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.     

Nonlinear optical properties in SrTiO3 thin films by pulsed laser deposition

Well-crystallized 250 nm-thick SrTiO₃ thin films on fused-quartz substrate were prepared by pulsed laser deposition. The band-gap of SrTiO₃ thin film by transmittance spectra is equal to 3.50 eV, larger than 3.22 eV for the bulk crystal. The nonlinear optical properties of the films were examined with picosecond pulses at 1.064 μm excitation. A large two-photon absorption (TPA) with absorption coefficient of 87.7 cm/GW was obtained, larger than 51.7 cm/GW for BaTiO₃ thin films. The nonlinear refractive index n₂ is equal to 5.7×10⁻¹⁰ esu with a negative sign, larger than 0.267×10⁻¹¹ esu for bulk SrTiO₃. The large TPA is attributed to intermediate energy levels introduced by the grain boundaries, and the optical limiting behaviors stemming from both TPA and negative nonlinear refraction were also discussed.     

Third-order optical nonlinearity of (Ba0.7Sr0.3)TiO3 ferroelectric thin films fabricated by soft solution processing

(Ba_0.7Sr_0.3)TiO₃ (BST) ferroelectric thin films with perovskite crystal structure were fabricated by soft solution processing on a quartz substrate. The third-order nonlinear optical properties were investigated by using Z-scan technique. Positive nonlinear refractive index and nonlinear absorption coefficient were determined to be 4×10⁻⁷ esu and 1.2×10⁻⁶ m/w, respectively. The real part and imaginary part of third-order optical nonlinear susceptibility were calculated and the values were 6.43×10⁻⁸ and 5.14×10⁻⁸ esu, respectively. All of these results show ferroelectric BST thin film is promising for applications in nonlinear optical devices.     

Optical properties of poly(methyl methacrylate)–titania nanostructure thin films containing ellipsoid-shaped titania nanoparticles from ex-situ sol-gel method at low growth temperature

This paper reports on the linear and nonlinear optical responses of the PMMA-TiO₂ nanohybrid thin films which are synthesized by a flexible ex-situ sol-gel/polymerization process, assisted by spin coating and multi-step baking. Triethanolamine (TEOA) as surfactant and shape controller is used to modify the interface between PMMA and TiO₂, allowing a highly homogeneous dispersion of the ellipsoid-shaped TiO₂ nanoparticles. The resulting nanohybrid thin films have highly optical transparency as proved by the linear absorption photon-energy spectra and indicate an enhanced nonlinear optical (NLO) response as confirmed by the Z-scan technique using 800-nm, 120-femtosecond (fs) laser pulses, highlighting the potential of the nanocomposites for efficient optical devices.     

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.     

Organic thin films based on a dicyanovinyl-quaterthiophene: Influence of electrode configuration on third-order nonlinear optical properties measured by electroabsorption spectroscopy

Electroabsorption (EA) studies at room temperature on organic thin films based on a dicyanovinyl-quaterthiophene 4T-V(CN)₂ are reported. An electric field modulation is applied to the samples for two different electrode geometries, i.e. sandwich and coplanar versus the organic layer. Changes in optical absorption coefficient of 4T-V(CN)₂ based thin films are measured and analyzed to determine the character of the optical transition in the visible range (400-800 nm). Depending on the experimental electrode configuration, magnitude of electroabsorption responses are different, possibly due to different distribution of the externally applied electric field. The results indicate a higher resolution of EA response for the sandwich electrode configuration and confirm the charge transfer exciton character of 4T-V(CN)₂ in contrast to the unsubstituted quaterthiophene 4T. Finally, a third-order nonlinear susceptibility χ⁽³⁾ (−ω; ω, 0, 0) of 16 × 10⁻¹² e.s.u. is obtained.     

