Spectroscopic properties of mixed Langmuir-Blodgett films of rhodamine dyes and poly(N,N-diallyl-N-octadecylamine-alt-maleic acid)

Langmuir-Blodgett (LB) films of poly(N,N-diallyl-N-octadecylamine-alt-maleic acid) as well as mixed films consisting of polyampholyte and two amphiphilic fluorophores - alkyl substituted rhodamine dyes - were prepared and investigated. The π-A isotherm of the polyampholyte at air-water interface is typical for monolayer in the liquid state. Mixed monolayers of polyampholyte and rhodamine amphiphiles show improved packing of the hydrophobic chains. Absorption and fluorescence spectroscopic studies of the mixed LB films reveal the aggregation of dyes in the densely packed multilayer films.     

Probing and modeling of carrier motion in organic devices by optical second harmonic generation

We here report a novel optical second harmonic generation (SHG) measurement that allows an electric field formed in organic solid to be probed. We examined the SHG intensity profile that changes depending on a space charge field caused by carrier injection. Experiments making use of time-resolved SHG technique has revealed dynamic changes of SHG intensity profiles arising from pentacene, and that carrier transport in OFET was diffusion-like. Calculations using drift-diffusion equation well accounted for the visualized carrier motion probed by time-resolved SHG. That is, interface charge propagation process dominates the carrier transport, which is regulated by applied gate-source voltage.     

Incorporation in Langmuir and Langmuir-Blodgett films of symmetric fluorine substituted bent-core liquid crystals: Morphological and optical properties

Molecular mono- and multilayer films of a symmetric fluorine substituted bent-core liquid crystalline (LC) compound with hydrocarbon end-chains were prepared by the Langmuir and Langmuir-Blodgett (LB) technique. Langmuir films were characterized by surface pressure isotherms and Brewster angle microscopy. Likewise LB-films deposited onto amorphous glass substrates were characterized by ultraviolet-visible spectroscopy, the optical second harmonic generation technique and atomic force microscopy (AFM). Results show optimal non-centrosymmetric Z-type LB-film deposition for moderate number of layers (n < 20); thereafter, an apparent collapse of the Z-type structure occurs, giving rise to a decrease of the nonlinear optical (NLO) properties. AFM, NLO and linear optical measurements suggest a uniform molecular coverage on the glass substrates and anisotropic orientational distribution; where, according to NLO-experimental data, the LC-bent-shaped molecules are preferably aligned toward the dipping direction with the net molecular polarization perpendicularly aligned to the substrate layer. This observation leads us to implement a simplified model based on the monomeric rod-like approximation, in order to estimate the significant NLO-tensor components.     

Stability of dimethyldioctadecylammonium bromide Langmuir-Blodgett films on mica in aqueous salt solutions—implications for surface force measurements

Langmuir-Blodgett (LB) monolayer films of dimethyldioctadecylammonium bromide (DDOA) on muscovite mica have been studied using Wilhelmy plate type wetting measurements, surface force measurements, atomic force microscopy (AFM), and Brewster angle microscopy (BAM) on insoluble monolayers of DDOA before deposition. In particular, the effect of exposure to aqueous KBr salt solutions was investigated. BAM shows a heterogeneous monolayer with small condensed domains of dendritic shape under conditions normally used for deposition. A stick-jump behaviour of the meniscus is seen during deposition, leading to a large-scale heterogeneity measurable in wetting studies. These also show breakdown and hydrophilization of the LB film at the three-phase contact line (meniscus) and when exposed to salt solutions of approximately 10⁻² M concentration. The advancing contact angle against water is approximately 105°. Surface force measurements show long-range attraction in water, but also a surface charge which depends on salt concentration, and breakdown when surfaces are brought into contact in high salt concentrations. AFM images of untreated films show small holes, and breakdown when exposed to salt solution, especially at the three-phase line. The LB film is judged to be less suitable as a model hydrophobic surface owing to its heterogeneity and instability in salt solution.     

