Effects of the ZnSe concentration on the structural and optical properties of ZnSe/PVA nanocomposite thin film

This study investigated the effects of ZnSe nanoparticles (NPs) on the structural and (linear and nonlinear) optical properties of polyvinyl alcohol (PVA) thin film. Three samples of ZnSe NP-doped PVA thin films with different concentrations of ZnSe were produced on a glass substrate. The ZnSe NPs were synthesized by pulsed laser ablation of the ZnSe bulk target immersed in distilled water using a 1064 nm wavelength and a high frequency pulsed Nd:YAG laser. The optical bandgap energies of the films were extracted from their UV-Vis-NIR absorption spectra. The corresponding energy bandgaps of the nanocomposite films declined as the ZnSe NPs doping concentration increased. X-ray diffraction analysis was used to characterize the crystalline phases of the ZnSe/PVA nanocomposite films. The concentration-dependent nonlinear optical absorption and nonlinear refraction behaviors of the films after exposure to 532-nm nanosecond laser pulses were investigated using the Z-scan technique. The nonlinear absorption response of the films was positive when measured using an open aperture scheme, which was attributed to the two-photon absorption mechanism. In addition, the nonlinear refraction indices had a negative value and they increased as the concentration of ZnSe NPs in the films increased.     

Synthesis and characterization of CdS/PVA nanocomposite films

A series CdS/PVA nanocomposite films with different amount of Cd salt have been prepared by means of the in situ synthesis method via the reaction of Cd²⁺-dispersed poly vinyl-alcohol (PVA) with H₂S. The as-prepared films were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), ultraviolet-visible (UV-vis) absorption, photoluminescence (PL) spectra, Fourier transform infrared spectroscope (FTIR) and thermogravimetric analysis (TGA). The XRD results indicated the formation of CdS nanoparticles with hexagonal phase in the PVA matrix. The primary FTIR spectra of CdS/PVA nanocomposite in different processing stages have been discussed. The vibrational absorption peak of CdS bond at 405 cm⁻¹ was observed, which further testified the generation of CdS nanoparticles. The TGA results showed incorporation of CdS nanoparticles significantly altered the thermal properties of PVA matrix. The photoluminescence and UV-vis spectroscopy revealed that the CdS/PVA films showed quantum confinement effect.     

Nonlinear change in refractive index of Co2+:ZnSe at short-pulse single-beam 1.54-μm Z-scan probing

An experimental study and theoretical modeling of the nonlinear change in refractive index of a Co^{2 +}: ZnSe crystal at the short-pulse single-beam probing at the wavelength 1.54 μm is reported. In the experimental conditions of negligible contributions in the index non-linearity stemming from the Kerr-effect and inhomogeneous heating, the nonlinear change in refractive index in Co^{2 +}:ZnSe is shown to be caused by the resonant Co^{2 +} population-perturbation effect (i.e., by the Co^{2 +} ground-state absorption saturation). The Z-scan single-beam technique and novel theoretical approach addressing the resonant nonlinear refraction in a saturable doped medium are used, respectively, for an experimental and theoretical inspection of the phenomenon. For a set of Co^{2 +}:ZnSe samples with different concentrations of Co^{2 +} ions at the short-pulse (200 ns) mJ-range probing, we show that the maximal nonlinear change in refractive index is about of units of 10^{− 4} at the chosen wavelength.     

Two photon absorption in Mn-doped ZnSe quantum dots

The nonresonant third order nonlinear optical properties of three different sized Mn²⁺-doped ZnSe quantum dots (QDs) are investigated. The nonlinear absorption is measured at 532 nm using 35 picosecond laser pulses in an open-aperture Z-scan setup. Two photon absorption (2PA) cross-section in ZnSe QDs is found to be three orders of magnitude higher than its bulk value. These nanostructures show size dependent nonlinear absorption coefficients. It is found that the 2PA further enhances with decrease in size of the QD and is twice that of its undoped counterpart due to change in the local electric field.     

Effect of deposition parameters on structural, optical and electrical properties of nanocrystalline ZnSe thin films

This paper presents the chemical bath deposition of zinc selenide (n-ZnSe) nanocrystalline thin films on non-conducting glass substrates, in an aqueous alkaline medium using sodium selenosulphate as Se²⁻ ion source. The X-ray diffraction studies show that the deposited ZnSe material is nanocrystalline with a mixture of hexagonal and cubic phase. The direct optical band gap ‘E_g’ for the as-deposited n-ZnSe films is found to be 3.5 eV. TEM studies show that the ZnSe nanocrystals (NCs) are spherical in shape. Formation of ZnSe has been confirmed with the help of infrared (IR) spectroscopy by observing bands corresponding to the multiphonon absorption. We demonstrate the effect of the deposition temperature and reactant concentration on the structural, optical and electrical properties of ZnSe films.     

