Fabrication of cuprous and cupric oxide thin films by heat treatment

Cuprous oxide (Cu₂O) and cupric oxide (CuO) thin films were prepared by thermal oxidation of copper films coated on indium tin oxide (ITO) glass and non-alkaline glass substrates. The formation of Cu₂O and CuO was controlled by varying oxidation conditions such as, oxygen partial pressure, heat treatment temperature, and oxidation time. The microstructure, crystal direction, and optical properties of copper oxide films were measured with X-ray diffraction, atomic force microscopy, and optical spectroscopy. The results indicated that the phase-pure Cu₂O and CuO films were produced in the oxidation process. Optical transmittance and reflectance spectra of Cu₂O and CuO clearly exhibited distinct characteristics related to their phases. The electrical properties indicated that these films formed ohmic contacts with Cu and ITO electrode materials. Multilayers of Cu₂O/CuO were fabricated by choosing the oxidation sequence. The experimental results in this paper suggest that the thermal oxidation method can be employed to fabricate device quality Cu₂O and CuO films that are up to 200–300 nm thick.     

Morphological and optical characterization of thermally evaporated copper sulphide thin films

Thin films of Cu₂S on opaque gold layers and quartz substrates at the temperature of 393 K were deposited by a thermal evaporation technique. The surface morphology of the Cu₂S thin films at different thicknesses is investigated by AFM. It is seen that all the films are composed of highly coordinated spherical nano-sized particles well adhered to the substrate. The transmittance and reflectance spectra of Cu₂S thin films on the quartz substrate were recorded by a UV–visible spectrophotometer. The results show that the thermally evaporated Cu₂S thin films have the characteristic transmittance and reflectance suitable for optoelectronic applications. The stoichiometry and surface morphology of a grown Cu₂S thin film were confirmed by energy-dispersive X-ray spectroscopy (EDAX) and scanning electron microscopy (SEM), respectively. The dependence of the refractive index and the extinction coefficient on the photon energy for both the surface film and the opaque gold layer have been determined by ellipsometry. From the spectral behaviour of the absorption coefficient at two distinct absorption regions, a dual-band scheme of optical absorption for a Cu₂S thin film is described. The indirect and direct edges of Cu₂S are found to be about at 0.91 eV and 2.68 eV, respectively.     

The structural and optical property dependence of disordered copper oxide on oxygen content

This study has investigated the optical and structural properties of reactively sputtered copper oxide. The investigated Cu to O ratio (oxygen content) spans the metal-insulator transition. Initially, the number of copper crystallites reduces and Cu₂O crystallite numbers increase with increasing oxygen content, this then turns to a crystallite evolution of Cu₂O to CuO as the oxygen content is increased above the nominal value for Cu₂O, with no copper crystallites remaining. Along with the change in the structure, the system smoothly evolves from optically being metallic in nature to being band gap like, with increasing oxygen content.     

Frohlich interaction and associated resonance enhancement in nanostructured copper oxide films

Nanostructured copper oxide films were prepared by the oxidation of copper films by thermal evaporation of metallic copper. Analysis of HRTEM images showed that the films of Cu₂O and CuO phases had. The band gap of the nanostructured sample of Cu₂O was suitable for resonance scattering by intraband Fröhlich interaction in this sample. Micro‐Raman studies revealed an intense resonance Raman peak corresponding to a forbidden mode of Cu₂O. Copyright © 2011 John Wiley & Sons, Ltd.     