Second-order nonlinear optical properties of mexylaminotriazine-functionalized glass-forming azobenzene derivatives

The second-order nonlinear optical coefficients of thin films of mexylaminotriazine-functionalized azobenzene molecular glass derivatives were measured using second harmonic generation. The thin films were poled using a custom corona poling set-up and the second harmonic light from a pulsed 1064-nm laser was detected. Four out of the six tested compounds showed optical nonlinearity and a maximum coefficient of 75 pm/V was obtained. The time dependence of the nonlinear coefficients was studied under ambient light and under dark; the second harmonic generation intensity stayed constant for thiazole-containing derivatives while a significant decay was measured for the other compounds.     

Quasi-phase-matched second harmonic generation device in Mg-doped LiNbO3 and its application to high-density optical disk system

The resistance to photorefractive damage is investigated for several nonlinear crystals. A quasi-phase-matched (QPM) second harmonic generation (SHG) waveguide device is fabricated in 5 mol% Mg-doped LiNbO₃ which has high resistance to optical damage. The SHG blue laser of the QPM-SHG waveguide device and a tunable distributed Bragg reflector (DBR) laser diode is demonstrated, wherein output stability of continuous blue light is measured. The SHG blue laser, using the QPM-SHG waveguide device with broadened flat matching response, shows good modulation characteristics. The pulsed peak power of 23 mW with rectangular modulated waveform is generated. The SHG blue laser is installed to an optical head, and good recording and readout characteristics are demonstrated. Moreover, butt-coupled SHG blue laser is examined to gain a miniature module with volume of 0·8 cc.     

Influence of Nb dopant on the structural and optical properties of nanocrystalline TiO2 thin films

In this study, preparation of Nb-doped (0-20 mol% Nb) TiO₂ dip-coated thin films on glazed porcelain substrates via sol-gel process has been investigated. The effects of Nb on the structural, optical, and photo-catalytic properties of applied thin films have been studied by X-ray diffraction, Raman spectroscopy, and scanning electron microscopy. Surface topography and surface chemical state of thin films was examined by atomic force microscope and X-ray photoelectron spectroscopy. XRD and Raman study showed that the Nb doping inhibited the grain growth. The photo-catalytic activity of the film was tested on degradation of methylene blue. Best photo-catalytic activity of Nb-doped TiO₂ thin films were measured in the TiO₂-1 mol% Nb sample. The average optical transmittance of about 47% in the visible range and the band gap of films became wider with increasing Nb doping concentration. The Nb⁵⁺ dopant presented substitutional Ti⁴⁺ into TiO₂ lattice.     

Effect of silane flow rate on structural,electrical and optical properties of silicon thin films grown by VHF PECVD technique

Hydrogenated silicon thin films deposited by VHF PECVD process for various silane flow rates have been investigated. The silane flow rate was varied from 5 sccm to 30 sccm, maintaining all other parameters constant. The electrical, structural and optical properties of these films were systematically studied as a function of silane flow rate. These films were characterized by Raman spectroscopy, Scanning Electron Microscopy (SEM), atomic force microscopy (AFM), Fourier transform infrared (FTIR) spectroscopy and UV–visible (UV–Vis) spectroscopy. Different crystalline volume fraction (22%–60%) and band gap (∼1.58 eV–∼1.96 eV) were achieved for silicon thin films by varying the silane concentration. A transition from amorphous to nanocrystalline silicon has been confirmed by Raman and FTIR analysis. The film grown at this transition region shows the high conductivity in the order of 10⁻⁴ Ω⁻¹ cm⁻¹.     

