Effects of deposition temperature on the surface roughness and the nonlinear optical susceptibility of sprayed deposited ZnO:Zr thin films

Zirconium doped zinc oxide thin films were deposited by reactive chemical pulverization spray pyrolysis technique on heated glass substrates at 400 °C, 450 °C and 500 °C using zinc and zirconium chlorides as precursors. The effect of zirconium dopant and surface roughness on the nonlinear optical properties was investigated using atomic force microscopy (AFM) and third harmonic generation (THG). The best value of susceptibility χ⁽³⁾ was obtained from the doped films with less roughness. A strong third order nonlinear optical susceptibility χ⁽³⁾ = 20.49 × 10⁻¹² (esu) of the studied films was found for the 5% doped sample at 450 °C.     

Cathodoluminescent and nonlinear optical properties of undoped and erbium doped nanostructured ZnO films deposited by spray pyrolysis

We have deposited zinc oxide (ZnO) and erbium doped zinc oxide (ZnO:Er) thin films on heated glass substrates using spray pyrolysis technique. The effect of erbium dopant on structural, morphological, luminescent and nonlinear optical properties was studied. The deposited films have been analyzed using X-ray diffraction (XRD), scanning electron microscopy (SEM), ex situ compositional analysis (ESCA), profilometry, cathodoluminescence (CL) and third harmonic generation (THG) measurements. All films were polycrystalline, having a preferential growth orientation along the ZnO (0 0 2) plane, with a corresponding average crystallite size of less than 41 nm. Addition of erbium can effectively control the film surface morphology and its cathodoluminescent properties. The films containing low erbium concentration show a uniform surface covered with hexagonal shaped grains and a strong UV light emission intensity as well as TH response. In contrast, when the erbium doping ratio exceeds 3%, a porous surface with columnar textural growth becomes more pronounced, and a substantial reduction of the cathodoluminescent and TH response. A strong TH signal was obtained for the film with good crystalline quality at the concentration of 2%. Third order nonlinear optical susceptibility (χ^〈3〉) values of the studied materials were in the remarkable range of 10⁻¹² esu.     

Synthesis of CdZnO thin film as a potential candidate for optical switches

Cadmium doped zinc oxide thin films have been prepared using a thermal decomposition technique. The influence of Cd as a doping agent on the structure, optical and nonlinear optical properties was carefully investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM) and a UV-vis spectrophotometer. A deep correlation has been found between the surface roughness and the optical properties. The roughness is found to deteriorate the nonlinear response, such that the highest nonlinear susceptibility χ⁽³⁾ is obtained for the smoothest layer. The third-order nonlinear susceptibility χ⁽³⁾ has been calculated using the Frumer model, and is estimated to be 3.37×10⁻¹⁰ esu. The dispersion of the refractive index of the prepared thin film is shown to follow the single electronic oscillator model. From the model, the values of oscillator strength (E_d), oscillator energy (E_o) and dielectric constant (ε_∞) have been determined. The conductivity has been measured as a function of the energy of the photons, revealing marginal change at energies below 3.15 eV, while above this value there is a large increase in the conductivity. This suggests that CdZnO is a potential candidate for applications in optical devices such as optical limiter and optical switching.     

Influence of strain/stress on the nonlinear-optical properties of sprayed deposited ZnO:Al thin films

Nanocrystalline ZnO:Al thin films were deposited by reactive chemical pulverization spray pyrolysis technique on heated glass substrates at 450 °C to study their crystalline structure, composition, strain, stress, roughness characteristics and nonlinear optical susceptibility as a function of Al concentration (0, 2, 3, 5 at.%). The films were characterized by X-ray diffractometer (XRD), EDAX 9100 analyser, atomic force microscopy (AFM) and third harmonic generation (THG). The Al (3 at.%) doped ZnO thin films exhibited the lower strain/stress than undoped films. The nonlinear properties of the ZnO:Al thin films have been found to be influenced by the films strain/stress.     

Properties of Dy-doped ZnO nanocrystalline thin films prepared by pulsed laser deposition

Highly transparent conductive Dy₂O₃ doped zinc oxide (ZnO)_1-x(Dy₂O₃)_x nanocrystalline thin films with x from 0.5% to 5% have been deposited on glass substrate by pulsed laser deposition technique. The structural, electrical and optical properties of Dy₂O₃ doped thin films were investigated as a function of the x value. The experimental results show that the Dy concentration in Dy-doped ZnO thin films has a strong influence on the material properties especially electrical properties. The resistivity decreased to a minimum value of 5.02 × 10⁻⁴ Ω cm with x increasing from 0.5% to 1.0%, then significantly increased with the further increasing of x value. On the contrary, the optical direct band gap of the (ZnO)_1-x(Dy₂O₃)_x films first increased, then decreased with x increasing. The average transmission of Dy₂O₃ doped zinc oxide films in the visible range is above 90%.     