Fabrication of nanostructured CuInS2 thin films by ion layer gas reaction method

CuInS₂ thin films were prepared by a two-stage ion layer gas reaction (ILGAR) process in which the Cu and In precursors were deposited on glass substrate by using a simple and low-cost dip coating technique and annealed in H₂S atmosphere at different temperatures. The influence of the annealing temperature (250-450 °C) on the particle size, crystal structure and optical properties of the CuInS₂ thin films was studied. Transmission electron microscopy revealed that the particle radii varied in the range 6-21 nm with annealing. XRD and SAED patterns indicated polycrystalline nature of the nanoparticles. The optical band gap (E_g) varied from 1.48 to 1.56 eV with variation of particle size. The variation of Urbach tail with temperature indicated higher density of the defects for the films annealed at lower temperature. From the Raman study, it was observed that the FWHM of the A₁ mode at ∼292 cm⁻¹ corresponding to the chalcopyrite phase of CuInS₂ decreased with increasing annealing temperature.     

Structural, optical properties and VCNR mechanisms in vacuum evaporated iodine doped ZnSe thin films

Iodine doped ZnSe thin films were prepared onto uncoated and aluminium (Al) coated glass substrates using vacuum evaporation technique under a vacuum of 3 × 10⁻⁵ Torr. The composition, structural, optical and electrical properties of the deposited films were analyzed using Rutherford backscattering spectrometry (RBS), X-ray diffraction (XRD), spectroscopic ellipsometry (SE) and study of I-V characteristics, respectively. In the RBS analysis, the composition of the deposited film is calculated as ZnSeI_0.003. The X-ray diffractograms reveals the cubic structure of the film oriented along (1 1 1) direction. The structural parameters such as crystallite size, strain and dislocation density values are calculated as 32.98 nm, 1.193 × 10⁻³ lin⁻² m⁻⁴ and 9.55 × 10¹⁴ lin/m², respectively. Spectroscopic ellipsometric (SE) measurements were also presented for the prepared iodine doped ZnSe thin films. The optical band gap value of the deposited films was calculated as 2.681 eV by using the optical transmittance measurements and the results are discussed. In the electrical studies, the deposited films exhibit the VCNR conduction mechanism. The iodine doped ZnSe films show the non-linear I-V characteristics and switching phenomena.     

Synthesis and investigation of nonlinear optical properties of semiconductor ZnS nanoparticles

ZnS nanoparticles were prepared by a simple chemical method and using PVP (poly vinylpyrrolidone) as capping agent. The sample was characterized by UV-vis spectrophotometer, X-ray diffraction (XRD) and Z-scan technique. XRD pattern showed that the ZnS nanoparticles had zinc blende structure with an average size of about 2.18 nm. The value of band gap of these nanoparticles was measured to be 4.20 eV. The nonlinear optical properties of ZnS nanoparticles in aqueous solution were studied by Z-scan technique using CW He-Ne laser at 632.8 nm. The nonlinear absorption coefficient (β) was estimated to be as high as 3.2×10⁻³ cm/W and the nonlinear refractive index (n₂) was in order of 10⁻⁸ cm²/W. The sign of the nonlinear refractive index obtained negative that indicated this material exhibits self-defocusing optical nonlinearity.     

Synthesis and photoluminescent and nonlinear optical properties of manganese doped ZnS nanoparticles

In this work we synthesized ZnS:Mn²⁺ nanoparticles by chemical method using PVP (polyvinylpyrrolidone) as a capping agent in aqueous solution. The structure and optical properties of the resultant product were characterized using UV-vis optical spectroscopy, X-ray diffraction (XRD), photoluminescence (PL) and z-scan techniques. UV-vis spectra for all samples showed an excitonic peak at around 292 nm, indicating that concentration of Mn²⁺ ions does not alter the band gap of nanoparticles. XRD patterns showed that the ZnS:Mn²⁺ nanoparticles have zinc blende structure with the average crystalline sizes of about 2 nm. The room temperature photoluminescence (PL) spectrum of ZnS:Mn²⁺ exhibited an orange-red emission at 594 nm due to the ⁴T₁-⁶A₁ transition in Mn²⁺. The PL intensity increased with increase in the Mn²⁺ ion concentration. The second-order nonlinear optical properties of nanoparticles were studied using a continuous-wave (CW) He-Ne laser by z-scan technique. The nonlinear refractive indices of nanoparticles were in the order of 10⁻⁸ cm²/W with negative sign and the nonlinear absorption indices of these nanoparticles were obtained to be about 10⁻³ cm/W with positive sign.     

