Optical characterization of PLD grown nitrogen-doped TiO2 thin films

Nitrogen-doped TiO₂ thin films were prepared by pulsed laser deposition (PLD) by ablating metallic Ti target with pulses of 248 nm wavelength in reactive atmospheres of O₂/N₂ gas mixtures. The layers were characterized by UV-VIS spectrophotometry and variable angle spectroscopic ellipsometry with complementary profilometry for measuring the thickness of the films. Band gap and extinction coefficient values are presented for films deposited at different substrate temperatures and for varied N₂ content of the gas mixture. The shown tendencies are correlated to nitrogen incorporation into the TiO_2-xN_x layers. It is shown that layers of significantly increased visible extinction coefficient with band gap energy as low as 2.89 eV can be obtained. A method is also presented how the spectroscopic ellipsometric data should be evaluated in order to result reliable band gap values.     

Post-deposition atomic terraces growth of ZnO thin films deposited on epi-GaN templates

We demonstrate how growth processes affect on ZnO film properties, which are to be essential guides to prevent defect formation in order to synthesize reproducible high quality ZnO films. First, we reveal that deposition at a low temperature is indispensable to transfer underlying GaN atomic terraces to ZnO surface. As the film thickness is increased, however, the terraces disappear to develop island morphology. It is found that the thick film surface is smoothed to the extent that atomic terraces can be seen after an appropriate thermal treatment. Adverse effects associated with high annealing temperatures are then demonstrated as evidenced by cracks formation, increased yellow cathode-luminescence and intermixing at the interface.     

Thickness influence on surface morphology and ozone sensing properties of nanostructured ZnO transparent thin films grown by PLD

Transparent zinc oxide (ZnO) thin films with a thickness from 10 to 200 nm were prepared by the PLD technique onto silicon and Corning glass substrates at 350 °C, using an Excimer Laser XeCl (308 nm). Surface investigations carried out by atomic force microscopy (AFM) and X-ray diffraction (XRD) revealed a strong influence of thickness on film surface topography. Film roughness (RMS), grain shape and dimensions correlate with film thickness. For the 200 nm thick film, the RMS shows a maximum (13.9 nm) due to the presence of hexagonal shaped nanorods on the surface. XRD measurements proved that the films grown by PLD are c-axis textured. It was demonstrated that the gas sensing characteristics of ZnO films are strongly influenced and may be enhanced significantly by the control of film deposition parameters and surface characteristics, i.e. thickness and RMS, grain shape and dimension.     

Optical and structural studies on Ba(Mg1/3Ta2/3)O3 thin films obtained by radiofrequency assisted pulsed plasma deposition

Single-phase Ba(Mg_1/3Ta_2/3)O₃ thin films were prepared by radiofrequency plasma beam assisted pulsed laser deposition (RF-PLD) starting from a bulk ceramic target synthesized by solid state reaction. Atomic force microscopy, X-ray diffraction and spectroscopic ellipsometry were used for morphological, structural and optical characterization of the BMT thin films. The X-ray diffraction spectra show that the films exhibit a polycrystalline cubic structure. From spectroscopic ellipsometry analysis, the refractive index varies with the thin films deposition parameters. By using the transmission spectra and assuming a direct band to band transition a band gap value of ≈4.72 eV has been obtained.     

Surface modification of doped ZnO thin films

Effects of photo-assisted electrodeless and ion RF-sputter etching on the structural and optical properties of sputtered ZnO:Al thin films were investigated. Photo-assisted electrodeless etching was appropriate for getting “smooth” surfaces and ion RF-sputter etching by high power has significantly modified the surface roughness with an increase of the light diffuse transmittance.     