Nonlinear optical properties of Au/ZnO nanoparticle arrays

The triangular-shaped Au/ZnO nanoparticle arrays were fabricated on fused quartz substrate using nanosphere lithography. The structural characterization of the Au/ZnO nanoparticle arrays was investigated by atomic force microscopy. The absorption peak due to the surface plasmon resonance of Au particles at the wavelength of about 570 nm was observed. The nonlinear optical properties of the nanoparticle arrays were measured using the z-scan method at a wavelength of 532 nm with pulse duration of 10 ns. The real and imaginary part of third-order nonlinear optical susceptibility, Re χ⁽³⁾ and Im χ⁽³⁾, were determined to be 1.15 × 10⁻⁶ and −5.36 × 10⁻⁷ esu, respectively. The results show that the Au/ZnO nanoparticle arrays have great potential for future optical devices.     

Effect of doping concentration on the structural and optical properties of pure and tin doped zinc oxide thin films by nebulizer spray pyrolysis (NSP) technique

Pure and tin doped zinc oxide (Sn:ZnO) thin films were prepared for the first time by NSP technique using aqueous solutions of zinc acetate dehydrate, tin (IV) chloride fendahydrate and methanol. X-ray diffraction patterns confirm that the films are polycrystalline in nature exhibiting hexagonal wurtzite type, with (0 0 2) as preferred orientation. The structural parameters such as lattice constant (‘a’ and ‘c’), crystallite size, dislocation density, micro strain, stress and texture coefficient were calculated from X-ray diffraction studies. Surface morphology was found to be modified with increasing Sn doping concentration. The ZnO films have high transmittance 85% in the visible region, and the transmittance is found to be decreased with the increase of Sn doping concentration. The corresponding optical band gap decreases from 3.25 to 3.08 eV. Room temperature photoluminescence reveals the sharp emission of strong UV peak at 400 nm (3.10 eV) and a strong sharp green luminescence at 528 nm (2.34 eV) in the Sn doped ZnO films. The electrical resistivity is found to be 10⁶ Ω-cm at higher temperature and 10⁵ Ω-cm at lower temperature.     

Nonlinear optical properties of erbium doped zinc oxide (EZO) thin films

Undoped and Erbium (Er) doped zinc oxide (EZO) thin films were deposited on glass substrate by sol–gel method using spin coating technique with different doping concentration. EZO films were characterized using X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), UV–VIS-NIR transmission and single beam z scan method under illumination of frequency doubled Nd:YAG laser. The deposited films were found to be well crystallized with hexagonal wurtzite structure having a preferential growth orientation along the ZnO (002) plane. A blue-shift was observed in the band gap of EZO films with increasing Er concentration. All the films exhibited a negative value of nonlinear refractive index (n₂) at 532 nm which is attributed to the two photon absorption and weak free carrier absorption. Third order nonlinear optical susceptibility, χ⁽³⁾ values of EZO films were observed in the remarkable range of 10^? 6 esu. EZO (0.4 at.%) sample was found to be the best optical limiter with limiting threshold of 1.95 KJ/cm².     

Investigation on the effect of Zr doping in ZnO thin films by spray pyrolysis

Zirconium doped zinc oxide thin films with enhanced optical transparency were prepared on Corning 1737 glass substrates at the substrate temperature of 400 °C by spray pyrolysis method for various doping concentrations of zirconium (IV) chloride in the spray solution. The X-ray diffraction studies reveal that the films exhibit hexagonal crystal structure with polycrystalline grains oriented along (0 0 2) direction. The crystalline quality of the films is found to be deteriorating with the increase of doping concentration and acquires amorphous state for higher concentration of 8 at.% in precursor solution. The average transmittance for 5 at.% (solution) zirconium doped ZnO film is significantly increased to ∼92% in the visible region of 500-800 nm. The room temperature photoluminescence (PL) spectra of films show a band edge between 3.41 and 3.2 eV and strong blue emission at 2.8 eV irrespective of doping concentration and however intensity increases consistently with doping levels. The vacuum annealing at 400 °C reduced the resistivity of the films significantly due to the coalescence of grains and the lowest resistivity of 2 × 10⁻³ Ω cm is observed for 3 at.% (solution) Zr doped ZnO films which envisages that it is a good candidate for stable TCO material.     

