of low-aspect-ratio porous alumina films for metal-oxide sensor application

Thin nanoporous anodic alumina films, of low aspect ratio (1:1), with two distinctive pore sizes and morphologies were prepared by two-step constant-current anodising of aluminium layers on SiO₂/Si substrates in 0.4 mol dm⁻³ tartaric (TA) and malonic acid (MA) electrolytes and then modified by open-circuit dissolution. The anodic films were employed as a support material for sputtering-deposition of thin WO₃ layers in view of exploiting their gas sensing properties. The films and deposits were characterized by scanning electron microscopy, X-ray diffraction and electric resistance measurements at fixed temperatures in the range of 100-300 °C upon NH₃ and CO gas exposures. Test sensors prepared from the annealed and stabilized alumina-supported WO₃ active layers were insensitive to CO but showed considerably enhanced responses to NH₃ at 300 °C, the sensitivity depending upon the anodic film nature, the pore size and the surface morphology. The increased sensor sensitivity is due to the substantially enlarged film surface area of the TA-supported WO₃ films and the nanostructured, camomile-like morphology of the MA-supported WO₃ films. Sensing mechanisms in the alumina-supported WO₃ active layers are discussed.     

Electrodeposition of tungsten from ZnCl2-NaCl-KCl-KF-WO3 melt and investigation on tungsten species in the melt

The electrodeposition of tungsten in ZnCl₂-NaCl-KCl-KF-WO₃ melt at 250 °C was further studied to obtain a thicker deposit. In the ordinary electrolysis at 0.08 V vs. Zn(II)/Zn, the current density decreased from 1.2 mA cm⁻² to 0.3 mA cm⁻² in 6 h. A thickness of the obtained tungsten layer was 2.1 μm and the estimated current efficiency was 93%. A supernatant salt and a bottom salt were sampled after 6 h from the melting and were analyzed by ICP-AES and XRD. It was found that the soluble tungsten species slowly changes to insoluble ones in the melt. The soluble species was suggested to be WO₃F⁻ anion. One of the insoluble species was confirmed to be ZnWO₄ and the other one was suggested to be K₂WO₂F₄. Electrodeposition was carried out under the same condition as above except for the intermittent addition of WO₃ every 2 h. The current density was kept at the initial value and the thickness was 4.2 μm. The intermittent addition of WO₃ was confirmed to be effective to obtain a thicker tungsten film.     

Direct anodic growth of thick WO3 mesosponge layers and characterization of their photoelectrochemical response

Thick mesoporous tungsten oxide (WO₃) layers can be formed by anodization of tungsten in a 10 wt% K₂HPO₄/glycerol electrolyte, if the electrolyte temperature is around 80-100 °C. At 90 °C, a regular mesoporous WO₃ layer was grown up to a thickness of approximately 9 μm. This WO₃ mesosponge layer consists of typical feature sizes of 20-30 nm and pore widths of 10-30 nm. The photoresponse of different layer thicknesses and different annealing treatments was characterized in a photoelectrochemical cell. The highest photocurrents were observed with a 2.5 μm thick WO₃ layer annealed at 550 °C consisting of a mixture of orthorhombic, triclinic and monoclinic phases. Incident photon to current efficiencies (IPCEs) of the samples were 73.4% in a 1 M HClO₄ electrolyte and 167.5% for methanol photo-oxidation in 0.1 M CH₃OH/1 M HClO₄ electrolyte, at 1 V vs. Ag/AgCl under illumination at a wavelength of 420 nm.     

Electrochemical synthesis of WO3/PANI composite for electrocatalytic reduction of iodate

Composite film of polyaniline (PANI) and tungsten oxide (WO₃) was electrodeposited by cyclic voltammetric technique from a solution of aniline and tungstic acid. The obtained WO₃/PANI film displayed a significant enhancement of electrocatalytic activity for iodate reduction and a better stability than that of pure WO₃ and PANI films. Result of amperometric experiment revealed a good linear relationship with concentration of IO₃⁻ from 20 to 500 μM, with a high sensitivity of 0.54 μA/μM and a detection limit of 2.7 μM for the determination of iodate. This composite film was also successfully applied in determination of iodate in commercial table salt.     

