Fabrication of hydrophobic surface of titanium dioxide films by successive ionic layer adsorption and reaction (SILAR) method

Titanium dioxide (TiO₂) films were fabricated on fluorine doped tin oxide (FTO) coated glass substrate using successive ionic layer adsorption and reaction (SILAR) method. The X-ray diffraction, scanning electron microscopy, transmission electron microscopy, optical absorption and contact angle measurement were applied to study the structural, surface morphological, optical and surface wettability properties of the as-deposited and annealed TiO₂ films. The X-ray diffraction studies revealed both as-deposited and annealed TiO₂ films are amorphous. Irregular shaped spherical grains of random size and well covered to the fluorine doped tin oxide coated glass substrates were observed from SEM studies with some cracks after annealing. The optical band gap values of virgin TiO_2, annealed, methyl violet and rose bengal sensitized TiO₂ were found to be 3.6, 3.5, 2.87 and 2.95 eV, respectively. Surface wettability studied in contact with liquid interface, showed hydrophobic nature as water contact angles were greater than 90°. The adsorption of dyes, as confirmed by the photographs, is one of the prime requirements for dye sensitized solar cells (DSSC).     

Deposition of copper iodide thin films by chemical bath deposition (CBD) and successive ionic layer adsorption and reaction (SILAR) methods

In this paper, we report structural, morphological, electrical studies of copper iodide (CuI) thin films deposited onto glass substrates by chemical bath deposition (CBD) and successive ionic layer adsorption and reaction (SILAR) methods. CuI thin films were characterized for their structural, morphological and wettability studies by means of X-ray diffraction (XRD), FT-Raman spectroscopy, scanning electron microscopy (SEM), optical absorption, and contact angle measurement methods. Thickness of thin films was 1 ± 0.1 μm measured by gravimetric weight difference method. The CuI thin films were nanocrystalline, with average crystal size of ～60 nm. The FT-IR study confirmed the formation of CuI on the substrate surface. SEM images revealed the compact and cube like structure for CuI thin films deposited by CBD and SILAR methods, respectively. Optical absorption study revealed optical energy gaps as 2.3 and 3.0 eV for CBD and SILAR methods, respectively. Wettability study indicated that CuI thin films deposited by SILAR method are more hydrophobic as compared to CBD method.     

Structural properties of the titanium dioxide thin films grown by atomic layer deposition at various numbers of reaction cycles

A dependence of structural properties of TiO₂ films grown on both Si- and Ti-substrates by atomic layer deposition (ALD) at the temperature range of 250-300 °C from titanium ethoxide and water on the number of reaction cycles N was investigated using Fourier-transform infrared (FTIR) spectroscopy and X-Ray diffraction (XRD). TiO₂ films grown on both Si- and Ti-substrates revealed amorphous structure at low values of N < 400. However, an increase of N up to values 400-3600 resulted in the growth of polycrystalline TiO₂ with structure of anatase on both types of substrates and according to XRD-measurements the sizes of crystallites rose with the increase of N. The maximum anatase crystallite size for TiO₂ grown on Ti-substrate was found to be on ∼35% lower in comparing with that for TiO₂ grown on Si-substrate. A use of titanium methoxide as a Ti precursor with the ligand size smaller than in case of titanium ethoxide allowed to observe an influence of the ligand size on both the growth per cycle and structural properties of TiO₂. The average growth per cycle of TiO₂ deposited from titanium methoxide and water (0.052 ± 0.01 nm/cycle) was essentially higher than that for TiO₂ grown from titanium ethoxide and water (0.043 ± 0.01 nm/cycle). Ligands of smaller sizes were found to promote the higher crystallinity of TiO₂ in comparison with the case of using the titanium precursor with ligands of bigger sizes.     

Preparation and characterization of ZnTe thin films by SILAR method

Nanocrystalline zinc telluride (ZnTe) thin films were prepared by using successive ionic layer adsorption and reaction (SILAR) method from aqueous solutions of zinc sulfate and sodium telluride. The films were characterized by X-ray diffraction, scanning electron microscopy, energy dispersive X-ray analysis and optical absorption measurement techniques. The synthesized ZnTe thin films were nanocrystalline with densely aggregated particles in nanometer scale and were free from the voids or cracks. The optical band gap energy of the film was found to be thickness dependent. The elemental chemical compositional stoichiometric analysis revealed good Zn:Te elemental ratio of 53:47.     