Effect of cadmium oxide incorporation on the microstructural and optical properties of pulsed laser deposited nanostructured zinc oxide thin films

CdO doped (doping concentration 0, 1, 3 and 16 wt%) ZnO nanostructured thin films are grown on quartz substrate by pulsed laser deposition and the films are annealed at temperature 500 °C. The structural, morphological and optical properties of the annealed films are systematically studied using grazing incidence X-ray diffraction (GIXRD), energy dispersive X-ray analysis (EDX), scanning electron microscopy (SEM), atomic force microscopy (AFM), Micro-Raman spectra, UV–vis spectroscopy, photoluminescence spectra and open aperture z-scan. 1 wt% CdO doped ZnO films are annealed at different temperatures viz., 300, 400, 500, 600, 700 and 800 °C and the structural and optical properties of these films are also investigated. The XRD patterns suggest a hexagonal wurtzite structure for the films. The crystallite size, lattice constants, stress and lattice strain in the films are calculated. The presence of high-frequency E₂ mode and the longitudinal optical A₁ (LO) modes in the Raman spectra confirms the hexagonal wurtzite structure for the films. The presence of CdO in the doped films is confirmed from the EDX spectrum. SEM and AFM micrographs show that the films are uniform and the crystallites are in the nano-dimension. AFM picture suggests a porous network structure for 3% CdO doped film. The porosity and refractive indices of the films are calculated from the transmittance and reflectance spectra. Optical band gap energy is found to decrease in the CdO doped films as the CdO doping concentration increases. The PL spectra show emissions corresponding to the near band edge (NBE) ultra violet emission and deep level emission in the visible region. The 16CdZnO film shows an intense deep green PL emission. Non-linear optical measurements using the z-scan technique indicate that the saturable absorption (SA) behavior exhibited by undoped ZnO under green light excitation (532 nm) can be changed to reverse saturable absorption (RSA) with CdO doping. From numerical simulations the saturation intensity (I_s) and the effective two-photon absorption coefficient (β) are calculated for the undoped and CdO doped ZnO films.     

Effect of thermal annealing time on optical and structural properties of TeO2 thin films

TeO₂ thin films were deposited on quartz substrates by rf reactive sputtering technique from a Te metal target. The obtained samples were annealed in an argon atmosphere at 450 °C for different annealing times up to 90 min. X-ray diffraction studies revealed that the as-grown samples were amorphous and there was no appreciable change in structure for a short annealing time. Thin films became polycrystalline with the tetragonal (α-phase) structure of tellurium dioxide crystal with the increase of the thermal annealing time. The refractive index and optical energy gap of the films were calculated by modelling transmittance spectra. The optical energy gap decreased continuously from 3.83 eV to 3.71 eV with increasing thermal annealing time.     

Effect of Al dopants on the structural,optical and gas sensing properties of spray-deposited ZnO thin films

Undoped and Al-doped ZnO thin films were deposited on glass substrates by the spray pyrolysis method. The structural, morphological and optical properties of these films were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), UV–Vis spectroscopy, photoluminescence (PL) and photoconductivity (PC) measurements, respectively. XRD analyses confirm that the films are polycrystalline zinc oxide with the hexagonal wurtzite structure, and the crystallite size has been found to be in the range 20–40 nm. SEM and AFM analyses reveal that the films have continuous surface without visible holes or faulty zones, and the surface roughness decreases on Al doping. The Al-doped films have been found to be highly transparent (>85%) and show normal dispersion behavior in the wavelength range 450–700 nm. The doped films show only ultraviolet emission and are found to be highly photosensitive. Among all the films examined, at 300 °C the 1.0 at% Al-doped film shows the selective high response (98.2%) to 100 ppm acetone concentration over to methanol, ethanol, propan-2-ol, formaldehyde and hydrogen.     

Effect of high-temperature annealing on the optical and photoluminescence properties of nanocrystalline SiC films

The optical and photoluminescence (PL) properties of nanocrystalline 3C-SiC films and the effect of the boundary regions between the nanocrystals were studied for two sets of films: (a) films with 10-15 nm nanocrystal size obtained by direct ion deposition method and (b) similar films annealed in oxygen at 850-950 °C. It was shown that annealing of the nanocrystalline SiC films resulted in weaker absorption in a broad spectral range, and to the increase of the optical band gap from 1.8 to 2.2 eV. On the contrary, the edge PL bands in the UV range (2.2 to 2.4 eV) remained similar. In the IR range, three maxima absent in the as-grown films, appeared at 1.52 eV, 1.56 eV and 1.63 eV. Measurement of the intensity of PL maxima as a function of the excitation power showed a nonlinear dependence that was attributed to the onset of stimulated emission.     