Synthesis and characterization of highly stable optically passive CeO2-ZrO2 counter electrode

Transparent and adherent CeO₂-ZrO₂ thin films having film thicknesses ∼543-598 nm were spray deposited onto the conducting (fluorine doped tin oxide coated glass) substrates from a blend of equimolar concentrations of cerium nitrate hexahydrate and zirconium nitrate having different volumetric proportions (0-6 vol.% of Zr) in methanol. CeO₂-ZrO₂ films were polycrystalline with cubic fluorite crystal structure and the crystallinity was improved with increasing ZrO₂ content. Films were highly transparent (T ∼ 92%), showing decrease in band gap energy from 3.45 eV for pristine CeO₂ to 3.08-3.14 eV for CeO₂-ZrO₂ films. The different morphological features of the film obtained at various CeO₂-ZrO₂ compositions had pronounced effect on the ion storage capacity and electrochemical stability. CeO₂-ZrO₂ film prepared at 5 vol.% Zr concentration exhibited higher ion storage capacity of 24 mC cm⁻² and electrochemical stability of 10,000 cycles in 0.5 M LiClO₄ + PC electrolyte due to its film thickness (584 nm) coupled with relatively larger porosity (8%). The optically passive behavior of such CeO₂-ZrO₂ film (with 5 vol.% Zr) is affirmed by its negligible transmission modulation irrespective of repeated Li⁺ and electron insertion/extraction. The coloration efficiency of spray deposited WO₃ thin film is found to enhance from 47 to 107 cm² C⁻¹ when CeO₂-ZrO₂ is coupled as a counter electrode with WO₃ in an electrochromic device (ECD). These films can be used as stable ‘passive’ counter electrodes in electrochromic smart windows as they retain full transparency in both the oxidized and reduced states and ever-reported longevity.     

Effect of decreasing film thickness on the electrochemical responses of cations adsorbed in clay-modified electrodes

Clay-modified electrodes ranging in thickness from 3.4 μm to 8 nm, as estimated from the clay loadings, were prepared using three different smectites by spin-coating, solvent evaporation or electrophoretic deposition. For all three clays, the voltammetic waves obtained for [Ru(bpy)₃]²⁺ or [Os(bpy)₃]²⁺ adsorbed in these CMEs were independent of the film thickness for all films thicker than 100 nm. Only in very thin films, ≤40 nm were significant decreases in the peak currents observed. However, when the contributions to the peak currents from the electroactive concentrations, C* and effective diffusion coefficients, D_eff were separated, the values of C* were found to increase with decreasing film thickness, while D_eff decreased by several orders of magnitude. This was attributed to increase contributions to the electrochemical responses from less mobile electrostatically bound cations in the thinner films. Similar variations in C* and D_eff were obtained in films prepared by solvent evaporation. However, C* obtained in 20 nm thick electrodeposited films were significantly lower than in 40 nm spin-coated films. For [Ru(NH₃)₆]³⁺, the peak currents increased rapidly with the film thickness. However, no significant changes in the values of C* and D_eff with film thickness were found for this ion. This is consistent with the greater mobility of [Ru(NH₃)₆]³⁺ in clays films that allows a larger fraction of the adsorbed ions to remain electroactive even in thicker films. Results obtained for [Fe(bpy)₃]²⁺ were intermediate. While, the peak currents were independent of film thickness, the values of C* or D_eff obtained for this ion were also independent of the clay loadings.     

