Enhancement in hydrophobicity of silica films using metal acetylacetonate and heat treatment

Water is one of the most affecting chemicals that can cause damage to the solid surface. To protect the surface due to the action of water, the surface should be made hydrophobic. In the present study, the improvement in hydrophobicity of silica films using metal acetylacetonate (M-acac) by employing heat treatment to methyltrimethoxy silane (MTMS) based silica coatings is reported as a novel attempt. Instead of following the established trends of the surface derivatization or co-precursor method, iron acetylacetonate Fe(acac)₃, copper acetylacetonate Cu(acac)₂ and heat treatment were used to incorporate hydrophobicity with silica coatings. As M-acac is readily soluble in organic solvents, Fe(acac)₃ and Cu(acac)₂ were dissolved in methanol (MeOH) and their concentration was varied from 0 to 0.025 M. The coating solution was prepared by optimizing molar ratio of MTMS:MeOH:basic H₂O to 1:7.15:6.34, respectively. Gelation time (t_g) for Cu(acac)₂ containing silica sol and that containing Fe(acac)₃ were noted to be 30 and 55 min, respectively. The substrates were taken out after gelation and heat treated at 150 °C for 2 h. The heat treated films showed a dramatic increase in the static water contact angle from 82° to as high as 142°.     

Properties of conductive polymer films deposited by infrared laser ablation

Thin films of the conducting polymer poly(3,4-ethylenedioxy-thiophene):poly(styrenesulfonate) (PEDOT:PSS) were deposited by resonant infrared laser vapor deposition (RIR-LVD). The PEDOT:PSS was frozen in various matrix solutions and deposited using a tunable, mid-infrared free-electron laser (FEL). The films so produced exhibited morphologies and conductivities that were highly dependent on the solvent matrix and laser irradiation wavelength used. When deposited from a native solution (1.3% by weight in water), as in matrix-assisted pulsed laser evaporation (MAPLE), films were rough and electrically insulating. When the matrix included other organic “co-matrices” that were doped into the solution prior to freezing, however, the resulting films were smooth and exhibited good electrical conductivity (0.2 S/cm), but only when irradiated at certain wavelengths. These results highlight the importance of the matrix/solute and matrix/laser interactions in the ablation process.     

TMOS based water repellent silica thin films by co-precursor method using TMES as a hydrophobic agent

The present paper describes the room temperature synthesis of dip coated water repellent silica coatings on glass substrates using trimethylethoxysilane (TMES) as a co-precursor. Silica sol was prepared by keeping the molar ratio of tetramethoxysilane (TMOS) precursor, methanol (MeOH) solvent, water (H₂O) constant at 1:29.27:2.09 respectively, with 0.5 M NH₄OH throughout the experiments and the TMES/TMOS molar ratio (M) was varied from 0 to 3.8. It was found that with an increase in M value, the roughness and hydrophobicity of the films increased, however the optical transmission decreased from 93% to 57% in the visible range. The hydrophobic silica films retained their hydrophobicity up to a temperature of 250 °C and above this temperature the films became hydrophilic. The hydrophobic silica thin films were characterized by taking into consideration the surface roughness studies, Fourier transform infrared (FT-IR) spectroscopy, percentage of optical transmission, scanning electron microscopy (SEM) and contact angle measurements.     

Superhydrophobic silica films by sol–gel co-precursor method

Wetting phenomena of water droplets on solid are of crucial concern in our daily life as well as in engineering and science. The present paper describes the room temperature synthesis of superhydrophobic silica films on glass substrates using trimethylethoxysilane (TMES) as a co-precursor. The coating sol was prepared by keeping the molar ratio of tetraethoxysilane (TEOS) precursor, methanol (MeOH) solvent, water (H₂O) constant at 1:38.6:8.68, respectively, with 2 M NH₄OH throughout the experiments and the TMES/TEOS molar ratio (M) was varied from 0 to 1.1. It was found that with an increase in M value, the hydrophobicity of the films increased, however the optical transmission decreased from 88% to 82% in the visible range. The hydrophobic silica films retained their hydrophobicity up to a temperature of 275 °C and above this temperature the films became superhydrophilic. The hydrophobic silica films were characterized by Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM), Fourier Transform Infrared (FT-IR) spectroscopy, percentage of optical transmission, humidity test and static and dynamic contact angle measurements.     

