Laser synthesis of nanostructures based on transition metal oxides

Nanostructures based on iron oxides in the form of thin films were synthesized while laser chemical vapor deposition (LCVD) of elements from iron carbonyl vapors (Fe(CO)₅) under the action of Ar⁺ laser radiation (λ_L = 488 nm) on the Si substrate surface with power density about 10² W/cm² and vapor pressure 666 Pa. Analysis of surface morphology and relief of the deposited films was carried out with scanning electron microscopy (SEM) and atomic force microscopy (AFM). This analysis demonstrated their cluster structure with average size no more than 100 nm. It was found out that the thicker the deposited film, the larger sizes of clusters with more oxides of higher oxidized phases were formed. The film thickness (d) was 10 and 28 nm. The deposited films exhibited semiconductor properties in the range 170-340 K which were stipulated by oxide content with different oxidized phases. The width of the band gap E_g depends on oxide content in the deposited film and was varied in the range 0.30-0.64 eV at an electrical field of 1.6 × 10³ V/m. The band gap E_g was varied in the range 0.46-0.58 eV at an electrical field of 45 V/m. The band gap which is stipulated by impurities in iron oxides E_i was varied in the range 0.009-0.026 eV at an electrical field of 1.6 × 10³ V/m and was varied in the range 0-0.16 eV at an electrical field 45 V/m. These narrow band gap semiconductor thin films displayed of the quantum dimensional effect.     

Optical properties of selenium-tellurium nanostructured thin film grown by thermal evaporation

Se-Te nanostructured thin films were deposited on glass substrates in the presence of oxygen and argon by thermal evaporation. The properties of Se-Te thin films strongly depend on the deposition method. During the process used, the substrate is cooled to a temperature of 77 K employing liquid nitrogen. The nanostructured thin films of Se_100−xTe_x (where x=4, 8 and 16) are deposited on glass substrate. The surface morphology of the deposited films was investigated through Scanning Electron Microscopy (SEM). The typical size of these nanostructures is in the range 40-100 nm and the length is of the order of several micrometers. The optical parameters i.e. optical gap (E_g), absorption coefficient (α), and extinction coefficient (k) are calculated in the wavelength range 190-1100 nm. It was found that the optical band gap decreased from 3.4 to 2.9 eV when Te concentration was increased in the Se_100−xTe_x nanostructured thin films. The large bandgap may be attributed to the decrease in particle size which clearly exhibits a quantum size effect. XRD analysis was performed to confirm glassy nature of the nanostructured thin films.     

Laser-assisted synthesis of semiconductor chromium disilicide films

Different photo-assisted techniques were employed for chromium disilicide (CrSi₂) semiconductor film fabrication. Flash evaporation of CrSi₂ powder on the Si substrate heated to ∼740 K leads to the formation (according to XRD study) of amorphous films. Post-annealing at 920 K leads to the formation of polycrystalline CrSi₂ phase. Crystallization is improved by further annealing with 1500 Q-Switched Nd:YAG laser pulses. Optical properties of the as deposited and annealed CrSi₂ films have been investigated in the 240-1100 nm spectral range by using spectroscopic ellipsometry. The formation of CrSi₂ semiconductor phase was additionally confirmed by the temperature dependence of electrical resistance of the films treated by Q-switched Nd:YAG laser. The band gap for intrinsic conductivity results E_g ≅ 0.2 eV. Backward laser-induced film transfer (LIFT) was also used for CrSi₂ film deposition from bulk material on Si substrates. Pulsed CO₂ laser was employed for this purpose, because of transparency of silicon at the 10.6 μm wavelength. Measurements of the electrical resistance of the deposited films as a function of temperature showed their semiconductor behavior (E_g = 6 × 10⁻⁴ eV). Chromium disilicide films were also deposited by congruent pulsed laser ablation deposition on Si substrates either at room temperature or heated to about 740 K. In this last case the deposit exhibits semiconducting properties with E_g ≅ 0.18 eV.     

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.     