The spatial uniformity and electromechanical stability of transparent, conductive films of single walled nanotubes

We have prepared thin films of arc discharge single walled nanotubes by vacuum filtration. For film thicknesses greater than 40 nm, the films are of high optical quality; the optical transmission varies by <2% over the film area when measured with a spatial resolution of 4 μm. However, the films become spatially non-uniform for film thickness below 40 nm. The in-plane DC conductivity correlates with the uniformity, increasing from ∼3800 S/m for a 10 nm thick film to ∼2-2.5 × 10⁵ S/m for films of thickness >40 nm. Conductive atomic force microscopy maps show reasonably uniform current flow out of the plane of the film. For all thicknesses, the optical transmittance scales with film thickness as expected for a thin conducting film with optical conductivity of 1.7 × 10⁴ S/m (λ = 550 nm). For films with t > 40 nm the ratio of DC to optical conductivity was σ_DC/σ_Op = 13.0, leading to values of transmittance and sheet resistance such as T = 80% and R_s = 110 Ω/□ for the t = 40 nm film. Electromechanically, these films were very stable showing conductivity changes of <5% and <2% when cycled over 2000 times in compression and tension respectively.     

Synthesis of high-performance electrochromic thin films by a low-cost method

Metal-doping is an effective method to adjust the physical and chemical properties of semiconductor metal oxides. This work adopts a simple solvothermal method to synthesize Mo-doped tungsten oxide nanoparticles. The high-performance electrochromic films can be homogenously formed on ITO glass without post-annealing. Compared with pure WO₃ films, the optimized Mo-doped WO₃ films show improved electrochromic properties with significant optical contrast (68.3% at 633 nm), the short response time (6.3 s and 3.9 s for coloring and bleaching, respectively), and excellent coloration efficiency (107.2 cm² C^?1). The improved electrochromic behavior is mainly due to the increasing diffusion rate of Li⁺ in Mo-doped WO₃ films (increased 20% than that of pure WO₃ films). The porous surface of Mo-doped WO₃ film shortens the diffusion path of Li⁺. Besides, Mo doping reduces the resistance and improves conductivity. Furthermore, 2at% Mo-doped WO₃ films indicate satisfactory energy-storage properties (the specific capacitance is 73.8 F g^?1), resulting from the enhanced electrochemical activity and fast electrical conductivity. This work presents a practical and economical way of developing high-performance active materials for bifunctional electrochromic devices.     

Electrochemical characterization of amorphous LiFe(WO4)2 thin films as positive electrodes for rechargeable lithium batteries

Amorphous LiFe(WO₄)₂ thin films have been fabricated by radio-frequency (R.F.) sputtering deposition at room temperature. The as-deposited and electrochemically cycled thin films are, respectively, characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, selected area electron diffraction, and X-ray photoelectron spectra techniques. An initial discharge capacity of 198 mAh/g in Li/LiFe(WO₄)₂ cells is obtained, and the electrochemical behavior is mostly preserved in the following cycling. These results identified the electrochemical reactivity of two redox couples, Fe³⁺/Fe²⁺ and W⁶⁺/W^x+ (x = 4 or 5). The kinetic parameters and chemical diffusion coefficients of Li intercalation/deintercalation are estimated by cyclic voltammetry and alternate-current (AC) impedance measurements. All-solid-state thin film lithium batteries with Li/LiPON/LiFe(WO₄)₂ layers are fabricated and show high capacity of 104 μAh/cm² μm in the first discharge. As-deposited LiFe(WO₄)₂ thin film is expected to be a promising positive electrode material for future rechargeable thin film batteries due to its large volumetric rate capacity, low-temperature fabrication and good electrode/electrolyte interface.     

Electrochromic WO3−x films with reduced lattice deformation stress and fast response time

Electrochromic properties of electrochemically deposited and etched (EDE) WO_3−x films have been investigated using voltammetry and nanogravimetry to elucidate the amount of residual stress associated with lattice polarization and deformation in WO_3−x nanoparticles. The cathodic WO_3−x deposition from pertungstic acid solution and unusual properties of the cathodic electroetching of the oxide in tetraethyl ammonium chloride solution are reported and elucidated on the basis of Electrochemical Quartz Crystal Nanogravimetry (EQCN) measurements. The stress enhanced resonant frequency shift was observed upon WO_3−x film coloration. However, the stress enhancement appeared to be much lower (up to 4-6 times) than that measured for films synthesized by other methods. The stress reduction in WO_3−x films under study has been attributed to the stress relaxing propensity of EDE film to suppress the compressive stress wave. A considerable isotopic effect has been observed in nanogravimetry of the H⁺ and D⁺ ion intercalation into WO_3−x films. We have found that the isotopic effect is primarily due to the true mass loading difference between hydrogen and deuterium ions, for the same concentration of color centers (2.65 × 10²¹ cm⁻³), since EQCN frequency shifts associated with stress in the film for H⁺ and D⁺ are very close to each other.     