Structural and optical properties of high refractive indices lead vanadate thin films

Glasses with the chemical formula xWO₃–50PbO–(50 − x)V₂O₅, (0 ≤ x ≤ 10 mol%) were prepared by the usual melt quenching technique. FTIR analysis revealed that, the incorporation of WO₃ into the lead-vanadate network increases the number of bridging oxygens, and replaces low-coordinated structural units such as PbO₄, and VO₄ with higher coordinated structural units WO₆ and VO₅ which increases the number of bonds and the average cross-link density. Thin films of these glasses onto quartz substrates have been obtained by thermal evaporation technique. Based only on the measured transmittance spectra in the wavelength range 200–2500 nm, both the film thickness and the complex index of refraction have been calculated precisely. The absorption edge was shifted toward the long wavelength side (i.e. red shift of the optical band gap) as the WO₃ content increases. The dispersion of the refractive index was discussed in terms of the single oscillator model. The allowed non-direct transitions successfully describe the absorption mechanism in these films. Based on generalized Miller's rule, the third-order non-linear optical susceptibility χ⁽³⁾ has been investigated. The obtained values of χ⁽³⁾ values are rather large, indicating that the films under study are interesting materials for non-linear optical devices.     

Influence of the growth conditions on the stoichiometry and on the optical properties of titanium oxide thin films prepared by reactive sputtering

Titanium oxide thin films are deposited at room temperature by reactive DC sputtering onto glass and Si (100) substrates. Different conditions of deposition were varied such as sputtering power, deposition time and oxygen partial pressure to study their influence on the titanium oxide thin films growth. The absolute amount of oxygen and the relative O/Ti composition of films have been determined by Nuclear Reaction Analysis and Rutherford Backscattering Spectroscopy, respectively. Additionally, the band-gap was determined by measuring the optical absorption and its behavior correlated with the oxygen film content. From the present study, it is possible to establish that the optical band-gap energy depends mainly on the sputtering oxygen partial pressure used at the preparation and that films prepared with a partial oxygen pressure of 4 × 10^− 2 Pa allows titanium oxide with near stoichiometric composition. Additionally, from the optical point of view, band-gap energies of 3.4 eV are obtained for near stoichiometric films and a decrease is observed for samples prepared with higher oxygen concentrations.     

Effect of Zr (IV) doping on the optical properties of sol–gel based nanostructured indium oxide films on glass

Zr (IV) doped indium oxide thin films (55 nm) were deposited onto pure silica glass by the sol–gel dip coating technique utilizing the precursors of 6 wt% equivalent oxide content. Three different Zr (IV) oxide (ZrO₂) dopant concentrations (5.0, 10.0 and 15.0 wt% w.r.t. total oxides) were chosen. XRD patterns suggested the films were of distinct cubic symmetry of In₂O₃. Nanostructured surface feature was revealed by FESEM images. Average cluster size decreased with increasing dopant concentration as evidenced from TEM study. Blue shift of band gap and UV cut off wavelength (lambda-50) occurred with increase in dopant concentration. The refractive index gradually increased with doping. Baking atmosphere plays an important role in tailoring the refractive index (RI) of the films and relatively high RI was obtained in the case of baking in pure oxygen. Presence of both free and bound excitons was detected by the photoluminescence (PL) study. The 5 wt% doped film exhibited relatively high PL intensity at 380 nm responsible for free exciton. The PL emissions gradually quenched with increase in dopant concentration. Similar behaviour was also observed when the film was baked in pure oxygen atmosphere.     

Studies on the optical band gap and cluster size of the polyaniline thin films irradiated with swift heavy Si ions

Polyaniline thin films prepared by RF plasma polymerisation were irradiated with 92 MeV Si ions for various fluences of 1×10¹¹, 1×10¹² and 1×10¹³ ions/cm². FTIR and UV-vis-NIR measurements were carried out on the pristine and Si ion irradiated polyaniline thin films for structural evaluation and optical band gap determination. The effect of swift heavy ions on the structural and optical properties of plasma-polymerised aniline thin film is investigated. Their properties are compared with that of the pristine sample. The FTIR spectrum indicates that the structure of the irradiated sample is altered. The optical studies show that the band gap of irradiated thin film has been considerably modified. This has been attributed to the rearrangement in the ring structure and the formation of CC terminals. This results in extended conjugated structure causing reduction in optical band gap.     