Cd0.5Zn0.5Se wide range composite thin films for solar cell buffer layer application

Cd_0.5Zn_0.5Se composite thin films were obtained on glass substrate using aqueous alkaline solution at low temperature using cadmium acetate and zinc acetate as Cd²⁺ and Zn²⁺ and Se²⁻ ion sources. Different phases of individuals i.e. CdSe and ZnSe, spherical and needle shape surface morphology and good elemental chemical stoichiometric ratio were observed from X-ray diffraction, scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX) studies, respectively. The band gap and electrical resistivity of the composite film were 2.35 eV and about 10⁷ Ω cm, respectively.     

Structural and electrical properties of evaporated Fe thin films

Series of Fe thin films have been prepared by thermal evaporation onto glass and Si(1 0 0) substrates. The Rutherford backscattering (RBS), X-ray diffraction (XRD), Scanning electron microscopy (SEM) and the four point probe techniques have been used to investigate the structural and electrical properties of these Fe thin films as a function of the substrate, the Fe thickness t in the 76-431 nm range and the deposition rate. The Fe/Si samples have a 〈1 1 0〉 for all thicknesses, whereas the Fe/glass grows with a strong 〈1 0 0〉 texture; as t increases (>100 nm), the preferred orientation changes to 〈1 1 0〉. The compressive stress in Fe/Si remains constant over the whole thickness range and is greater than the one in Fe/glass which is relieved when t > 100 nm. The grain size D values are between 9.2 and 30 nm. The Fe/glass films are more electrically resistive than the Fe/Si(1 0 0) ones. Diffusion at the grain boundary seems to be the predominant factor in the electrical resistivity ρ values with the reflection coefficient R greater in Fe/glass than in Fe/Si. For the same thickness (100 nm), the decrease of the deposition rate from 4.3 to 0.3 Å/s did not affect the texture and the reflection coefficient R but led to an increase in D and a decrease in the strain and in ρ for both Fe/glass and Fe/Si systems. On the other hand, keeping the same deposition rate (0.3 Å/s) and increasing the thickness t from 76 to 100 nm induced different changes in the two systems.     

Effect of [Cu]/[In] ratio on properties of CuInS2 thin films prepared by successive ionic layer absorption and reaction method

CuInS₂ ternary films were prepared by a soft solution processing, i.e. successive ionic layer absorption and reaction (SILAR) method. The films were deposited on glass substrates at room temperature and heat-treated under Ar atmosphere at 500 °C for 1 h. CuCl₂ and InCl₃ mixed solutions with different ionic ratios ([Cu]/[In]) were used as cation precursor and Na₂S as the anion precursor. The effect of the [Cu]/[In] ratio in precursor solution on the structural, chemical stoichiometry, topographical, optical and electrical properties of CuInS₂ thin films was investigated. XPS results demonstrated that stoichiometric CuInS₂ film can be obtained by adjusting [Cu]/[In] ratios in solution. Chalcopyrite structure of the film was confirmed by XRD analysis. The near stoichiometric CuInS₂ film has the optical band gap E_g of 1.45 and resistivity decreased with increase of [Cu]/[In] ratios.     

Bismuth oxide thin films prepared by chemical bath deposition (CBD) method: annealing effect

Bismuth oxide thin films have been deposited by room temperature chemical bath deposition (CBD) method and annealed at 623 K in air. They were characterized for structural, surface morphological, optical and electrical properties. From the X-ray diffraction patterns, it was found that after annealing a non-stoichiometric phase, Bi₂O_2.33, was removed and phase pure monoclinic Bi₂O₃ was obtained. Surface morphology of Bi₂O₃ film at lower magnification SEM showed rod-like structure, however, higher magnification showed a rectangular slice-like structure perpendicular to substrate, giving rise to microrods on the surface. The optical studies showed the decrease in band gap by 0.3 eV after annealing. The electrical resistivity variation showed semiconductor behavior and from thermoemf measurements, the electrical conductivity was found to be of n-type.     