Optical properties of ITO/TiO2 single and double layer thin films deposited by RPLAD

Indium tin oxide (ITO) and titanium dioxide (TiO₂) single layer and double layer ITO/TiO₂ films were prepared using reactive pulsed laser ablation deposition (RPLAD) with an ArF excimer laser for applications in dye-sensitized solar cells (DSSCs). The films were deposited on SiO₂ substrates either at room temperatures (RT) or heated to 200-400 °C. Under optimized conditions, transmission of ITO films in the visible (vis) range was above 89% for films produced at RT and 93% for the ones deposited at higher temperatures. Increasing the substrate temperature from RT to 400 °C enhances the transmission of TiO₂ films in the vis-NIR from about 70% to 92%. High transmission (≈90%) was observed for the double layer ITO/TiO₂ with a transmission cut-off above 900 nm. From the transmission data, the energies gaps (E_g), as well as the refractive indexes (n) for the films were estimated. n ≈ 2.03 and 2.04, respectively for ITO films and TiO₂ film deposited at 400 °C in the visible region. Post-annealing of the TiO₂ films for 3 h at 300 and 500 °C was performed to enhance n. The refractive index of the TiO₂ films increases with the post-annealing temperature. The direct band gap is 3.6, 3.74 and 3.82 eV for ITO films deposited at RT, 200, and 400 °C, respectively. The TiO₂ films present a direct band gap of 3.51 and 3.37 eV for as deposited TiO₂ films and when annealed at 400 °C, respectively. There is a shift of about 0.1 eV between ITO and ITO/TiO₂ films deposited at 200 °C. The shift decreases by half when the TiO₂ film was deposited at 400 °C. Post-annealing was also performed on double layer ITO/TiO₂.     

Characterization of ZnO-SnO2 thin film composites prepared by pulsed laser deposition

Thin films of ZnO-SnO₂ composites have been deposited on Si(1 0 0) and glass substrates at 500 °C by pulsed laser ablation using different composite targets with ZnO amount varying between 1 and 50 wt%. The effect of increasing ZnO-content on electrical, optical and structural properties of the ZnO-SnO₂ films has been investigated. X-ray diffraction analysis indicates that the as-deposited ZnO-SnO₂ films can be both crystalline (for ZnO <1 wt%) and amorphous (for ZnO ≥ 10 wt%) in nature. Atomic force microscopy studies of the as-prepared composite films indicate that the surfaces are fairly smooth with rms roughness varying between 3.07 and 2.04 nm. The average optical transmittance of the as-deposited films in the visible range (400-800 nm), decreases from 90% to 72% for increasing ZnO concentration in the film. The band gap energy (E_g) seems to depend on the amount of ZnO addition, with the maximum obtained at 1 wt% ZnO. Assuming that the interband electron transition is direct, the optical band gap has been found to be in the range 3.24-3.69 eV for as-deposited composite films. The lowest electrical resistivity of 7.6 × 10⁻³ Ω cm has been achieved with the 25 wt% ZnO composite film deposited at 500 °C. The photoluminescence spectrum of the composite films shows a decrease in PL intensity with increasing ZnO concentration.     

Particulate assisted growth of ZnO nanorods and microrods by pulsed laser deposition

Zinc oxide (ZnO) thin films were deposited on the gallium nitride (GaN) and sapphire (Al₂O₃) substrates by pulsed laser deposition (PLD) without using any metal catalyst. The experiment was carried out at three different laser wavelengths of Nd:YAG laser (λ = 1064 nm, λ = 532 nm) and KrF excimer laser (λ = 248 nm). The ZnO films grown at λ = 532 nm revealed the presence of ZnO nanorods and microrods. The diameter of the rods varies from 250 nm to 2 μm and the length varies between 9 and 22 μm. The scanning electron microscopy (SEM) images of the rods revealed the absence of frozen balls at the tip of the ZnO rods. The growth of ZnO rods has been explained by vapor-solid (V-S) mechanism. The origin of growth of ZnO rods has been attributed to the ejection of micrometric and sub-micrometric sized particulates from the ZnO target. The ZnO films grown at λ = 1064 nm and λ = 248 nm do not show the rod like morphology. X-ray photoelectron spectroscopy (XPS) has not shown the presence of any impurity except zinc and oxygen.     

Growth, structural and optical properties of non-stoichiometric CuIn(S1−xSex)2 thin films deposited by solution growth technique for photovoltaic application

Polycrystalline thin films of p-CuIn(S_1−xSe_x)₂ have been deposited by a solution growth technique. The deposition parameters such as pH, temperature and time have been optimized. In order to achieve uniformity of thin film, triethanolamine (TEA) has been used. As deposited films have been annealed at 450 °C in air for 5 min. The surface morphology, compositional ratio, structural properties have been studied by SEM, EDAX and XRD technique, respectively. It has been found that films have chalcopyrite structure with the lattice parameters a=5.28 Å and c=11.45 Å at composition x=0.5. The grain size of all composition x measured from SEM and XRD is varied in between 450 and 520 nm. The optical transmittance spectra have been recorded in the range 350-1000 nm. The absorption coefficient has been calculated at the absorption edge for each of the composition x and it is in the range of 10⁴ cm⁻¹. The material shows the direct allowed band gap, which varies from 1.07 to 1.44 eV with change in composition (0≤x≤1.0). These parameters are useful for the photovoltaic application.     