Transparent Superhydrophobic silica coatings on glass by sol-gel method

Wetting behavior of solid surfaces is a key concern in our daily life as well as in engineering and science. In the present study, we demonstrate a simple dip coating method for the preparation of Thermally stable, transparent superhydrophobic silica films on glass substrates at room temperature by sol-gel process. The coating alcosol was prepared by keeping the molar ratio of methyltriethoxysilane (MTES), trimethylmethoxysilane (TMMS), methanol (MeOH), water (H₂O) constant at 1:0.09:12.71:3.58, respectively with 13 M NH₄OH throughout the experiments and the films were prepared with different deposition time varied from 5 to 25 h. In order to improve the hydrophobicity of as deposited silica films, the films were derivatized with 10% trimethylchlorosilane (TMCS) as a silylating agent in hexane solvent for 24 h. Enhancement in wetting behavior was observed for surface derivatized silica films which showed a maximum static water contact angle (172°) and minimum sliding angle (2°) for 25 h of deposition time. The superhydrophobic silica films retained their superhydrophobicity up to a temperature of 550 °C. The silica films were characterized by field emission scanning electron microscopy (FE-SEM), surface profilometer, Fourier transform infrared (FT-IR) spectroscopy, thermo-gravimetric and differential thermal analysis (TG-DTA), percentage of optical transmission, water contact angle measurements. The imperviousness behavior of the films was tested with various acids.     

Optical properties of Fe-doped silica films on Si

Optical properties of Fe-doped silica films on Si were investigated by ellipsometric technique in the region 1-5 eV. Samples were produced by sol-gel method. Precursors were prepared by mixing tetraethoxysilane (TEOS) solution in ethanol and water with aqueous solution of Fe-chloride or Fe-acetate. The coating solution was deposited on Si substrates by spin on technique. The size of Fe-containing nanometric-sized particles depended on technology and varied from 20 to 100 nm. Optical response of complex hybrid samples SiO₂:Fe/Si was interpreted in a multi-layer model. In the inverse problem, the Maxwell equations were solved by transfer matrix technique. Dielectric function of Fe-doped silica layers was calculated in the model of effective media. Analysis of optical data has shown that various Fe-oxides formed. Experimental data for films obtained from precursors with Fe-acetate and annealed in hydrogen were well described by the model calculations taking into account a small contribution 1-5% of metal Fe imbedded in silica. The Fe/Fe-O contribution to optical response increased for samples grown from FeCl₃-precursor. Ellipsometric data for Fe-doped silica films on Si were interpreted taking into account the structural AFM studies as well as the results of magnetic measurements.     

Enhanced flux pinning in pulsed laser deposited Y Ba2Cu3O7−δ : BaTiO3 nanocomposite thin films

The effect of incorporation of BaTiO₃(BTO) nanoparticles on the flux pinning properties of pulsed laser deposited YBCO:BTO thin films was studied. Substantial increase in the critical current density (J_C) and the pinning force density (F_p) of the nanocomposite thin films was observed. At 77 K, and zero applied magnetic field, the value of J_C for YBCO and YBCO:BTO (2%) thin films were 2.93 MA/cm² and 6.43 MA/cm², respectively. At the same temperature and an applied magnetic field of 4 T, the value of J_C increases from 3.6×10⁴ A/cm² for YBCO thin film to 2.7×10⁵ A/cm² for YBCO:BTO (2%) nanocomposite thin film. The study of temperature and field dependence of of YBCO and YBCO:BTO thin films indicates similar type of pinning. The lattice mismatch between YBCO and BTO seems to introduce more defects resulting in the improvement of flux pinning properties.     