A comparative study of structural, compositional, thermal and optical properties of non stoichiometric (Zn,Fe)S chalcogenide pellets and thin films

Non-stiochiometric ternary chalcogenides Zn_1−xFe_xS, were prepared in the bulk form by co-precipitation of ZnS and FeS by Na₂S from aqueous solution containing FeSO₄ and ZnSO₄ and sintering of pellets of the co-precipitate repeatedly at 1073K in vacuum sealed quartz ampoules. Concomitant with the bulk form; thin fims of (Zn,Fe)S were synthesized by pyrolytic spray deposition method on quartz substrates from aqueous precursor solution containing ZnCl₂, FeCl₂ and thiourea in varying concentration under optimized conditions of substrate temperature (653K) carrier gas flowrate (11 l min⁻¹) and solution flow rate (8-6 ml min⁻¹).The structure, chemical composition, optical and thermoelectrical properties of the (bulk) pellets and thin films are studied as a function of initial solution concentration.X-ray diffraction of the pellets and thin films indicated the presence of solid solutions Zn_1−xFe_xS (sphalerite), while surface morphology as determined by SEM revealed a granular structure. Electrical resistivity of pellets and thin films, measured using two probe method (for pellets) and four probe van der Pauw method (for thin films) indicated that they are semiconducting while resistivity studies could not be carried out for a few thin films due to their high resistance (>20 MΩ).The chemical composition of the resulting solids as analyzed by X-ray fluorescence and that of thin films as analyzed by energy dispersive X-ray, reflected the composition of the solutions from which precipitation (for pellets) and deposition (for thin films) was carried out, with Fe contents up to x=0.4.SEM micrograph of pellets and thin films reveal that later have smaller grain size.Thermoelectric studies revealed that both solids and thin films possess the ability of ‘n’ as well as ‘p’ type conductivity.The diffuse optical reflectance measurements of pellets and transmittance measurements for thin films; as a function of wavelength reveal the dependence of direct optical band-gap on Fe content.     

Anisotropic nonlinear optical absorption of gold nanorods in a silica matrix

Nanocomposite films consisting of gold nanospheres or gold nanorods embedded in a silica matrix have been prepared using a hybrid deposition technique consisting of plasma-enhanced chemical vapor deposition of SiO₂ and co-sputtering of gold, followed by annealing at 900 °C. Subsequent irradiation with 30 MeV heavy ions (Cu⁵⁺) was used to form gold nanorods. Linear and nonlinear optical properties of this material are closely related with the surface plasmon resonance in the visible. The nonlinear absorption coefficient (α₂@532 nm) for the films containing gold nanospheres was measured by Z-scan and P-scan techniques, and it was found to be isotropic and equal to −4.8 × 10⁻² cm/W. On the contrary, gold nanorods films exhibited two distinct surface plasmon resonance absorption bands giving rise to a strong anisotropic behavior, namely a polarization-dependent linear absorption and saturable absorption. Z-scan and P-scan measurements using various light polarization directions yielded nonlinear absorption coefficient (α₂@532 nm) values varying from −0.9 × 10⁻² cm/W up to −3.0 × 10⁻² cm/W. Linearity of the P-scan method in the context of nanocomposite saturable absorption is also discussed.     

Diagnostic study of the roughness surface effect of zirconium on the third-order nonlinear-optical properties of thin films based on zinc oxide nanomaterials

Zinc oxide (ZnO) and zirconium doped zinc oxide (ZnO:Zr) thin films were deposited by reactive chemical pulverization spray pyrolysis technique on heated glass substrates at 500 °C using zinc and zirconium chlorides as precursors. Effects of zirconium doping agent and surface roughness on the nonlinear optical properties were investigated in detail using atomic force microscopy (AFM) and third harmonic generation (THG) technique. The best value of nonlinear optical susceptibility χ⁽³⁾ was obtained from the doped films with less roughness. A strong third order nonlinear optical susceptibility χ⁽³⁾ = 20.12 × 10⁻¹² (esu) of the studied films was found for the 3% doped sample.     