Structural, electrical and optical properties of Gd doped and undoped ZnO:Al (ZAO) thin films prepared by RF magnetron sputtering

The influence of the gadolinium doping on the structural features and opto-electrical properties of ZnO:Al (ZAO) films deposited by radio frequency (RF) magnetron sputtering method onto glass substrates was investigated. X-ray analysis showed that the films were polycrystalline fitting well with a hexagonal wurtzite structure and have preferred orientation in [0 0 2] direction. The Gd doped ZAO film with a thickness of 140 nm showed a high visible region transmittance of 90%. The optical band gap was found to be 3.38 eV for pure ZnO film and 3.58 eV for ZAO films while a drop in optical band gap of ZAO film was observed by Gd doping. The lowest resistivities of 8.4 × 10⁻³ and 10.6 × 10⁻³ Ω cm were observed for Gd doped and undoped ZAO films, respectively, which were deposited at room temperature and annealed at 150 °C.     

Structural and optical properties of sputtered ZnO thin films

Zinc oxide (ZnO) and aluminium-doped zinc oxide (ZnO:Al) thin films were prepared by RF diode sputtering at varying deposition conditions. The effects of negative bias voltage and RF power on structural and optical properties were investigated. X-ray diffraction measurements (XRD) confirmed that both un-doped and Al-doped ZnO films are polycrystalline and have hexagonal wurtzite structure. The preferential 〈0 0 1〉 orientation and surface roughness evaluated by AFM measurements showed dependence on applied bias voltage and RF power. The sputtered ZnO and ZnO:Al films had high optical transmittance (>90%) in the wavelength range of 400-800 nm, which was not influenced by bias voltage and RF power. ZnO:Al were conductive and highly transparent. Optical band gap of un-doped and Al-doped ZnO thin films depended on negative bias and RF power and in both cases showed tendency to narrowing.     

Structural and optical properties of the SiCN thin films prepared by reactive magnetron sputtering

Silicon carbonitride (SiCN) thin films were deposited on n-type Si (1 0 0) and glass substrates by reactive magnetron sputtering of a polycrystalline silicon target in a mixture of argon (Ar), nitrogen (N₂) and acetylene (C₂H₂). The properties of the films were characterized by scanning electron microscope with an energy dispersive spectrometer, X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectrometry and ultraviolet-visible spectrophotometer. The results show that the C₂H₂ flow rate plays an important role in the composition, structural and optical properties of the films. The films have an even surface and an amorphous structure. With the increase of C₂H₂ flow rate, the C content gradually increases while Si and N contents have a tendency to decrease in the SiCN films, and the optical band gap of the films monotonically decreases. The main bonds are Si-O, N-H_n, C-C, C-N, Si-N, Si-C and Si-H in the SiCN films while the chemical bonding network of Si-O, C-C, C-O, C-N, N-Si and CN is formed in the surface of the SiCN films.     

Photosensitivity of nanocrystalline ZnO films grown by PLD

We have studied the properties of ZnO thin films grown by laser ablation of ZnO targets on (0 0 0 1) sapphire (Al₂O₃), under substrate temperatures around 400 °C. The films were characterized by different methods including X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and atomic force microscopy (AFM). XPS analysis revealed that the films are oxygen deficient, and XRD analysis with θ-2θ scans and rocking curves indicate that the ZnO thin films are highly c-axis oriented. All the films are ultraviolet (UV) sensitive. Sensitivity is maximum for the films deposited at lower temperature. The films deposited at higher temperatures show crystallite sizes of typically 500 nm, a high dark current and minimum photoresponse. In all films we observe persistent photoconductivity decay. More densely packed crystallites and a faster decay in photocurrent is observed for films deposited at lower temperature.     