Transparent water repellent silica films by sol-gel process

Non-wettable surfaces with high contact angles and facile sliding angle of water droplets have received tremendous attention in recent years. The present paper describes the room temperature (∼27 °C) synthesis of dip coated water repellent silica coatings on glass substrates using iso-butyltrimethoxysilane (iso-BTMS) as a co-precursor. Emphasis is given to the influence of the hydrophobic reagent (iso-BTMS) on the water repellent properties of the silica films. Silica sol was prepared by keeping the molar ratio of tetraethoxysilane (TEOS) precursor, methanol (MeOH) solvent, water (H₂O) constant at 1:16.53:8.26 respectively, with 0.01 M NH₄F throughout the experiment and the molar ratio of iso-BTMS/TEOS (M) was varied from 0 to 0.965. The effect of M on the surface structure and hydrophobicity has been researched. The static water contact angle values of the silica films increased from 65° to 140° and water sliding angle values decreased from 42° to 16° with an increase in the M value from 0 to 0.965. The water repellent silica films are thermally stable up to a temperature of 280 °C and above this temperature the film shows hydrophilic behavior. The water repellent silica films were characterized by the Fourier Transform Infrared (FT-IR) Spectroscopy, Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM), % of optical transmission, thermal and chemical aging tests, humidity tests, static and dynamic water contact angle measurements.     

Work function of sol-gel indium tin oxide (ITO) films on glass

Indium tin oxide (ITO) films (physical thickness, 250-560 ± 25 nm) were deposited on soda lime silica (SLS) glass and silica layer coated (∼200 nm physical thickness) SLS glass substrates by sol-gel technique using alcohol based precursors containing different In:Sn atomic percentages, namely, 90:10, 70:30, 50:50, 30:70. Cubic phase of In₂O₃ was observed up to 50 at.% Sn while cassiterite SnO₂ phase was observed for 70 at.% Sn. Work function of the films was evaluated from inelastic secondary electron cutoff of ultraviolet photoelectron spectroscopy (UPS) energy distribution curve (EDC) obtained under two experimental conditions (i) as-introduced (ii) after the cleaning of the surface by sputtering. Elemental distribution and the presence of oxygen containing contaminant and carbon contaminant of the samples were done by XPS analysis under same conditions. The work function changed little due to the presence of surface contaminants. It was in the range, 3.9-4.2 eV (±0.1 eV).     

Control on wetting properties of spin-deposited silica films by surface silylation method

Control on the wettability of solid materials by liquid is a classical and key issue in surface engineering. Optically transparent water-repellent silica films have been spin-deposited on glass substrates at room temperature (∼27 °C). The wetting behavior of silica films was controlled by surface silylation method using dimethylchlorosilane (DMCS) as a silylating reagent. A coating sol was prepared by keeping the molar ratio of methyltrimethoxysilane (MTMS) precursor, methanol (MeOH) solvent, water (H₂O) constant at 1:8.8:2.64 respectively, with 4 M NH₄OH as a catalyst throughout the experiments and the amount of DMCS in hexane was varied from 0 to 12 vol.%. It was found that with an increase in vol.% of DMCS, the water contact angle values of the films increased from 78° to 136°. At 12 vol.% of DMCS, the film shows static water contact angle as high as 136° and water sliding angle as low as 18°. The hydrophobic silica films retained their water repellency up to a temperature 295 °C and above this temperature the films show superhydrophilic behavior. These results are compared with our earlier research work done on silylation of silica surface using hexamethyldisilazane (HMDZ) and trimethylchlorosilane (TMCS). The hydrophobic silica films were characterized by taking into consideration the Fourier transform infrared (FT-IR) spectroscopy, thermo gravimetric-differential thermal (TG-DT) analyses, scanning electron microscopy (SEM), atomic force microscopy (AFM), % of optical transmission, thermal and chemical aging tests, humidity tests, static and dynamic water contact angle measurements.     