Influences of the iron ion (Fe)-doping on structural and optical properties of nanocrystalline TiO2 thin films prepared by sol-gel spin coating

Titanium dioxide (TiO₂) thin films doping of various iron ion (Fe³⁺) concentrations were deposited on silicon (Si) (100) and quartz substrates by sol-gel Spin Coating technique followed by a thermal treatment at 600 °C. The structure, surface morphology and optical properties, as a function of the doping, have been studied by X-ray diffractometer (XRD), Raman, ultraviolet-visible (UV-vis) and Spectroscopic Ellipsometry (SE). XRD and Raman analyzes of our thin films show that the crystalline phase of TiO₂ thin films comprised only the anatase TiO₂, but the crystallinity decreased when the Fe³⁺ content increased from 0% to 20%. During the Fe³⁺ addition to 20%, the phase of TiO₂ thin film still maintained the amorphous state. The grain size calculated from XRD patterns varies from 29.3 to 22.6 nm. The complex index and the optical band gap (E_g) of the films were determined by the spectroscopic ellipsometry analysis. We have found that the optical band gap decreased with an increasing Fe³⁺ content.     

Optical properties of Ge-As-Te thin films

Different compositions of Ge_xAs₁₀Te_90−x (x=5, 10, 15, 20, and 25 at%) chalcogenide glasses were prepared by the usual melt quench technique. Amorphous Ge_xAs₁₀Te_90−x thin films were deposited onto cleaned glass substrates using the thermal evaporation method. Transmission spectra, T(λ), of the films at normal incidence were measured in the wavelength range 400-2500 nm. A straightforward analysis proposed by Swanepoel based on the use of the maxima and minima of the interference fringes has been used to drive the film thickness, d, the complex index of refraction, n, and the extinction coefficient, k. It was found that, the addition of Ge content at the expense of Te atoms shifts the optical band gap to the short wavelength side (blue shift of the optical band gap) while the refractive index are found to decreases. The obtained results of the refractive index were discussed in terms of the electronic polarizability and the single-oscillator Wemple and DiDomenico model (WDD). The optical absorption is due to the allowed non-direct optical transitions. The observed increase in the optical band gap with the increase in Ge content was discussed in terms of the width of the tail states in the gap and the covalent bond approach.     

Characterization of pulsed laser deposited chalcogenide thin layers

In this work we report on pulsed laser deposition (PLD) of chalcogenide thin films from the systems (AsSe)_100−xAgI_x and (AsSe)_100−xAg_x for sensing applications. A KrF* excimer laser (λ = 248 nm; τ_FWHM = 25 ns) was used to ablate the targets that had been prepared from the synthesised chalcogenide materials. The films were deposited in either vacuum (4 × 10⁻⁴ Pa) or argon (5 Pa) on silicon and glass substrates kept at room temperature. The basic properties of the films, including their morphology, topography, structure, and composition were characterised by complementary techniques. Investigations by X-ray diffraction (XRD) confirmed the amorphous nature of the films, as no strong diffraction reflections were found. The film composition was studied by energy dispersive X-ray (EDX) spectroscopy. The morphology of the films investigated by scanning electron microscopy (SEM), revealed a particulate-covered homogeneous surface, typical of PLD. Topographical analyses by atomic force microscopy (AFM) showed that the particulate size was slightly larger in Ar than in vacuum. The uniform surface areas were rather smooth, with root mean square (rms) roughness increasing up to several nanometers with the AgI or Ag doping. Based upon the results from the comprehensive investigation of the basic properties of the chalcogenide films prepared by PLD and their dependence on the process parameters, samples with appropriate sorption properties can be selected for possible applications in cantilever gas sensors.     

Band gap energy and bowing parameter of In-rich InAlN films grown by magnetron sputtering

The crystal structure, band gap energy and bowing parameter of In-rich In_xAl_1−xN (0.7 < x < 1.0) films grown by magnetron sputtering were investigated. Band gap energies of In_xAl_1−xN films were obtained from absorption spectra. Band gap tailing due to compositional fluctuation in the films was observed. The band gap of the as-grown InN measured by optical absorption method is 1.34 eV, which is larger than the reported 0.7 eV for pure InN prepared by molecular beam epitaxy (MBE) method. This could be explained by the Burstein-Moss effect under carrier concentration of 10²⁰ cm⁻³ of our sputtered films. The bowing parameter of 3.68 eV is obtained for our In_xAl_1−xN film which is consistent with the previous experimental reports and theoretical calculations.     