Electrical and optical properties of Ga doped zinc oxide thin films deposited at room temperature by continuous composition spread

Ga doped ZnO (GZO) thin films were deposited on glass substrates at room temperature by continuous composition spread (CCS) method. CCS is thin films growth method of various Ga_xZn_1−xO(GZO) thin film compositions on a substrate, and evaluating critical properties as a function position, which is directly related to material composition. Various compositions of Ga doped ZnO deposited at room temperature were explored to find excellent electrical and optical properties. Optimized GZO thin films with a low resistivity of 1.46 × 10⁻³ Ω cm and an average transmittance above 90% in the 550 nm wavelength region were able to be formed at an Ar pressure of 2.66 Pa and a room temperature. Also, optimized composition of the GZO thin film which had the lowest resistivity and high transmittance was found at 0.8 wt.% Ga₂O₃ doped in ZnO.     

Third-order nonlinear optical studies of new anthraquinone derivatives

Four new donor-acceptor-donor anthraquinone derivatives were synthesized and characterized by UV, IR, ¹H NMR and elemental analysis. Their off-resonant third-order nonlinear optical properties were measured using femtosecond laser and degenerate four-wave mixing technique. The third-order nonlinear optical susceptibilities χ⁽³⁾ were 3.36-3.76 × 10⁻¹³ esu. The nonlinear refractive indexes n₂ were 6.19-6.91 × 10⁻¹² esu. The second-order hyperpolarizabilities γ of the molecules were 3.36-3.76 × 10⁻³¹ esu. The response times were 101-115 fs. The results show that these compounds have potential nonlinear optical applications.     

Identification of optical nonlinearities of dye-doped nematic and polymer-dispersed liquid crystals using Z-scan technique

This study investigates the nonlinear optical properties of azo-dye-doped nematic and polymer-dispersed liquid crystal (ADDPDLC) films with nano-sized LC droplets using the Z-scan technique, which is a simple but powerful technique for measuring the optical Kerr constants of materials. The results indicate that the optical Kerr constant (n₂) of the azo-dye-doped nematic LC (ADDLC) film is large because of the photoisomerization effect and the thermal effect. Therefore, the optical Kerr constant of this material can be modulated by varying the temperature of the sample and the direction of polarization of incident laser. The range of n₂ modulated is from −5.26 × 10⁻³ to 1.62 × 10⁻³ cm²/W. The optical Kerr constants of ADDPDLC films at various temperatures are also measured. The experimental results reveal that liquid crystals in the ADDPDLC film strengthen the nonlinearity. The n₂ of the ADDPDLC film is maximal at ∼35 °C, because of the decrease in the clearing temperature of the ADDPDLC films. The clearing temperatures of the liquid crystals (E7), and the ADDPDLC film used in this work were found to be 61 °C and 43 °C, respectively.     

Effect of deposition pressure on structural, optical and electrical properties of zinc selenide thin films

ZnSe thin films have been prepared by inert gas condensation method at different gas pressures. The influence of deposition pressure, on structural, optical and electrical properties of polycrystalline ZnSe films have been investigated using X-ray diffraction (XRD), optical transmission and conductivity measurements. The X-ray diffraction study reveals the sphalerite cubic structure of the ZnSe films oriented along the (1 1 1) direction. The structural parameters such as particle size [6.65-22.24 nm], strain [4.01-46.6×10⁻³ lin⁻² m⁻⁴] and dislocation density [4.762-18.57×10¹⁵ lin m⁻²] have been evaluated. Optical transmittance measurements indicate the existence of direct allowed optical transition with a corresponding energy gap in the range 2.60-3.00 eV. The dark conductivity (σ_d) and photoconductivity (σ_ph) measurements, in the temperature range 253-358 K, indicate that the conduction in these materials is through an activated process having two activation energies. σ_d and σ_ph values decrease with the decrease in the crystallite size. The values of carrier life time have been calculated and are found to decrease with the reduction in the particle size. The conduction mechanism in present samples has been explained, and the density of surface states [9.84-21.4×10¹³ cm⁻²] and impurity concentration [4.66-31.80×10¹⁹ cm⁻³] have also been calculated.     