Spectroscopic study of an atmospheric pressure plasma generated for the deposition of titanium dioxide thin films

TiO₂ thin films are applied in various domains, e.g. air or water purification, self-cleaning surfaces etc. The deposition of titanium dioxide at industrial scale remains challenging. Atmospheric pressure plasma chemical vapor deposition methods are currently developed to provide an easy and viable method for deposition at industrial scale. Even though those methods lead to promising applicative coatings their formation mechanisms remain poorly investigated. In order to investigate the effect of the plasma parameters, i.e. plasma power and introduction of oxygen, on the plasma chemistry, optical emission spectroscopy (OES) is employed to monitor the various species present in the discharge. X-ray Photoelectron Spectroscopy (XPS) analyses of the deposited thin films are carried out and show that by either decreasing the plasma power or introducing oxygen the carbon impurities in the layer can be reduced. By comparing OES and XPS data, the ratio of carbon containing species (CH and C₂) to oxygen, i.e. I_CH/I_O or I_C2/I_O, in the discharge is shown to be related to the carbon/oxygen composition ratio in the layer.     

Photocatalytic and optical properties of titanium dioxide thin films prepared by metalorganic chemical vapor deposition

Titanium dioxide thin films have been deposited by metalorganic chemical vapor deposition (MOCVD) over sodalime glass substrates at substrate temperatures ranging from 250 °C to 450 °C. The effect of deposition temperature on the structure and microstructure of the obtained films has been studied by x-rays diffraction (XRD) and scanning electron microscopy (SEM), respectively. Diffraction patterns show the existence of a pure anatase phase beside a texture change with the increase of deposition temperature. Micrographs show grain fragmentation with the increase in deposition temperature. UV–Vis. spectra have been recorded by spectrophotometery. The optical energy gap has been calculated for the deposited films from the spectrophotometrical data. Photocatalytic experiments have been carried out. The photocatalytic activity has been found to decrease with the increase in deposition temperature.     

Use of modified chemical route for ZnSe nanocrystalline thin films growth: Study on surface morphology and physical properties

The zinc selenide thin films have been deposited using modified chemical bath deposition (M-CBD) method. Zinc acetate and sodium selenosulphate were used as Zn²⁺ and Se²⁻ ion sources, respectively. The preparative parameters such as concentration, pH, number of deposition cycles have been optimized in order to deposit ZnSe thin films. The as-deposited ZnSe thin films are specularly reflective and faint yellowish in color. The as-deposited ZnSe films are annealed in an air atmosphere at 473 K for 2 h. The films are characterized using structural, morphological, compositional, optical and electrical properties.     

Rapid growth of nanocrystalline CuInS2 thin films in alkaline medium at room temperature

Layer-by-layer (LbL) deposition of CuInS₂ (CIS) thin films at room temperature (25 °C) from alkaline CuSO₄ + In₂(SO₄)₃ and Na₂S precursor solutions was reported. The method allowed self-limited growth of CIS films with nanocrystalline structure and composed of densely packed nanometer-sized grains. The as-deposited CIS film was 250 nm thick and composed of closely packed particles of 20-30 nm in diameter. The alkaline cationic precursor solution was obtained by dissolving CuSO₄ and InSO₄ in deionized water with a appropriate amount of hydrazine monohydrate (H-H) and 2,2′,2″-nitrilotriethanol (TEA). CIS films were annealed at 200 °C for 2 h and effect of annealing on structural, optical, and surface morphological properties was thoroughly investigated by means of X-ray diffraction, scanning electron microscopy, transmission electron microscopy, UV-vis spectrometer, C-V, and water contact angle techniques, respectively.     

The growth and structure of titanium dioxide films on a Re(1 0 −1 0) surface: Rutile(0 1 1)-(2 × 1)

Titanium dioxide films were grown on Re(1 0 −1 0) by Ti vapor deposition in oxygen at T = 830 K and studied by means of low-energy electron diffraction (LEED), X-ray photoelectron spectroscopy (XPS), low-energy ion scattering (LEIS) and X-ray diffraction (XRD). The Ti oxide stoichiometry was determined by XPS as Ti:O = 1:2, with the Ti oxidation state (4+). The TiO₂ growth was monitored by means of LEED as a function of film thickness. Extending the coverage from the submonolayer into the multilayer regime gives rise to a p(2 × 2) pattern, a (poorly ordered) (1 × 1), and, finally, a stable (2 × 2) structure, the latter being associated with a homogeneous TiO₂ phase. For normal electron incidence, the (2 × 2) LEED pattern exhibits systematically extinguished beams at (n ± 1/2, 0) positions, indicating a glide mirror plane. The pg(2 × 2) structure could be explained by both a rutile(0 1 1)-(2 × 1) reconstructed surface and a bulk truncated brookite(0 0 1) surface. Faceting phenomena, i.e. running LEED spots, observed with thin TiO₂ films point to the formation of a rutile(0 1 1)-(2 × 1) surface with two domains and {0 1 1}-(2 × 1) facets and rule out the brookite alternative. Confirmation of this assignment was obtained by an XRD analysis performed at the Berlin synchrotron facility BESSY.     