Highly crystalline macroporous β-MnO2: Hydrothermal synthesis and application in lithium battery

A highly crystalline macroporous β-MnO₂ was hydrothermally synthesized using stoichiometric reaction between KMnO₄ and MnCl₂. The as-prepared material has a pore size of ca. 400 nm and a shell thickness of 300-500 nm. The formation of the macroporous morphology is related to self-assembling from nanowires of α-MnO₂, and could be obtained at high reactant concentrations (e.g., 0.8 M KMnO₄) but not at low ones (e.g., below 0.04 M KMnO₄). Compared to conventional bulk β-MnO₂ processing very low capacity, our macroporous material exhibits good electrochemical activity, e.g., obtaining an initial discharge capacity of 251 mAh g⁻¹ and sustaining as ca. 165 mAh g⁻¹ at 10 mA g⁻¹. The electrochemical activity of the as-prepared β-MnO₂ is related to its macroporous morphology and small shell thickness; the former leads to that electrolyte can flood pore of the material and its inner surface is available for lithium ion diffusion, while the latter helps to release the stress from phase transformation during the initial discharging. The X-ray diffraction characterizations of the macroporous β-MnO₂ electrodes suggest that, upon initial discharging, such a β-MnO₂ will be irreversibly transformed to an orthorhombic Li_xMnO₂ and then cycled within the new developed phase in the subsequent lithium insertion/extraction processes.     

Formation of porous anodic titanium oxide films in hot phosphate/glycerol electrolyte

The present study reveals the formation of porous anodic films on titanium at an increased growth rate in hot phosphate/glycerol electrolyte by reducing the water content. A porous titanium oxide film of 12 μm thickness, with a relatively low content of phosphorus species, is developed after anodizing at 5 V for 3.6 ks in 0.6 mol dm⁻³ K₂HPO₄ + 0.2 mol dm⁻³ K₃PO₄/glycerol electrolyte containing only 0.04% water at 433 K. The growth efficiency is reduced by increasing the formation voltage to 20 V, due to formation of crystalline oxide, which induces gas generation during anodizing. The film formed at 20 V consists of two layers, with an increased concentration of phosphorus species in the inner layer. The outer layer, comprising approximately 25% of the film thickness, is developed at low formation voltages, of less than 10 V, during the initial anodizing at a constant current density of 250 A m⁻². The pore diameter is not significantly dependent upon the formation voltage, being ∼10 nm.     

Film thickness dependence of the dielectric properties of SrTiO3/BaTiO3 multilayer thin films deposited by double target RF magnetron sputtering

Four-layer SrTiO₃/BaTiO₃ thin films ((ST/BT)₄) with various thicknesses deposited on Pt/Ti/SiO₂/Si substrates at 500 °C by double target RF magnetron sputtering have been investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), profilometry, capacitance-voltage and current-voltage measurements. The XRD patterns reveal the frame formation of the sputter deposited (ST/BT)₄ with controlled modulation. The adhesion between the Pt bottom electrode layer and the BT layer is excellent. The dielectric constant of the (ST/BT)₄ multilayer thin film increases with increasing film thickness. The effects of temperature, frequency, and bias voltage on the dielectric constant of the (ST/BT)₄ multilayer thin films are discussed in detail. The leakage current density of the (ST/BT)₄ multilayer with a thickness of 450.0 nm is lower than 1.0 × 10⁻⁸ A/cm² for the applied voltage of less than 5 V, showing that the multilayer thin films with such a characteristic could be applied for use in dynamic random access memory (DRAMs) capacitors.     