Substrate temperature influence on the properties of nanostructured ZnO transparent ultrathin films grown by PLD

Zinc oxide films of 40 nm thickness have been deposited on glass substrates by pulsed laser deposition using an excimer XeCl laser (308 nm) at different substrate temperatures ranging from room temperature to 650 °C. Surface investigations carried out by using atomic force microscopy have shown a strong influence of temperature on the films surface topography. UV-VIS transmittance measurements have shown that our ZnO films are highly transparent in the visible wavelength region, having an average transmittance of ∼90%. The optical band gap of the films was found to be 3.26 eV, which is lower than the theoretical value of 3.37 eV. Besides the normal absorption edge related to the transition between the valence and the conduction band, an additional absorption band was also recorded in the wavelength region around 364 nm (∼3.4 eV). This additional absorption band may be due to excitonic, impurity, and/or quantum size effects. Photoreduction/oxidation in ozone of the ZnO films lead to larger conductivity changes for higher deposition temperature. In conclusion, the ozone sensing characteristics as well as the optical properties of the ZnO thin films deposited by pulsed laser deposition are strongly influenced by the substrate temperature during growth. The sensitivity of the films towards ozone might be enhanced significantly by the control of the films deposition parameters and surface characteristics.     

Influence of substrate temperature on the optical and piezoelectric properties of ZnO thin films deposited by rf magnetron sputtering

In this study, ZnO thin films were fabricated using the rf magnetron sputtering method and their piezoelectrical and optical characteristics were investigated for various substrate temperatures. The ZnO thin film has the largest crystallization orientation for the (0 0 2) peak and the smallest FWHM value of 0.56° at a substrate temperature of 200 °C. The surface morphology shows a relatively dense surface structure at 200 °C compared to the other substrate temperatures. The surface roughness shows the smallest of 1.6 nm at a substrate temperature of 200 °C. The piezoelectric constant of the ZnO thin film measured using the pneumatic loading method (PLM) has a maximum value of 11.9 pC/N at a substrate temperature of 200 °C. The transmittance of the ZnO thin film measured using spectrophotometry with various substrate temperatures ranged from 75 to 93% in the visible light region. By fitting the refractive index from the transmittance to the Sellmeir dispersion relation, we can predict the refractive index of the ZnO thin film according to the wavelength. In the visible light range, the refraction index of the ZnO thin film deposited at a substrate temperature of 200 °C is the range of 1.88-2.08.     

Structural and optical properties of thin films porous amorphous silicon carbide formed by Ag-assisted photochemical etching

In this work, we present the formation of porous layers on hydrogenated amorphous SiC (a-SiC: H) by Ag-assisted photochemical etching using HF/K₂S₂O₈ solution under UV illumination at 254 nm wavelength. The amorphous films a-SiC: H were elaborated by d.c. magnetron sputtering using a hot pressed polycrystalline 6H-SiC target. Because of the high resistivity of the SiC layer, around 1.6 MΩ cm and in order to facilitate the chemical etching, a thin metallic film of high purity silver (Ag) has been deposited under vacuum onto the thin a-SiC: H layer. The etched surface was characterized by scanning electron microscopy, secondary ion mass spectroscopy, infrared spectroscopy and photoluminescence. The results show that the morphology of etched a-SiC: H surface evolves with etching time. For an etching time of 20 min the surface presents a hemispherical crater, indicating that the porous SiC layer is perforated. Photoluminescence characterization of etched a-SiC: H samples for 20 min shows a high and an intense blue PL, whereas it has been shown that the PL decreases for higher etching time. Finally, a dissolution mechanism of the silicon carbide in 1HF/1K₂S₂O₈ solution has been proposed.     

Superconducting molybdenum nitride epitaxial thin films deposited on MgO and α-Al2O3 substrates by molecular beam epitaxy

Molybdenum nitride Mo₂N_x films were grown on MgO(0 0 1) and on α-Al₂O₃(0 0 1) substrates by molecular beam epitaxy under nitrogen radical irradiation. X-ray photoelectron spectroscopy revealed that the composition of the film varied in the range of Mo₂N_1.4-Mo₂N_2.8 depending on the growth temperature. The deposition at 973 K gave well-crystallized films on both substrates. The high-resolution reciprocal space mapping by X-ray diffraction showed that the nitrogen-rich γ-Mo₂N crystalline phase (the composition: Mo₂N_1.4) was epitaxially grown on MgO at 923 K with a slight tetragonal distortion (a = 0.421 and c = 0.418 nm) to fit the MgO lattice (a = 0.421 nm). On α-Al₂O₃(0 0 1), nitrogen-rich γ-Mo₂N (Mo₂N_1.8) was grown at 973 K with (1 1 1) planes parallel to the substrate surface. X-ray diffraction analysis with a multi-axes diffractometer revealed that the γ-Mo₂N on α-Al₂O₃(0 0 1) had a slight rhombohedral distortion (a = 0.4173(2) and α = 90.46(3)°). Superconductivity was observed below 2.8-3 K for the films grown at 973 K on MgO and on α-Al₂O₃(0 0 1).     