Fabrication and characterization of Pt intermediate transparent and conducting ITO/Pt/ITO multilayer films

Platinum intermediate transparent and conducting ITO/metal/ITO (IMI) multilayered films were deposited by RF and DC magnetron sputtering on polycarbonate substrates without intentional substrate heating. Changes in the microstructure and optoelectrical properties of the films were investigated with respect to the thickness of the intermediate Pt layer in the IMI films. The thickness of Pt film was varied from 5 to 20 nm.In XRD measurements, neither ITO single-layer films nor IMI multilayer films showed any characteristic diffraction peaks for In₂O₃ or SnO₂. Only a weak diffraction peak for Pt (1 1 1) was obtained in the XRD spectra. Thus, it can be concluded that the Pt-intermediated films in the IMI films did not affect the crystallinity of the ITO films. However, equivalent resistivity was dependent on the presence and thickness of the Pt-intermediated layer. It decreased as low as 3.3×10⁻⁴ Ω cm for ITO 50 nm/Pt 20 nm/ITO 30 nm films. Optical transmittance was also strongly influenced by the Pt-intermediated layer. As Pt thickness in the IMI films increased, optical transmittance decreased to as low as 30% for ITO 50 nm/Pt 20 nm/ITO 30 nm films.     

Preparation and characterization of ZrO2:Sm amorphous thin films by solid state photochemical deposition method

Thin films of ZrO₂ loaded with 10, 30 and 50 mol% Sm were prepared by a photochemical method using thin films of metal acetylacetonate complexes as precursors. The photolysis of these films induces the fragmentation of the acetylacetonate ligand and the partial reduction of metal ion together with volatile organic compounds. When the metallic complex is exposed to air, the product of the reaction is metal oxide. The photoreactivity of these films was monitored by FT-IR spectroscopy, followed by a post-annealing treatment process. The obtained films were characterized by X-ray photoelectron spectroscopy and atomic force microscopy.Photoluminescense studies of the films employed 400 nm radiation for excitation of the Sm ions present. The emission spectra showed signals arising from the ⁴G_5/2→⁶H_J (J=3/2, 7/2, 9/2) transitions, where the ⁴G_5/2→⁶H_3/2 transition has the highest intensity. The concentration dependence of the PL intensity was also studied. A maximum PL intensity was observed with 10 mol% Sm content but then diminished with higher Sm concentrations.     

Preparation and characterization of Cd2Nb2O7 thin films on Si substrates

Thin Cd₂Nb₂O₇ films were grown on single-crystal p-type SiO₂/Si substrates by the metallo-organic decomposition (MOD) technique. The films were investigated by X-ray diffraction, X-ray energy-dispersive spectroscopy, and field emission scanning electron microscopy, and showed a single phase (cubic pyrochlore), a crack-free spherical grain structure, and nanoparticles with a mean size of about 68 nm. A Cauchy model was also used in order to obtain the thickness and index of refraction of the stack layers (transparent layer/SiO₂/Si) by spectroscopic ellipsometry (SE). The dielectric constant (K) of the films was calculated to be about 25 from the capacitance-voltage (C-V) measurements.     

Influence of N2 flow ratio on the properties of hafnium nitride thin films prepared by DC magnetron sputtering

Hafnium nitride (Hf-N) thin films were deposited on fused silica at different N₂ flow ratio (N₂/N₂ + Ar) using a reactive DC magnetron sputtering system. A gradual evolution in the composition of the films from Hf₃N₂, HfN, to higher nitrides was found through X-ray diffraction (XRD). Films of Hf₃N₂ and HfN show positive temperature coefficients of resistivity, while higher nitride has a negative one. Highly oriented growth of (0 0 1) Hf₃N₂ and NaCl-structure (1 0 0) HfN films were fabricated on fused silica substrate at relatively lower temperature of 300 °C. The electrical resistivity values of both as-deposited and post-deposition annealed films were measured by a four-point probe method. The obtained minimum resistivity of as-deposited film is 20 μΩ cm, and this result shows potential application of HfN films as electrode materials in electronic devices.     