Structure and optical properties of chemically synthesized titanium oxide deposited by evaporation technique

Titanium oxide inorganic ion exchange material was synthesized by hydrolysis with water and ammonia solution. Structural feature of the synthesized titanium oxide was analyzed using X-ray diffraction, X-ray fluorescence and infrared spectrometer technique. Tentative formula of titanium oxide was determined and written as TiO₂·0.58H₂O. Titanium oxide films were deposited on glass substrates by means of an electron beam evaporation technique at room temperature from bulk sample. The films were annealed at 250, 350, 450, and 550 °C temperatures. Transmittance, reflectance, optical energy gap, refractive index and extinction coefficient were investigated. The transmittance values of 85% in the visible region and 88% in the near infrared region have been obtained for titanium oxide film annealed at 550 °C. Kubelka-Munk function was used to evaluate the absorption coefficient which was used to determine the optical band gap. It was found that the optical band gap increases with increasing annealing temperature whereas the refractive index and extinction coefficient decreases.     

Fabrication of Cu2O nanocrystalline thin films photosensor prepared by RF sputtering technique

Cuprous oxide (Cu₂O) nanocrystalline thin films were prepared on two types of substrates known as crystalline silicon and amorphous glass, by radio frequency reactive magnetron sputtering method. Scanning electron microscopy images confirmed that Cu₂O particles covered the entire surface of both substrates with smoothing distribution. The root mean square surface roughness for the prepared Cu₂O thin films on glass and Si (111) substrates is 4.16, and 3.36 nm, respectively. Meanwhile, X-ray diffraction results demonstrated that the two phases of Cu₂O and CuO were produced on Si (111) and glass substrates. The optical bandgap of Cu₂O thin films synthesised on glass substrate is 2.42 eV. Furthermore, the prepared Cu₂O nanocrystalline thin films have showed low reflectance value in the visible spectrum. Metal-Semiconductor-Metal photodetector based Cu₂O nanocrystalline thin films deposited onto Si (111) was fabricated using aluminium and platinum, with the current-voltage and photoresponse characteristic investigated under various applied bias voltages. The fabricated Metal-Semiconductor-Metal (M-S-M) photodetector had shown 126% sensitivity in the presence of 10 mW/cm² of 490 nm light with 1.0 V bias, displaying 90 and 100 ms response and recovery times, respectively. These findings have demonstrated the suitability of M-S-M Cu₂O photodetector as an affordable photosensor in the future.     

Optical properties of cuprous telluride films

The structure of vacuum-deposited cuprous telluride Cu₂Te films deposited on carbon substrates was observed by means of an electron microscope. Films on glass substrates were also investigated by X-ray diffraction. The optical constants (the refractive index n and the extinction coefficient k) of Cu₂Te thin films were determined from the measured transmittance and reflectance at normal incidence of light in the wavelength range 0.4 m to 2.5 m. The variation of the optical constants with thickness for different evaporated films have been determined.     

Effect of post-annealing on the properties of copper oxide thin films obtained from the oxidation of evaporated metallic copper

Thin films of copper oxide were obtained through thermal oxidation (100-450 °C) of evaporated metallic copper (Cu) films on glass substrates. The X-ray diffraction (XRD) studies confirmed the cubic Cu phase of the as-deposited films. The films annealed at 100 °C showed mixed Cu-Cu₂O phase, whereas those annealed between 200 and 300 °C showed a single cubic Cu₂O phase. A single monoclinic CuO phase was obtained from the films annealed between 350 and 450 °C. The positive sign of the Hall coefficient confirmed the p-type conductivity in the films with Cu₂O phase. However, a relatively poor crystallinity of these films limited the p-type characteristics. The films with Cu and CuO phases show n-type conductivity. The surface of the as-deposited is smooth (RMS roughness of 1.47 nm) and comprised of uniformly distributed grains (AFM and SEM analysis). The post-annealing is found to be effective on the distribution of grains and their sizes. The poor transmittance of the as-deposited films (<1%) is increased to a maximum of ∼80% (800 nm) on annealing at 200 °C. The direct allowed band gap is varied between 2.03 and 3.02 eV.     