Investigation of growth mechanism of nano-scaled cadmium sulfide within titanium dioxide nanotubes via solution deposition method

The growth mechanism of cadmium sulfide nanomaterials, including nanodots, nanotubes, and nanorods, within titanium dioxide nanotubes via solution deposition method was investigated. The materials obtained were characterized by field emission scanning electron microscopy, UV-visible spectroscopic and photoelectrochemical techniques. The results revealed that: (1) the concentration of ions introduced into the tubes influenced the morphology of the cadmium sulfide obtained: at low concentration, defects on the tube walls induce heterogeneous nucleation hence cadmium sulfide was observed attaching to the walls; at high concentration, particle aggregation occur due to negligible repulsion between the nuclei resulting in sedimentation of cadmium sulfide particles; (2) cadmium sulfide prefers to grow on seeds formed initially, so that nanodots or nanotubes and nanorods were formed at low and at high concentrations respectively; (3) the order of ions introduction also influences the morphology of cadmium sulfide formed within the tubes, (4) the photoresponse of the obtained nanomaterials was extended efficiently; and (5) the photoelectrochemical properties were strongly influenced by both the amount and the morphology of the deposited CdS sensitizer.     

Effect of cycle numbers on the structural,linear and nonlinear optical properties in Fe2O3 thin films deposited by SILAR method

Fe₂O₃ thin films were deposited by Successive Ionic Layer Adsorption and Reaction (SILAR) method onto glass substrates at different cycle numbers to investigate structural, linear and nonlinear optical properties. X-Ray Diffraction (XRD) analysis revealed that the Fe₂O₃ thin films have a non-crystalline nature. The morphological properties of the films were investigated by Field Emission-Scanning Electron Microscopy (FE-SEM) and the results show that the films’ surfaces are porous. The linear and nonlinear optical parameters were evaluated and analyzed by using transmittance and absorbance measurements. For these measurements, UV–Vis spectroscopy at room temperature was used. The refractive index values were calculated in the range of 1.45–3.23 for visible region (400–700 nm). Obtained results reveal that direct optical band gap changed between 2.62 and 2.68 eV and indirect optical band gap changed between 1.67 and 1.77 eV. Additionally, optical electronegativity, optical dielectric constants, surface and volume energy loss functions, nonlinear refractive index, linear optical susceptibility, third-order nonlinear optical susceptibility, optical and electrical conductivity, and loss tangent values were calculated and discussed in detail. It was found that each parameter studied is dependent on the cycle numbers. Also, it can be stated that Fe₂O₃ thin films are promising candidate for solar cells and optoelectronic device technology.     

Preparation and characterization of nanocrystalline ITO thin films on glass and clay substrates by ion-beam sputter deposition method

Nanocrystalline indium tin oxide (ITO) thin films were prepared on clay-1 (Clay-TPP-LP-SA), clay-2 (Clay-TPP-SA) and glass substrates using ion-beam sputter deposition method. X-ray diffraction (XRD) patterns showed that the as-deposited ITO films on both clay-1 and clay-2 substrates were a mixture of amorphous and polycrystalline. But the as-deposited ITO films on glass substrates were polycrystalline. The surface morphologies of as-deposited ITO/glass has smooth surface; in contrast, ITO/clay-1 has rough surface. The surface roughnesses of ITO thin films on glass and clay-1 substrate were calculated as 4.3 and 83 nm, respectively. From the AFM and SEM analyses, the particle sizes of nanocrystalline ITO for a film thickness of 712 nm were calculated as 19.5 and 20 nm, respectively. Optical study showed that the optical transmittance of ITO/clay-2 was higher than that of ITO/clay-1. The sheet resistances of as-deposited ITO/clay-1 and ITO/clay-2 were calculated as 76.0 and 63.0 Ω/□, respectively. The figure of merit value for as-deposited ITO/clay-2 (12.70 × 10⁻³/Ω) was also higher than that of ITO/clay-1 (9.6 × 10⁻³/Ω), respectively. The flexibilities of ITO/clay-1 and ITO/clay-2 were evaluated as 13 and 12 mm, respectively. However, the ITO-coated clay-2 substrate showed much better optical and electrical properties as well as flexibility as compared to clay-1.     