Investigation of third-order nonlinear optical properties of conjugated benzodioxal derivatives

An investigation of third-order nonlinear optical characterization of newly synthesized conjugated benzodioxal derivatives has been done by using nanosecond Z-scan technique at 532 nm. The molecules demonstrate self-defocusing effect with intensity dependent refractive index (n₂) of the order of 10⁻¹⁴ cm²/W. The measured molecular TPA cross-section is ranging from 2.47 ×10⁻⁴⁷ cm⁴ s/photon to 6.00 cm⁴ s/photon. Their input-output curves indicate that there is a clear optical power limiting behavior with the limiting threshold in the range 125-181 μJ. The main factor to exhibit the observed nonlinearity in these molecules is the presence of charge donor and acceptor groups. The increased conjugation length increases the nonlinear refraction and increased electron density enhances the nonlinear absorption. The molecules exhibit good nonlinear optical properties, comparable to those of regular azoaromatic compounds. Therefore, the molecules investigated here are promising candidates for optical power limiting devices.     

Optimal growth conditions for GdBa2Cu3O7 thin-film coated conductors characterized by polarized Raman scattering spectroscopy

High temperature superconducting GdBa₂Cu₃O₇ (GdBCO) thin films were grown by pulsed laser ablation. Textured MgO on metal substrates was used as a template for second generation wire applications. Growth conditions of GdBCO thin films were investigated for substrate temperature (T_s) and oxygen partial pressure (PO₂) during deposition. Superconducting critical currents of the films were obtained in the films grown at 790–810 °C of T_s and at 100–700 mTorr of PO₂. Scanning electron micrographs of the films revealed uniform and well-connected grains with some outgrown structures. X-ray θ–2θ scans of the films grown at 810 °C and 300–500 mTorr exhibited c-axis oriented texture. In-plane alignment and c-axis mosaic spread of the films were determined from X-ray Φ scans and rocking curves, respectively. Polarized Raman scattering spectroscopy was used to characterize optical phonon modes, oxygen content, cation disorder, and some possible second phases of the films. The Raman spectra of the films with large critical current density showed modes at 326–329 cm⁻¹, 444–447 cm⁻¹, 500–503 cm⁻¹ related to vibration of oxygen atoms. Origin of small peaks near 600 cm⁻¹ will be discussed as well. The information obtained from Raman scattering measurements will be useful for quality control of the conductors as well as optimization of the process conditions.     

Influence of [S2O3]/[Sm] on Sm2S3 thin films deposited by liquid phase deposition method on self-assembled monolayers

Sm₂S₃ thin films were prepared on Si (1 0 0) substrates using SmCl₃ and Na₂S₂O₃ as precursors by liquid phase deposition method on self-assembled monolayers. The influence of the molar concentration ratio of [S₂O₃²⁻]/[Sm³⁺] on the phase compositions, surface morphologies and optical properties of the as-deposited films were investigated. The as-deposited Sm₂S₃ thin films were characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), ultraviolet-visible (UV-vis) and photoluminescence spectrum (PL). Results show that it is important to control the [S₂O₃²⁻]/[Sm³⁺] during the deposition process and monophase Sm₂S₃ thin films with orientation growth along (0 1 1) direction can be achieved when [S₂O₃²⁻]/[Sm³⁺] = 2.0, pH 3.0, with citric acid as a template agent. The as-deposited thin films exhibit a dense and crystalline surface morphology. Good transmittance in the visible spectrum and excellent absorbency of ultraviolet light of the thin films are observed, and the band gap of the thin films first decrease and then increase with the increase of the [S₂O₃²⁻]/[Sm³⁺]. The as-deposited thin films also exhibit red photoluminescence properties under visible light excitation. With the increase of the [S₂O₃²⁻]/[Sm³⁺] in the deposition solution, the PL properties of Sm₂S₃ thin films are obviously improved.