Preparation and optical properties of nanocrystalline thin films in the ZnO-TiO<Subscript>2</Subscript> system

Nanocrystalline compound thin films of ZnO-TiO₂ with different Zn/Ti atomic ratios were prepared by radio frequency magnetron reactive sputtering. The optical constants and the optical band gap were investigated using spectroscopic ellipsometry and the optical absorption spectrum. It was found that the cubic ZnTiO₃ phase can be obtained with the atomic ratio of Zn to Ti of about 1:1, and transforms to rhombohedral ZnTiO₃ phase and a phase mixture of rhombohedral ZnTiO₃ and ZnO with increasing Zn content. The refractive index decreases with the increase of Zn content, and the extinction coefficient in the visible range is near zero. The optical band gap was derived from the modeling of ellipsometry data and extinction coefficient spectra, and compared with that obtained from optical absorption spectrum, and it was found that the optical band gaps obtained by these three methods are consistent with each other. PACS 42.70.-a; 68.55.Jk; 78.20.Ci; 81.15.Cd     

Ellipsometric study of a-Be3N2 thin films prepared by radio frequency magnetron sputtering

The ellipsometric characterizations of amorphous beryllium nitride (a-Be₃N₂) thin films deposited on Si (1 0 0) and quartz at temperature <50 °C using reactive RF sputtering deposition were examined in the wavelength range 280-1600 nm. X-ray diffraction of the films showed no structure, suggesting the Be₃N₂ films grown on the substrates are amorphous. The composition and chemical structures of the amorphous thin films were determined by using electron spectroscopy for chemical analysis. The surface morphology of a-Be₃N₂ was characterized by atomic force microscopy. The thicknesses and optical constants of the films were derived from spectroscopic ellipsometry measurements. The variation of the optical constants with thickness of the deposited films has been investigated. From the angle dependence of the polarized reflectivity we deduced a Brewster angle of 64°. At any angle of incidence, the a-Be₃N₂ shown high transmissivity (80-99%) and low reflectivity (<18%) in the visible and near infrared regions. Hence, the a-Be₃N₂ could be a good candidate for antireflection optical coatings under conditions of optimized the type of polarization and the angle of incidence.     

Correlation between microstructure and optical properties of nano-crystalline TiO2 thin films prepared by sol-gel dip coating

Titanium dioxide thin films have been prepared from tetrabutyl-orthotitanate solution and methanol as a solvent by sol-gel dip coating technique. TiO₂ thin films prepared using a sol-gel process have been analyzed for different annealing temperatures. Structural properties in terms of crystal structure were investigated by Raman spectroscopy. The surface morphology and composition of the films were investigated by atomic force microscopy (AFM). The optical transmittance and reflectance spectra of TiO₂ thin films deposited on silicon substrate were also determined. Spectroscopic ellipsometry study was used to determine the annealing temperature effect on the optical properties and the optical gap of the TiO₂ thin films. The results show that the TiO₂ thin films crystallize in anatase phase between 400 and 800 °C, and into the anatase-rutile phase at 1000 °C, and further into the rutile phase at 1200 °C. We have found that the films consist of titanium dioxide nano-crystals. The AFM surface morphology results indicate that the particle size increases from 5 to 41 nm by increasing the annealing temperature. The TiO₂ thin films have high transparency in the visible range. For annealing temperatures between 1000 and 1400 °C, the transmittance of the films was reduced significantly in the wavelength range of 300-800 nm due to the change of crystallite phase and composition in the films. We have demonstrated as well the decrease of the optical band gap with the increase of the annealing temperature.     

Some physical properties of In doped copper oxide films produced by ultrasonic spray pyrolysis

In this work, we have reported the effect of In doping on structural, optical and surface properties of copper oxide films obtained by a low-cost ultrasonic spray pyrolysis technique. Thicknesses, refractive indices and extinction coefficients of the films have been determined by Spectroscopic ellipsometry technique using Cauchy-Urbach model for fitting. A very good agreement was found between experimental and theoretical parameters with low MSE values. Transmission and reflectance spectra have been taken by UV Spectrophotometer, and band gap values have been determined by optical method. Structural properties of the films were investigated with X-ray diffraction patterns. In doping caused the films to growth through some certain directions. Atomic force microscope images have been taken to see the effect of In doping on surface topography and roughness of copper oxide films. Surface properties of undoped films have been improved by In doping. Lowest roughness values have been obtained for In doping at 1%. As a result, we have concluded that properties of copper oxide films which are commonly used in solar cells may have improved by In doping (especially In doped at 1%).     