Femtosecond Z-scan measurement of third-order optical nonlinearities in anatase TiO2 thin films

Anatase phase TiO₂ films have been grown on fused silica substrate by pulsed laser deposition technique at substrate temperature of 750 °C under the oxygen pressure of 5 Pa. From the transmission spectra, the optical band gap and linear refractive index of the TiO₂ films were determined. The third-order optical nonlinearities of the films were measured by Z-scan method using a femtosecond laser (50 fs) at the wavelength of 800 nm. The real and imaginary parts of third-order nonlinear susceptibility χ⁽³⁾ were determined to be −7.1 × 10⁻¹¹esu and −4.42 × 10⁻¹²esu, respectively. The figure of merit, T, defined by T=βλ/n₂, was calculated to be 0.8, which meets the requirement of all-optical switching devices. The results show that the anatase TiO₂ films have great potential applications for nonlinear optical devices.     

Formation of α-Si1−xCx:H and nc-SiC films grown by HWCVD under different process pressure

In this work, hydrogenated amorphous silicon carbide (α-Si_1−xC_x:H) and nanocrystalline SiC (nc-SiC) thin films were deposited by hot wire CVD (HWCVD) using SiH₄/C₂H₂/H₂ gas mixtures. It was found that the films prepared under low gas pressure were α-Si_1−xC_x:H and those prepared under high gas pressure were nc-3C-SiC. The α-Si_1−xC_x:H films showed enhanced density of C-H_n and Si-C bonds with increasing C₂H₂ fraction, which induced an increase in optical gap from 1.8 to 3.0 eV. For the deposition process of nc-SiC, the E_g opt of the deposited films varied from 1.9 eV to 2.5 eV as the filament temperature increased from 1700 to 2100 °C. The deposition rate decreased rapidly from 5.74 nm/min to 0.8 nm/min with increasing T_F.     

Pulsed laser deposition and characterization of nitrogen-substituted SrTiO3 thin films

Nitrogen-substituted cubic perovskite-type SrTiO₃ thin films were deposited in a one-step process using pulsed reactive crossed beam laser ablation (PRCLA) and RF-plasma assisted pulsed laser deposition (RF-PLD). Both techniques yield preferentially oriented films on SrTiO₃(0 0 1), LaAlO₃(0 0 1) and MgO(0 0 1) substrates with the unit cell parameters within 0.390(5) < a < 0.394(9) nm. The nitrogen content is higher in films deposited by PRCLA (0.84-2.40 at.%) as compared to films deposited by RF-PLD with nitrogen plasma (0.10-0.66 at.%). PRCLA with an ammonia gas pulse leads to a higher nitrogen content compared to the films grown with a nitrogen gas pulse, while films deposited by RF-PLD with ammonia plasma reveal only minor nitrogen contents (<0.10 at.%). The amount of the incorporated nitrogen can be tuned by adjusting the deposition parameters. Films deposited by PRCLA have a lower roughness of 1-3 nm compared to 12-18 nm for the films grown by RF-PLD. PRCLA yields partially reduced films, which exhibit electronic conductivity, while films deposited by RF-PLD are insulating. There is also a pronounced influence of the substrate material on the resistivity of the films deposited by PRCLA: films grown on SrTiO₃ substrates exhibit a metallic-like behaviour, while the corresponding films grown on MgO and LaAlO₃ substrates reveal a metal-to-semiconductor/insulator transition. Nitrogen incorporation into the SrTiO₃ films results in an increased optical absorption at 370-500 nm which is associated with N(2p) localized states with the energy about 0.7 eV higher than the valence band energy in strontium titanate. The optical band gap energies in the studied N-substituted SrTiO₃ films are 3.35-3.40 eV.     

Structure, electrical and optical properties of TiNx films by atmospheric pressure chemical vapor deposition

Titanium nitride (TiN_x) films with various nitride compositions (x) were prepared on glass substrates by atmospheric pressure chemical vapor deposition using TiCl₄ and NH₃ as precursors. The structural, compositional, electrical and optical properties of the films were studied and the results were discussed with respect to nitride composition. The results showed a linear relationship between the lattice constant and the nitride composition. Resistivity of the films was minimized near x = 1. All the TiN_x films exhibited a transmission band with a peak value of about 15% in the visible region (400-700 nm). As the wavelength increased to transition point (λ_T-R), the reflectance of the obtained films presented a sharp increase and then reached a high value of about 50% near 2000 nm. Moreover, the red-shift of transmission band and the transition wavelength (λ_T-R) with increasing the nitride composition were also discussed.     