Unique and facile solvothermal synthesis of mesoporous WO3 using a solid precursor and a surfactant template as a photoanode for visible-light-driven water oxidation

Mesoporous tungsten trioxide (WO₃) was prepared from tungstic acid (H₂WO₄) as a tungsten precursor with dodecylamine (DDA) as a template to guide porosity of the nanostructure by a solvothermal technique. The WO₃ sample (denoted as WO₃-DDA) prepared with DDA was moulded on an electrode to yield efficient performance for visible-light-driven photoelectrochemical (PEC) water oxidation. Powder X-ray diffraction (XRD) data of the WO₃-DDA sample calcined at 400°C indicate a crystalline framework of the mesoporous structure with disordered arrangement of pores. N₂ physisorption studies show a Brunauer-Emmett-Teller (BET) surface area up to 57 m² g^-1 together with type IV isotherms and uniform distribution of a nanoscale pore size in the mesopore region. Scanning electron microscopy (SEM) images exhibit well-connected tiny spherical WO₃ particles with a diameter of ca. 5 to 20 nm composing the mesoporous network. The WO₃-DDA electrode generated photoanodic current density of 1.1 mA cm^-2 at 1.0 V versus Ag/AgCl under visible light irradiation, which is about three times higher than that of the untemplated WO₃. O₂ (1.49 μmol; Faraday efficiency, 65.2%) was evolved during the 1-h photoelectrolysis for the WO₃-DDA electrode under the conditions employed. The mesoporous electrode turned out to work more efficiently for visible-light-driven water oxidation relative to the untemplated WO₃ electrode.     

Structures,morphological control,and antibacterial performance of tungsten oxide thin films

The present work describes structural, morphological, and antibacterial properties of thin film coatings based on tungsten oxide material on stainless-steel substrates. Thin films were prepared by RF magnetron sputtering of W targets in the oxygen/argon plasma environment in 60 W sputtering power. The characterization of the specimens was made on the basis of microstructure and antibacterial properties of the thin films surface. The effect of O₂/Ar ratio on the structure, morphology, and antibacterial properties of the tungsten oxide thin films was studied. Methods such as X-ray diffraction (XRD), scanning electron microscope (SEM), and Fourier Transform Infrared Spectroscopy (FTIR) were used to assess the properties of deposited thin films. XRD peak analysis indicates (100) and (200) of WO₃ phase with hexagonal structure. Moreover, the micro-strain, grain size, and dislocation density were obtained. It is noteworthy that by increasing the oxygen percentage from 10% to 20%, the grain size decreases from 81 to 23 nm while the film micro-strain and dislocation density increases. The SEM results illustrates that tungsten oxide thin films are made of interconnected nano-points in a chain shape with sphere-shaped grains with diameter variation from 10 to 100 nm. The FTIR spectra displays four distinct bands corresponds to O–W–O bending modes of vibrations and W–O–W stretching modes of the WO₃ films. The antibacterial effects of tungsten oxide thin films on steel stainless substrate against Escherichia coli bacteria are also examined for the first time and our observation shows that the number of bacteria on all tungsten oxide samples decreases after 24 h. The samples exhibit an excellent antibacterial performance. This paper renders a strategy through which the tungsten oxide thin films for antibacterial purpose and proposes that WO₃ thin films are ideal for various medical applications including stainless steel medical tools, optical coatings, and antibacterial coatings.     

Facile growth of 1‐D nanowire‐based WO3 thin films with enhanced photoelectrochemical performance

A flame reactor embedded with a constant tungsten wire feeding system to prepare one‐dimensional (1‐D) nanostructured tungsten oxide thin film for photoelectrochemical (PEC) water splitting was developed. Photoactive vertically‐aligned nanowire‐based WO₃ thin films could be obtained with a controlled thickness via a flame vapor deposition process followed by air‐annealing. The PEC performances of WO₃ photoelectrodes for different thin film thicknesses were examined. The optimum thickness of WO₃ thin film was found to be about 7.2 μm for PEC water splitting based on incident photon‐to‐current efficiency plots and I–V curves. The WO₃ prepared with optimum thickness showed better PEC performance than those of recently reported nanostructured WO₃ photoanodes. © 2015 American Institute of Chemical Engineers AIChE J, 62: 421–428, 2016     