Effect of the oxygen partial pressure on the microstructure and optical properties of ZnO:Cu films

Cu-doped zinc oxide (ZnO:Cu) films were deposited on Si substrates using radio frequency reactive magnetron sputtering at different oxygen partial pressures. The effect of oxygen partial pressure on the microstructures and optical properties of ZnO:Cu thin films were systematically investigated by X-ray diffraction (XRD), atomic force microscopy (AFM) and fluorescence spectrophotometer. The results indicated that the grain orientation of the films was promoted by appropriate oxygen partial pressures. And with increasing oxygen partial pressure, the compressive stress of the films increased first and then decreased. The photoluminescence (PL) of the samples were measured at room temperature. A violet peak, two blue peaks and a green peak were observed from the PL spectra of the four samples. The origin of these emissions was discussed and the mechanism of violet emission of ZnO:Cu thin films were suggested.     

Effect of boron doping on optical properties of sol-gel based nanostructured zinc oxide films on glass

Boron doped zinc oxide thin films (∼80 nm) were deposited onto pure silica glass by sol-gel dip coating technique from the precursor sol/solution of 4.0 wt.% equivalent oxide content. The boron concentration was varied from 0 to 2 at.% w.r.t. Zn using crystalline boric acid. The nanostructured feature of the films was visualized by FESEM images and the largest cluster size of ZnO was found in 1 at.% boron doped film (B1ZO). The presence of mixed crystal phases with hexagonal as major phase was identified from XRD reflections of the films. Particle size, optical band gap, visible specular reflection, room temperature photoluminescence (PL) emissions (3.24-2.28 eV), infra-red (IR) and Raman active longitudinal optical (LO) phonon vibration were found to be dependent on dopant concentration. For the first time, we report the room temperature fine structured PL emissions as phonon replicas originated from the LO phonon (both IR and Raman active) in 1 at.% boron doped zinc oxide film.     

Effect of sputtering power on the electrical and optical properties of Ca-doped ZnO thin films sputtered from nanopowders compacted target

In the present work, we have deposited calcium doped zinc oxide thin films by magnetron sputtering technique using nanocrystalline particles elaborated by sol–gel method as a target material. In the first step, the nanoparticles were synthesized by sol–gel method using supercritical drying in ethyl alcohol. The structural properties studied by X-ray diffractometry indicates that Ca doped ZnO has a polycrystalline hexagonal wurzite structure with a grain size of about 30 nm. Transmission electron microscopy (TEM) measurements have shown that the synthesized CZO is a nanosized powder. Then, thin films were deposited onto glass substrates by rf-magnetron sputtering at ambient temperature. The influence of RF sputtering power on structural, morphological, electrical, and optical properties were investigated. It has been found that all the films deposited were polycrystalline with a hexagonal wurtzite structure and preferentially oriented in the (0 0 2) crystallographic direction. They have a typical columnar structure and a very smooth surface. The as-deposited films show a high transmittance in the visible range over 85% and low electrical resistivity at room temperature.     

Effect of annealing treatment on structural, electrical, and optical properties of Ga-doped ZnO thin films deposited by RF magnetron sputtering

The effect of annealing on structural, electrical, and optical properties of Ga-doped ZnO (GZO) films prepared by RF magnetron sputtering was investigated in air and nitrogen. GZO films are polycrystalline with a preferred 002 orientation. The resistivities of annealed films are larger than the as-deposited. The transmittance in the near IR region increases greatly and the optical band gap decreases after annealing. The photoluminescence spectra is composed of a near band edge emission and several deep level emissions (DLE) which are dominated by a blue emission. After annealing, these DLEs are enhanced evidently.