Microstructure and optical properties of nanocrystalline ZnO and ZnO:(Li or Al) thin films

Zinc oxide thin films (ZnO, ZnO:Li, ZnO:Al) were deposited on glass substrates by a sol-gel technique. Zinc acetate, lithium acetate, and aluminum chloride were used as metal ion sources in the precursor solutions. XRD analysis revealed that Li doped and undoped ZnO films formed single phase zincite structure in contrast to Al:ZnO films which did not fully crystallize at the annealing temperature of 550 °C. Crystallized films had a grain size under 50 nm and showed c-axis grain orientation. All films had a very smooth surface with RMS surface roughness values between 0.23 and 0.35 nm. Surface roughness and optical band tail values increased by Al doping. Compared to undoped ZnO films, Li doping slightly increased the optical band gap of the films.     

Thickness dependent optical dispersion parameters and nonlinear optical properties of nanostructured Cr doped CdO thin films

Cr doped CdO thin films were deposited on glass substrates by reactive DC magnetron sputtering with varying film thickness from 250 to 400 nm. XRD studies reveal that the films exhibit cubic structure with preferred orientation along the (2 0 0) plane. The optical transmittance of the films decreases from 92 to 72%, whereas the optical energy band gap of the films decreased from 2.88 to 2.78 eV with increasing film thickness. The Wemple–DiDomenico single oscillator model has been used to evaluate the optical dispersion parameters such as dispersion energy (E_d), oscillator energy (E_o), static refractive index (n_o) and high frequency dielectric constant (ε_∞). The nonlinear optical parameters such as optical susceptibility (χ⁽¹⁾), third order nonlinear optical susceptibility (χ⁽³⁾) and nonlinear refractive index (n₂) of the films were also determined.     

Third-order optical nonlinearities of lead-free (Na1−xKx)0.5Bi0.5TiO3 thin films

(Na_1−xK_x)_0.5Bi_0.5TiO₃ (NKBT) (x = 0.1, 0.2, and 0.3) thin films with good surface morphology and rhombohedral perovskite structure were fabricated on quartz substrates by a sol-gel process. The fundamental optical constants (the band gaps, linear refractive indices and absorption coefficients) of the films were obtained through optical transmittance measurements. The nonlinear optical properties were investigated by Z-scan technique performed at 532 nm with a picosecond laser. A two-photon absorption effect closely related with potassium-doping content was found in thin films, and the nonlinear refractive index n₂ increases evidently with potassium-doping. The real part of the third-order nonlinear susceptibility χ⁽³⁾ is much larger than its imaginary part, indicating that the third-order optical nonlinear response of the NKBT films is dominated by the optical nonlinear refractive behavior. These results show that NKBT thin films have potential applications in nonlinear optics.     

Deposition and characterization of transparent and conductive sprayed ZnO:B thin films

Highly transparent and conductive Boron doped zinc oxide (ZnO:B) thin films were deposited using chemical spray pyrolysis (CSP) technique on glass substrate. The effect of variation of boron doping concentration in reducing solution on film properties was investigated. Low angle X-ray analysis showed that the films were polycrystalline fitting well with a hexagonal wurtzite structure and have preferred orientation in [002] direction. The films with resistivity 2.54×10⁻³ Ω-cm and optical transmittance >90% were obtained at optimized boron doping concentration. The optical band gap of ZnO:B films was found ∼3.27 eV from the optical transmittance spectra for the as-deposited films. Due to their excellent optical and electrical properties, ZnO:B films are promising contender for their potential use as transparent window layer and electrodes in solar cells.     

Device quality ZnO grown using a Filtered Cathodic Vacuum Arc

In this paper we report on the structural, electrical and optical characteristics of unintentionally doped ZnO films grown on a-plane sapphire substrates using the Filtered Cathodic Vacuum Arc (FCVA) technique. The resulting films showed considerable promise for device applications with properties including high transparency, moderate intrinsic carrier concentrations (10¹⁷–10¹⁹ cm⁻³), electron mobilities up to 30 cm²/Vs, low surface roughness (typically <2% of film thickness) and well-structured photoluminescence. Post-annealing in oxygen at temperatures up to 800 °C produced significant improvements in the properties of these films. Silver oxide Schottky diodes fabricated on FCVA ZnO showed ideality factors as low as 1.20 and good sensitivity to ultraviolet light.     

Effect of substrate temperature on properties of multilayer thin film based on ZnO and Mo-doped indium oxide

Zinc oxide/molybdenum-doped indium oxide/zinc oxide (ZnO/IMO/ZnO) multilayer thin films are grown using pulsed laser deposition technique. The effect of substrate temperature on structural, optical, and electrical properties of multilayer films is studied. It is observed that films grown at high substrate temperature are oriented along (0 0 2) and (2 2 2) direction for ZnO and IMO respectively. The crystallinity of these films increases with increase in substrate temperature. It is also seen that conductivity, carrier concentration, and mobility increase with increase in temperature. The multilayer film grown at 500 °C has low resistivity (7.67 × 10⁻⁵ Ω cm), high carrier concentration (3.90 × 10²⁰ cm⁻³), and high mobility (209 cm²/Vs).     