Write-once blue laser recording using silicon doped SbOx thin films prepared by reactive dc-magnetron sputtering

Si:SbO_x films have been deposited by reactive dc-magnetron sputtering from a Sb target with Si chips attached in Ar + O₂ with the relative O₂ content 7%. The as-deposited films contained Sb metal, Sb₂O₃, SiO, Si₂O₃ and SiO₂. The crystallization of Sb was responsible for the changes of optical properties of the films. The results of the blue laser recording test showed that the films had good writing sensitivity for blue laser beam (406.7 nm), and the recording marks were still clear even if the films were deposited in air 60 days, which demonstrated that doping silicon in SbO_x films can improve the stability of SbO_x films. High reflectivity contrast of about 36% was obtained at a writing power 6 mW and writing pulse width 300 ns.     

Berkovich nanoindentation and deformation mechanisms in GaN thin films

The deformation mechanisms of GaN thin films obtained by metal-organic chemical vapor deposition (MOCVD) method were studied using nanoindentation with a Berkovich diamond indenter, micro-Raman spectroscopy and the cross-sectional transmission electron microscopy (XTEM) techniques. Due to the sharpness of the tip of Berkovich indenter, the nanoindentation-induced deformation behaviors can be investigated at relatively lower load and, hence, may cover wider range of deformation-related phenomena over the same loading range. The load-displacement curves show the multiple “pop-ins” during nanoindentation loading. No evidence of nanoindentation-induced phase transformation and cracking patterns were found up to the maximum load of 300 mN, as revealed from the micro-Raman spectra and the scanning electron microscopy (SEM) observations within the mechanically deformed regions. In addition, XTEM observation performed near the cross-section of the indented area revealed that the primary deformation mechanism in GaN thin film is via propagation of dislocations on both basal and pyramidal planes. The continuous stiffness measurement (CSM) technique was used to determine the hardness and Young's modulus of GaN thin films. In addition, analysis of the load-displacement data reveals that the values of hardness and Young's modulus of GaN thin films are 19 ± 1 and 286 ± 25 GPa, respectively.     

Low temperature deposition of TiO2 thin films on polyvinyl alcohol fibers with photocatalytical and antibacterial activities

Fine particles of photoactive anatase-type TiO₂ coated polyvinyl alcohol (PVA) fibers (TiO₂/PVA) were prepared successfully via a simple dip-coating method. Tetrabutyl orthotitanate (TBOT) was hydrolyzed in presence of hydrolysis control agent tetrabutylammonium hydroxide (TBA)OH and the TiO₂ fine particles were crystallized under microwave (MW) irradiation. The X-ray diffraction (XRD) and selected-area electron diffraction (SAED) analyses indicated that the fine particles obtained with MW irradiation have much higher crystallinity with a single phase anatase compared with the non-MW-treated solution. The continuous layers of titania were found on PVA fibers by the scanning electron microscopy (SEM) analysis. The fibers with anatase coatings showed high photocatalytic property on the photodegradation of methylene blue (MB) and high antibacterial activity.     