Effect of Mg and Ti doping on the luminescence of Y2O3:Eu

The Y₂O₃:Eu³⁺,Mg²⁺,Ti^IV materials (x_Eu: 0.02, x_Mg: 0.08, x_Ti: 0.04) were prepared by solid state reaction. The purity and crystal structure of the material was studied with the X-ray powder diffraction. Luminescence properties were studied in the UV-VUV range with the aid of synchrotron radiation. The emission of Y₂O₃:Eu³⁺,Mg²⁺,Ti^IV had a maximum at 612 nm (λ_exc: 250 nm) due to the ⁵D₀→⁷F₂ transition of Eu³⁺. The excitation spectra (λ_em: 612 nm) showed a broad band at 233 nm, due to the charge transfer transition between O²⁻ and Eu³⁺, and at 297 nm due to the Ti→Eu³⁺ energy transfer. Only very weak persistent luminescence was discovered. In the room and 10 K temperature excitation spectra, the line at 208 nm is due to the formation of a free exciton (FE) and a broad band at 199 nm was related to the valence-to-conduction band absorption of the Y₂O₃ host lattice. The absorption edge was ca. 205 nm giving 6.1 eV as the energy gap of Y₂O₃.     

Pulsed laser deposition of polyhydroxybutyrate biodegradable polymer thin films using ArF excimer laser

We demonstrated the pulsed laser deposition (PLD) of high quality films of a biodegradable polymer, the polyhydroxybutyrate (PHB). Thin films of PHB were deposited on KBr substrates and fused silica plates using an ArF (λ = 193 nm, FWHM = 30 ns) excimer laser with fluences between 0.05 and 1.5 J cm⁻². FTIR spectroscopic measurements proved that at the appropriate fluence (0.05, 0.09 and 0.12 J cm⁻²), the films exhibited similar functional groups with no significant laser-produced modifications present. Optical microscopic images showed that the layers were contiguous with embedded micrometer-sized grains. Ellipsometric results determined the wavelength dependence (λ ∼ 245-1000 nm) of the refractive index and absorption coefficient which were new information about the material and were not published in the scientific literature. We believe that our deposited PHB thin films would have more possible applications. For example to our supposal the thin layers would be applicable in laser induced forward transfer (LIFT) of biological materials using them as absorbing thin films.     

Study on the structure and optical property of Zn1−xCuxO sol–gel thin films on quartz substrate

Zn_1−xCu_xO thin films (x=0, 1.0, 3.0, 5.0%) are prepared on quartz substrate by sol–gel method. The structure and morphology of the samples are investigated by X-ray diffraction (XRD) and atomic force microscopy (AFM). The results show that Cu ions were effectively penetrated into the ZnO crystal lattices with substitutional and interstitial impurities to form stable solid solutions without changing the polycrystalline wurtzite structure. Two peaks at 420 nm (2.95 eV, violet), 485 nm (2.56 eV, blue) have been observed from the photoluminescence (PL) spectra of the samples. It is concluded that the violet peak may correspond to the exciton emission; the blue emission corresponds to the electron transition from the bottom of the conduction band to the acceptor level of zinc vacancy. The optical test shows that the optical band gap E_g is decreased with the increase amount of Cu doping in ZnO. The band gap decrease from 3.40 eV to 3.25 eV gradually. It is also found that the transmission rate is increased rapidly with the increase of Cu ions concentration.     

Preparation and characterization of iron oxide thin films by spray pyrolysis using methanolic and ethanolic solutions

Iron oxide thin films have been obtained by spray pyrolysis using 100% methanolic and ethanolic solutions of iron tri-chloride. The films were deposited onto ITO-coated glass substrates. The preparative conditions have been optimized to obtain compact, pin-hole-free and smooth thin films which are adherent to the substrate. The structural, morphological and compositional characterizations have been carried out by X-ray diffraction, scanning electron microscopy and energy dispersive X-ray analysis. The films deposited using ethanolic solution results into pure hematite; α-Fe₂O₃ thin films, however, films deposited using methanolic solution consists of hematite and maghemite-c phases of iron oxide. The films are nanocrystalline with particle size of 30-40 nm. The optical absorbance of the film was of the order of 10⁵ cm⁻¹. The optical band gap of films was found to be 2.26 and 2.20 eV for the films deposited using methanolic and ethanolic solutions, respectively.