χ measurement and optical limiting studies of urea picrate

The molecular charge complex urea picrate (UP) was synthesized and its third order nonlinear optical properties have been investigated using a single beam Z-scan technique with nanosecond laser pulses at 532 nm. Open aperture data of the compound indicates two photon absorption at this wavelength. The nonlinear refractive index n₂, nonlinear absorption coefficient β, magnitude of effective third order susceptibility χ⁽³⁾, the second order hyperpolarizability γ_h and the coupling factor ρ have been estimated. The experimentally determined values of β, n₂, Re χ⁽³⁾ and Im χ⁽³⁾, γ_h and ρ of the compound UP are 2.146 cm/GW, −1.258×10⁻¹¹ esu, −1.347×10⁻¹³ esu, 0.377×10⁻¹³ esu, 0.69×10⁻³² esu and 0.28, respectively. The compound exhibits good optical limiting at 532 nm with the limiting threshold of 80 μJ/pulse. Our studies suggest that compound UP is a potential candidate for optical device applications such as optical limiters.     

The crystalline structure,conductivity and optical properties of Co-doped ZnO thin films

Transparent conductive Co-doped ZnO thin films were deposited by ultrasonic spray technique. Conditions of preparation have been optimized to get good quality. A set of cobalt (Co)-doped ZnO (between 0 and 3 wt%) thin films were grown on glass substrate at 350 °C. The thin films were annealed at 500 °C for improvement of the physical properties. Nanocrystalline films with hexagonal wurtzite structure and a strong (0 0 2) preferred orientation were obtained. The maximum value of grain size G = 63.99 nm is attained with undoped ZnO film. The optical transmissions spectra showed that both the undoped and doped ZnO films have transparency within the visible wavelength region. The band gap energy decreased after doping from 3.367 to 3.319 eV when Co concentration increased from 0 to 2 wt% with slight increase of electrical conductivity of the films from 7.71 to 8.33 (Ω cm)⁻¹. The best estimated structure, optical and electrical results are achieved in Co-doped ZnO film with 2 wt%.     

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.     

Synthesis and characterization of Ni-doped ZnO: A transparent magnetic semiconductor

We report synthesis of a transparent magnetic semiconductor by incorporating Ni in zinc oxide (ZnO) matrix. ZnO and nickel-doped zinc oxide (ZnO:Ni) thin films (∼60 nm) are prepared by fast atom beam (FAB) sputtering. Both undoped and doped films show the presence of ZnO phase only. The Ni concentration (in at%) as determined by energy dispersive X-ray (EDX) technique is ∼12±2%. Magnetisation measurement using a SQUID magnetometer shows that the Ni-doped films are ferromagnetic, having coercivity (H_c) values 192, 310 and 100 Oe and saturation magnetization (M_s) values of 6.22, 5.32 and 4.73 emu/g at 5, 15 and 300 K, respectively. The Ni-doped film is transparent (>80%) across visible wavelength range. Resistivity of the ZnO:Ni film is ∼2.5×10⁻³ Ω cm, which is almost two orders of magnitude lower than the resistivity (∼4.5×10⁻¹ Ω cm) of its undoped counterpart. Impurity d-band splitting is considered to be the cause of increase in conductivity. Interaction between free charges generated by doping and localized d spins of Ni is discussed as the reason for ferromagnetism in the ZnO:Ni film.     

Effects of rf power on surface-morphological, structural and electrical properties of aluminium-doped zinc oxide films by magnetron sputtering

Aluminium-doped zinc oxide (ZnO:Al) films were prepared by magnetron sputtering at different radio-frequency powers (P_rf) of 50, 100, 150 and 200 W. The properties of the films were characterised by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), Raman microscopy, and spectrophotometry with the emphasis on the evolution of compositional, surface-morphological, optical, electrical and microstructural properties. XPS spectra showed that within the detection limit the films are chemically identical to near-stoichiometric ZnO. AFM revealed that root-mean-square roughness of the films has almost linear increase with increasing P_rf. Optical band gap E_gopt of the films increases from 3.31 to 3.51 eV when P_rf increases from 50 to 200 W. A widening E_gopt of the ZnO:Al films compared to the band gap (∼3.29 eV) of undoped ZnO films is attributed to a net result of the competition between the Burstein-Moss effect and many-body effects. An electron concentration in the films was calculated in the range of 3.73 × 10¹⁹ to 2.12 × 10²⁰ cm⁻³. Raman spectroscopy analysis indicated that well-identified peaks appear at around 439 cm⁻¹ for all samples, corresponding to the band characteristics of the wurtzite phase. Raman peaks in the range 573-579 cm⁻¹ are also observed, corresponding to the A₁ (LO) mode of ZnO.