Preparation and characterization of Mn doped copper nitride films with high photocurrent response

The Mn-doped copper nitride (Cu₃N) films with Mn concentration of 2.0 at. % have high crystallinity and uniform surface morphology. We found that the as-synthesized Mn-doped Cu₃N films show suitable optical absorption in the visible region and the band gap is ∼1.48 eV. A simple photodetector based on Mn doped Cu₃N films was firstly fabricated via magnetron sputtering method. The fabricated device with doping of Mn demonstrated high photocurrent response and fast response shorter than 0.1 s both for rise and decay time superior to the pure Cu₃N. Furthermore, the energy levels of Mn-doped Cu₃N matched well with ITO and Ag electrode. The excellent photoelectric properties reflect a good balance between sensitivities and response rate. Our investigation reveals the excellent potential of Mn-doped Cu₃N films for application of photodetectors.     

A new dioxime ligand and its trinuclear copper(II) complex: Synthesis, characterization and optical properties

The synthesis and characterization of a new dioxime ligand, (H₂L), (III) and its trinuclear copper(II) complex, [Cu₃L₂(H₂O)₂](ClO₄)₂, (V) is described. IR spectra show that the ligand acts in a tetradentate manner and coordinates N₄ donor groups of H₂L to copper(II) ion. The structure of the metal chelate is clarified with the help of elemental analysis, magnetic moment, conductometric and spectroscopic measurements. The optical absorption studies reveal that the transition is direct with band gap energy values are calculated. The optical constants such as refractive index and dielectric constant of the compound were determined. The refractive index dispersion curves of the films obey the single-oscillator model and oscillator parameters. Optical dispersion parameters E₀ and E_d developed by Wemple-DiDomenico were calculated.     

Optical absorption spectrum of Cu2O-CaO-P2O5 glasses

Homogeneous CaO-P₂O₅ and Cu₂O-CaO-P₂O₅ glasses were prepared using a melt-quenched method under controlled conditions. The binary glasses were found to be colourless and transparent while the ternary glasses changed from light green to dark green as the Cu₂O content increased. From the absorption edge studies, the values of the optical band gap, E_opt and Urbach energy, ΔE were evaluated. The position of the absorption edge and hence the optical band gap were found to depend on the glass composition. Analysis of the optical band gap shows that for the binary glasses, the value increases as the content of CaO decreases, while for the ternary glasses, the value of the optical band gap increases as the content of the Cu₂O decreases. The density of the glasses was also measured and was found to increase with the increase in CaO and Cu₂O contents.     

Ellipsometric characterization of PbI2 thin film on glass

The optical properties of polycrystalline lead iodide thin film grown on Corning glass substrate have been investigated by spectroscopic ellipsometry. A structural model is proposed to account for the optical constants of the film and its thickness. The optical properties of the PbI₂ layer were modeled using a modified Cauchy dispersion formula. The optical band gap E_g has been calculated based on the absorption coefficient (α) data above the band edge and from the incident photon energy at the maximum index of refraction. The band gap was also measured directly from the plot of the first derivative of the experimental transmission data with respect to the light wavelength around the transition band edge. The band gap was found to be in the range of 2.385±0.010 eV which agrees with the reported experimental values. Urbach's energy tail was observed in the absorption trend below the band edge and was found to be related to Urbach's energy of 0.08 eV.     