Effects of tungsten thickness and annealing temperature on the electrical properties of W-TiO2 thin films

TiO₂ thin films were prepared by RF magnetron sputtering onto glass substrates and tungsten was deposited onto these thin films (deposition time 15-60 s) to form W-TiO₂ bi-layer thin films. The crystal structure, morphology, and transmittance of these TiO₂ and W-TiO₂ bi-layer thin films were investigated. Amorphous, rutile, and anatase TiO₂ phases were observed in the TiO₂ and W-TiO₂ bi-layer thin films. Tungsten thickness and annealing temperature had large effects on the transmittance of the W-TiO₂ thin films. The W-TiO₂ bi-layer thin films with a tungsten deposition time of 60 s were annealed at 200 °C-400 °C. The band gap energies of the TiO₂ and the non-annealed and annealed W-TiO₂ bi-layer thin films were evaluated using (αhν)^1/2 versus energy plots, showing that tungsten thickness and annealing temperature had major effects on the transmittance and band gap energy of W-TiO₂ bi-layer thin films.     

Graphene nanosheets-tungsten oxides composite for supercapacitor electrode

Graphene nanosheets-tungsten oxides (tungsten oxide/tungsten oxide hydrate mixture) (GNS-W) composite was successfully synthesized using a facile approach. WO₃/WO₃·H₂O mixtures were deposited on the graphene nanosheets (GNS) to form the GNS-W composite. The GNS-W composite was characterized by X-ray diffraction (XRD), Raman spectrum, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The as-prepared GNS-W composite was directly fabricated into a supercapacitor electrode for potential energy storage application, and electrochemically tested by cyclic voltammetry, galvanostatic charge/discharge and electrochemical impedance spectroscopy. The GNS-W composite electrode exhibits a better electrochemical performance than that of the WO₃/WO₃·H₂O mixtures electrode. A high specific capacitance of about 143.6 F g⁻¹ at a current density of 0.1 A g⁻¹ for the GNS-W composite delivers significant improvement than that for the WO₃/WO₃·H₂O mixtures and GNS electrodes. The impedance studies also suggest that the GNS-W composite electrode shows the lower resistance and high conductivity due to the good interaction between the graphene nanosheets and the WO₃/WO₃·H₂O mixtures. The good electrochemical performance for the GNS-W composite may be attributed to the interaction between the WO₃/WO₃·H₂O mixtures and the edges of graphene nanosheets, which increases the ion diffusion rate as well as the conductivity.     

Facile synthesis of mesoporous Ag-loaded TiO2 thin film and its photocatalytic properties

Ag nanoparticles highly dispersed into TiO₂ thin films are synthesized via a remarkably simple one-pot route in the presence of a P123 triblock copolymer as template directing and reducing agents, where the reduction of Ag⁺ to Ag⁰ by in situ heat-induced reduction through the oxidation of template at 400 °C and the controlled polymerization of TiO₂ take place simultaneously. The obtained mesoporous Ag/TiO₂ films deposited on soda-lime glass were optically transparent and crack-free. SEM and Kr adsorption clearly prove that Ag/TiO₂ films at different Ag contents are mesoporous with large surface area and regularly ordered mesopores and the thickness of the obtained films is ∼280 ± 20 nm. The pristine TiO₂ film exhibits a specific surface area of 63 cm²/cm² and specific pore volume of 0.013 mm³/cm² that it is decreased to 42 cm²/cm² and 0.010 mm³/cm² respectively as a result of Ag-loaded mesoporous TiO₂. The newly prepared photocatalysts Ag/TiO₂ films were evaluated for their photocatalytic degradation of 2-chlorophenol as a model reaction. It was found that the meso-ordered Ag/TiO₂ films are more photoactive 8 times than nonporous commercial photocatalysts Pilkington Glass Activ™. The recycling tests indicated that Ag/TiO₂ films was quite stable during that liquid-solid heterogeneous photocatalysis since no significant decrease in activity was observed even after being used repetitively for 10 times, showing a good potential in practical application. In general, the cubic mesoporous Ag/TiO₂ nanocomposites are stable and can be recycled without loss of their photochemical activity.