The influence of incorporating organic molecules or inorganic nanoparticles on the optical and electrical properties of carbon nanotube films

Organic molecules and inorganic nanoparticles were incorporated into transparent and conductive single- or double-wall carbon nanotube (SWNT or DWNT) films, and their electrical and optical properties were measured. When organic tetrafluoro-tetracyanoquinodimethane (F₄TCNQ) molecules were incorporated into the nanotube films, sheet resistance was reduced to ∼50% of those from the pristine SWNT and DWNT films. Larger improvements were observed with Au nanoparticle decoration or HNO₃/SOCl₂ dipping processes. The sheet resistances were measured to be at 75% of transmittance for HNO₃/SOCl₂-treated DWNT films and at 77% for Au-incorporated DWNT films, making their electrical conductivities 200%-300% better than those of the pristine DWNT films. It was observed that DWNTs have better electrical/optical performance than SWNTs. The relative influence of various dopants, F₄TCNQ, Au, and HNO₃/SOCl₂ as well as microwave irradiation on the optical and electrical properties was identified by using Raman and UV-vis-NIR spectra.     

Imperviousness of the hydrophobic silica aerogels against various solvents and acids

The experimental results on the imperviousness of the silica aerogels against various organic solvents and acids, are reported. Various types of hydrophobic silica aerogels were prepared using methyltrimethoxysilane (MTMS); tetraethoxysilane (TEOS) with ethyltriethoxysilane (ETES) and phenyltriethoxysilane (PTES) as co-precursors. The organic solvents used were: methanol, ethanol and acetone, and the acids used were: hydrochloric acid (HCl), nitric acid (HNO₃) and sulphuric acid (H₂SO₄). The imperviousness of the aerogels against these solvents and acids were tested with the variation of the percentage of organic solvents and acids in water from 10 to 100% and was characterized by the contact angle measurements. It was observed that in all the cases, the contact angle decreased with an increase in the percentage of solvent in water. While there was no absorption of the solvent up to 20% in water by the ETES and PTES modified aerogels, the MTMS-based aerogels showed the imperviousness up to 60% of the solvent in water. The MTMS aerogels were also impervious against all the three acids up to 100%, while the ETES and PTES modified aerogels could withstand only up to 80% of acids in water.     

Relative performances of effective medium formulations in interpreting specific composite thin films optical properties

Several powerful effective medium formulations/approximation (EMA) and associated theories with different origins and concepts have been discussed and utilized here in order to model the experimental refractive index evolutions of ZrO₂-SiO₂ and Gd₂O₃-SiO₂ composite films with respect to their compositional mixings. Amongst these formulations, the Böttcher's generalized theory has been noticed to have more versatility and can simulate varieties of experimental observations incorporating a form factor parameter to account for the grain structure and morphology to a great extent. The refractive index modeling results of most of the available theories were compared with respect to their functional evolutions and limitations. It was noticed that at higher silica fractions (>20%) in our composite films, the effective experimental refractive index parameters have remained close to the most modeling results and Böttcher's expression has shown to fit the observable parameters very accurately. However, under low silica compositions (<20%) the refractive index values of the composite films depicted different functional evolutions. Such deviations have been attributed to the various morphological, grain structure and band gap supremacies observed in these specific composite films which are not accounted by the effective medium formulations and approximations. These observations are well supported by the atomic force microscopy results.     