Structural-optical study of high-dielectric-constant oxide films

High-k polycrystalline Pr₂O₃ and amorphous LaAlO₃ oxide thin films deposited on Si(0 0 1) are studied. The microstructure is investigated using X-ray diffraction and scanning electron microscopy. Optical properties are determined in the 0.75-6.5 eV photon energy range using spectroscopic ellipsometry. The polycrystalline Pr₂O₃ films have an optical gap of 3.86 eV and a dielectric constant of 16-26, which increases with film thickness. Similarly, very thin amorphous LaAlO₃ films have the optical gap of 5.8 eV, and a dielectric constant below 14 which also increases with film thickness. The lower dielectric constant compared to crystalline material is an intrinsic characteristic of amorphous films.     

Preparation and characterization of thermally evaporated titanium phthalocyanine dichloride thin films

Titanium phthalocyanine dichloride (TiPcCl₂) thin films are prepared on glass substrates by vacuum-sublimation technique. The optical constants of thin films are obtained by means of thin film spectrophotometry. Planar structures for the study of electrical properties are fabricated with TiPcCl₂ as active layer and silver as the contact electrodes. The effects of post-deposition annealing on the optical band gap have been studied. The optical transition is found to be direct allowed in nature. The invariance in the optical band gap shows the thermal stability of the material. The activation energies are determined using the Arrhenius plots between electrical conductivity and inverse temperature. The variation in activation energy with post-deposition annealing is investigated. The unit cell dimensions of TiPcCl₂ thin films are also determined by indexing the powder diffraction data. The variations of the surface morphology and grain size with annealing have also been studied.     

Structural, optical and electrical properties of tin oxide thin film deposited by APCVD method

Tin oxide (SnO₂) thin films have been grown on glass substrates using atmospheric pressure chemical vapour deposition (APCVD) method. During the deposition, the substrate temperature was kept at 400°C–500°C. The structural properties, surface morphology and chemical composition of the deposited film were studied by X-ray diffraction (XRD), scanning electron microscope (SEM) and Rutherford back scattering (RBS) spectrum. XRD pattern showed that the preferred orientation was (110) having tetragonal structure. The optical properties of the films were studied by measuring the transmittance, absorbance and reflectance spectra between λ = 254 nm to 1400 nm and the optical constants were calculated. Typical SnO₂ film transmits ∼ 94% of visible light. The electrical properties of the films were studied using four-probe method and Hall-voltage measurement experiment. The films showed room temperature conductivity in the range 1.08 × 10² to 1.69 × 10² Ω⁻¹cm⁻¹.     

Derivation of the optical constants of spin coated CeO2-TiO2-ZrO2 thin films prepared by sol-gel route

Ternary thin films of cerium titanium zirconium mixed oxide were prepared by the sol-gel process and deposited by a spin coating technique at different spin speeds (1000-4000 rpm). Ceric ammonium nitrate, Ce(NO₃)₆(NH₄)₂, titanium butoxide, Ti[O(CH₂)₃CH₃]₄, and zirconium propoxide, Zr(OCH₂CH₂CH₃)₄, were used as starting materials. Differential calorimetric analysis (DSC) and thermogravimetric analysis (TGA) were carried out on the CeO₂-TiO₂-ZrO₂ gel to study the decomposition and phase transition of the gel. For molecular, structural, elemental, and morphological characterization of the films, Fourier Transform Infrared (FTIR) spectral analysis, X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS), cross-sectional scanning electron microscopy (SEM), and atomic force microscopy (AFM) were carried out. All the ternary oxide thin films were amorphous. The optical constants (refractive index, extinction coefficient, band gap) and thickness of the films were determined in the 350-1000 nm wavelength range by using an nkd spectrophotometer. The refractive index, extinction coefficient, and thickness of the films were changed by varying the spin speed. The oscillator and dispersion energies were obtained using the Wemple-DiDomenico dispersion relationship. The optical band gap is independent of the spin speed and has a value of about E_g≈2.82±0.04 eV for indirect transition.