Surface structure and composition of flat titanium thin films as a function of film thickness and evaporation rate

To correlate flat titanium film surface properties with deposition parameters, titanium flat thin films were systematically deposited on glass substrates with various thicknesses and evaporation rates by electron-beam evaporation. The chemical compositions, crystal structure, surface topographies as well as wettability were investigated by using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), atomic force microscopy (AFM) and water contact angle measurement, respectively. The films consisted mainly of TiO₂. Small percentages of Ti₂O₃ and metallic Ti were also found at the film surface using high-resolution XPS analysis. Quantitative XPS showed little differences regarding elemental compositions among different groups of films. The films were obtained by varying the deposition rate and the film thickness, respectively. XRD data showed consistent reflection patterns of the different titanium samples deposited using different film thicknesses. Without exception measurements of all samples exhibited contact angles of 80° ± 5°. Quantitative AFM characterization demonstrated good correlation tendency between surface roughness and film thickness or evaporation rate, respectively. It is important to notice that titanium films with different sizes of grains on their surfaces but having the same chemistry and film bulk structure can be obtained in a controllable way. By increasing the film thickness and evaporation rate, the surface roughness increased. The surface morphology and grain size growth displayed a corresponding trend. Therefore, the control of these parameters allows us to prepare titanium films with desired surface properties in a controllable and reproducible way for further biological investigations of these materials.     

A non-thermal chemical synthesis of hydrophilic and amorphous cobalt oxide films for supercapacitor application

Present work explored a room temperature, simple and low cost chemical route for the preparation of hydrophilic cobalt oxide films from alkaline cobalt chloride (CoCl₂:6H₂O) and double distilled water precursor solutions. As-deposited cobalt oxide films showed amorphous nature, which is one of the prime requirements for supercapacitor, as confirmed from X-ray diffraction studies. Changes in direct band gap energy and electrical resistivity of as-deposited cobalt oxide films were confirmed after annealing. Spherical grains of about 40-50 nm diameters were uniformly distributed over the substrate surface. Surface wettability studied in contact with liquid interface, showed hydrophilic nature as water contact angle was <90°. Finally, presence of cobalt-oxygen covalent bond was observed from Raman shift experiment.     

PbICl precursor solutions for all solid-state PbS quantum-dot sensitized TiO2 nanorod array solar cells using successive ionic layer adsorption and reaction method

In this work, PbICl precursor solution in N,N-dimethylformamide was successfully applied to deposit PbS quantum-dots on TiO₂ nanorod arrays by successive ionic layer adsorption and reaction method (SILAR). The influence of PbI₂, PbBr₂, PbICl precursor solution on the morphology, crystal size and optical absorption of PbS quantum-dots was investigated and the photovoltaic performance of the corresponding solid-state PbS quantum-dot sensitized TiO₂ nanorod array solar cells with spiro-OMeTAD was evaluated. The average crystal sizes of PbS quantum-dots were 9.0 nm of PbI₂, 8.6 nm of PbBr₂ and 8.4 nm of PbICl and the photoelectric conversion efficiency of the corresponding solar cells achieved 2.63%, 3.00%, 3.45%. The result revealed that PbICl precursor solution was superior to PbBr₂ and PbI₂.     

Improved electrical,magnetic and dielectric properties of polypyrol (PPy) substituted spinel ferrite composites

CoTb_0.03Fe_1.97O₄ ferrite and poypyrrole (PPy) polymer nano composites were prepared by mixing the nano crystalline ferrite with poypyrrole (PPy) by following the solid state reaction synthesis route. The XRD patterns of CoTb_0.03Fe_1.97O₄ spinel ferrite powders and polymer (PPy) exhibited single phase spinel structure. The amorphous nature of PPy was evidenced by the broad peaks of XRD patterns. The surface morphology unfolded heterogeneous distribution in composites and ferrite. The grains in ferrite were spherical in shape with clear boundaries. The morphology was appreciably altered by the inclusion of ferrite contents. The higher activation energy and resistivity aroused due to blocking of conduction mechanism owing to nanoparticles embedded in the PPy matrix. A downfall in the dielectric loss of the composites is observed as the frequency of the applied field is increased. The incorporation of ferrite contents optimized the magnetic parameters of the composites. The enhanced coercivity (Hc) of these nanocomposites might be beneficial for memory devices.