Structural characterization of single-wall carbon nanohorn aggregates hybridized with carbon nanocapsules and their formation mechanism

Three types of single-wall carbon nanohorn (SWNH) aggregates hybridized with carbon nanocapsules (CNCs) containing Fe₃C, Co, or Ag were produced by laser vaporization of graphite mixed with Fe, Co, or Ag in Ar gas. Characterization by transmission electron microscopy revealed that although the three hybrid structures had different diameter distributions with average diameters of 96, 90, and 85 nm, respectively, their SWNH layers had similar thicknesses (17-18 nm on average). The diameter difference is explained by the sizes (16-24 nm on average) of the encapsulated CNCs, the formation of which depended on the carbon solubility of the three metals and the precipitation of the graphitic layers. In addition, there was a stronger correlation between the diameters of the hybrids and the thicknesses of the SWNH layers for the three types. We suggest that the formation mechanism of the three structures is based on the assembly of SWNHs around a molten metal-carbon particle with certain ranges of lengths and diameters, respectively.     

Structural and optical properties of ZnO thin films prepared by sol-gel method with different thickness

In this work, ZnO thin films with different thickness were prepared by sol-gel method on glass substrates and the structural and optical properties of these films were studied by X-ray diffractometer, atomic force microscope, UV-visible spectrophotometer, ellipsometer and fluorophotometer, respectively. The structural analyses show that all the samples have a wurtzite structure and are preferentially oriented along the c-axis perpendicular to the substrate surface. The growth process of highly c-axis oriented ZnO thin films derived from sol-gel method is a self-template process. With the increase of film thickness, the structural disorder decreases and the crystalline quality of the films is gradually improved. A transition of crystal growth mode from vertical growth to lateral growth is observed and the transition point is found between 270 and 360 nm thickness. The optical analyses show that with the increase of film thickness, both the refractive index and ultraviolet emission intensity are improved. However, the transmittance in the visible range is hardly influenced by the film thickness, and the averages are all above 80%.     

Growth of Bi-Sb alloy thin films and their characterization by TEM, PIXE and RBS

Polycrystalline bulk materials of Bi₉₃Sb₇ Bi₈₈Sb₁₂, Bi₈₅Sb₁₅ and Bi₈₀Sb₂₀ were synthesized by melt-quench technique starting from the stoichiometric mixture of constituent elements. The phase purity and compositional uniformity of bulk materials were investigated using powder X-ray diffraction (XRD) and proton induced X-ray emission (PIXE) experiments. The single phase formation and the compositional analysis of thin films were confirmed by transmission electron microscopy (TEM) and Rutherford backscattering spectroscopy (RBS). X-ray diffraction studies confirmed the phase homogeneity of the materials. Atomic concentration ratio of constituent elements (Bi and Sb) determined by PIXE and RBS revealed that near-stoichiometric composition is nearly the same in the bulk as well as in thin film forms.     

Structural and optical properties of nano-structured tungsten-doped ZnO thin films grown by pulsed laser deposition

Novel highly c-oriented tungsten-doped zinc oxide (WZO) thin films with 1 wt% were grown by pulsed laser deposition (PLD) technique on corning 1737F glass substrate. The effects of laser energy on the structural, morphological as well as optical transmission properties of the films were studied. The films were highly transparent with average transmittance exceeding 87% in the wavelength region lying between 400 and 2500 nm. X-ray diffraction analysis (XRD) results indicated that the WZO films had c-axis preferred orientation with wurtzite structure. Film thickness and the full width at half maximum (FWHM) of the (0 0 2) peaks of the films were found to be dependent on laser fluence. The composition determined through Rutherford backscattering spectroscopy (RBS) appeared to be independent of the laser fluence. By assuming a direct band gap transition, the band gap values of 3.36, 3.34 and 3.31 eV were obtained for corresponding laser fluence of 1, 1.7 and 2.7 J cm⁻², respectively. Compared with the reported undoped ZnO band gap value of 3.37 eV, it is conjectured that the observed low band gap values obtained in this study may be attributable to tungsten incorporation in the films as well as the increase in laser fluence. The high transparency makes the films useful as optical windows while the high band gap values support the idea that the films could be good candidates for optoelectronic applications.