Ultrasound-assisted extraction of functional compound from mulberry (Morus alba L.) leaf using response surface methodology and effect of microencapsulation by spray drying on quality of optimized extract

This study aimed to optimize the ultrasound-assisted extraction (UAE) condition of mulberry leaf extract (MLE) using response surface methodology and to microencapsulate MLE by spray drying using different coating materials and ratios of coating material and MLE. The extraction results showed that MLE from condition of 60 °C (X₁, temperature), 30 min (X₂, time) and 60% v/v (X₃, ethanol concentration) exhibited the highest bioactive compound and antioxidant activity (DPPH and FRAP assay). Based on this optimal condition, MLE was further encapsulated by spray drying. It was found that MLE encapsulated with resistant maltodextrin at ratio of MLE and resistant maltodextrin 1:1 (w/w) showed the highest encapsulation yield (%) and encapsulation efficiency (%). Water solubility, moisture content and water activity were non-significant (p > 0.05) among the microcapsules. The scanning electron microscope (SEM) revealed that the types of coating material affected their microstructures and microcapsules prepared by resistant maltodextrin as coating material had a spherical shape, smooth surface and less shrinkage than microcapsules prepared by maltodextrin and gum arabic which had rough surfaces. The highest antioxidant activity was obtained from microcapsule prepared by gum arabic at ratio of MLE and gam arabic 1:2 (w/w). In conclusion, optimal condition from UAE and encapsulation by spray drying suggest the critical potential for production of functional food with improved bioactive compound stability and maximized antioxidant activity.     

Characterization of Cu(In,Ga)Se2 thin films prepared by evaporationfrom ternary compounds

Thin films of Cu(In,Ga)Se₂ were fabricated by evaporation from ternary CuGaSe₂ and CuInSe₂ compounds for photovoltaic device applications and their properties were investigated. From XRF analysis, the Cu:(In+Ga):Se atomic ratio in all thin films was approximately 1:1:2. The Ga/(In+Ga) atomic ratio in the thin films changed linearly from 0 to 1.0 with increasing the [CGS]/([CGS]+[CIS]) mole ratio in the evaporating materials. However, for thin films prepared at the [CGS]/([CGS]+[CIS]) mole ratio above 0.4, the composition by EPMA analysis was not consistent with that by XRF analysis. The result of EPMA analysis showed that the surface of a thin film was Cu-rich. XRD studies demonstrated that the thin films prepared at the [CGS]/([CGS]+[CIS]) mole ratio under 0.2 had a chalcopyrite Cu(In,Ga)Se₂ structure and the preferred orientation to the 112 plane. On the other hand, XRD patterns of the thin films produced at the [CGS]/([CGS]+[CIS]) mole ratio above 0.6 showed the diffraction lines from a chalcopyrite Cu(In,Ga)Se₂ and a foreign phase. The separation of a peak was observed near 2θ=27°, indicative the graded Ga concentration in Cu(In,Ga)Se₂ thin film.     

Thin porous Ni-YSZ films as anodes for a solid oxide fuel cell

Porous Ni-YSZ (YSZ—yttria-stabilized zirconia) films were fabricated by reactive co-sputtering of a Ni and a Zr-Y target, followed by sequentially annealing in air at 900 °C and in vacuum at 800 °C. The Ni-YSZ films comprised small grains and pores that were tens of nanometers in size. The porous Ni-YSZ films were used as an anode on one side of a YSZ electrolyte disc and a La_0.7Sr_0.3MnO₃ thick film was used as a cathode on the other side of the disc to form solid oxide fuel cells (SOFCs). The voltage-current curves of the SOFCs with single- and a triple-layered porous anodes were measured in a single-chamber configuration, in a mixture of CH₄ and air (CH₄:O₂ volume ratio=2:1). The maximum power density of the SOFC using the single-layered porous Ni-YSZ thin films as the anode was 0.38 mW cm⁻², which was lower than that of 0.76 mW cm⁻², obtained using a screen-printed Ni-YSZ thick anode. The maximum power density of the SOFC with a thin anode was increased, but varied between 0.6 and 1.14 mW cm⁻² when a triple-layered porous Ni-YSZ anode was used.