Simulation of nonlinear optical absorption in ZnSe:Co crystals

The paper presents theoretical approach to simulation of nonlinear optical absorption in zinc selenide crystals doped with cobalt (II) ions (ZnSe:Co²⁺), which was reported by us earlier (Opt. Laser Technology, V. 35, (2003), 169). We used ZnSe:Co²⁺ crystals as saturable absorbers for generation of giant-pulse eye-safe laser radiation. It was found that minimal optical losses (maximal final transmission) occurred for ZnSe samples containing 1.6×10¹⁹ cm⁻³ of Co²⁺ ions. Band structure and photoinduced molecular dynamics simulations were performed to explain the parabolic dependence of optical losses versus Co²⁺ concentration. The minimum was shown to be the result of photoinduced anharmonic electron–phonon interaction.     

Enhanced nonlinear optical responses in metal-glass nanocomposites

The “engineered” nonlinear nanocomposite materials with extremely large values of optical Kerr susceptibility and fast temporal responses that can be precisely tuned to satisfy the requirements of switching applications is of current interest in photonics. Metal quantum-dot composite glasses can exhibit enhanced optical susceptibility, χ⁽³⁾, whose real and imaginary parts are related to the intensity-dependent refractive index and two-photon absorption coefficient, respectively. Classical (dielectric) and quantum confinement effects come into play in the nonlinear optical responses of these nanocomposites. Metal nanocluster-glass composites have been synthesized by 200 keV Cu⁺ and 1.5 MeV Au⁺ ion implantations in fused silica glasses at a dose of 3 × 10¹⁶ ions/cm², followed by thermal annealing in reducing atmosphere to promote cluster growth. UV-Visible spectroscopy has revealed prominent linear absorption bands at characteristic surface plasmon resonance (SPR) frequencies signifying appreciable formation of copper and gold colloids in glass matrices. Third-order optical properties of the composite materials have been studied by Z-Scan and Anti-Resonant Interferometric Nonlinear Spectroscopy (ARINS) measurements. The sign of nonlinear refraction is readily obtained from the Z-Scan signatures. The ARINS technique utilizes the dressing of two unequal-intensity counter-propagating pulsed light beams with differential nonlinear phases, which occur upon traversing the sample if it exhibits nonlinear optical response. This difference in phase manifests itself in the intensity-dependent transmission. The nonlinear refractive index, nonlinear absorption coefficient, the real and imaginary parts of the third-order optical susceptibility have been extracted.     

A Simple Strategy to Prepare Colloidal Cu‐Doped ZnSe(S) Green Emitter Nanocrystals in Aqueous Media

A novel and simple method is described for preparing colloidal Cu‐doped ZnSe(S) quantum dots (QDs) in aqueous media by introducing copper ions using the same method as to prepare colloidal ZnSe(S). More specifically, the Cu‐doped ZnSe(S) are prepared through the nucleation‐doping method in the presence of 3‐mercaptopropionic acid as stabilizers using zinc perchlorate, copper sulphate, and NaHSe as precursors. Confirmation of the preparation of Cu‐doped ZnSe(S) nanocrystals (NCs) is done with absorption and emission spectroscopies (UV–vis and PL) as the QDs show intensive green emissions. The reduction of ions Cu²⁺ to Cu⁺ is confirmed by using electron paramagnetic resonance (EPR), in which Cu⁺ ions are silent. The size determination is performed by using transmission electron microscopy (TEM) and dynamic light scattering (DLS), resulting in Cu‐doped ZnSe(S) particles with a mean diameter of 4.6 ± 3.5 nm. The excellent stability observed for the nanoparticles overcomes the intrinsic instability of traditional aqueous Cu‐doped ZnSe(S) NCs.     

Structure,dielectric and optical properties of p-type (PVA/CuI) nanocomposite polymer electrolyte for photovoltaic cells

A novel PVA/CuI nanocomposite polymer electrolyte layer synthesized via the reduction of CuCl₂ by NaI in an aqueous PVA solution. The as-prepared films were characterized by X-ray diffraction, scanning electron microscope, as well as impedance spectroscopy. The obtained results indicated the formation of hexagonal CuI nano particles of ≈55 nm sizes embedded in the PVA matrix. In addition, the study of dielectric parameters and conductivity of PVA/CuI nanocomposite in wide range of temperature and frequency are given and discussed. The frequency dependence of ac-conductivity suggests power law with an exponent 0.026 < s < 0.73 which predicts hopping of charge carriers. The bulk conductivity showed activation with temperature, significant values of activation energy are deduced and discussed. An average value of the energy gap width, 2.05 eV obtained using optical absorption in UV–visible spectra for PVA/CuI nanocomposite polymer electrolyte.     

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.     

Large two-photon absorbance of chitosan–ZnS quantum dots nanocomposite film

ZnS semiconductor nanoparticles with average size of 3.4 nm were prepared in situ in chitosan film. TEM, UV–vis spectra and PL spectra show the ZnS nanoparticles in chitosan template were monodispersed and well passivated. The two-photon absorption coefficient (β) of the chitosan–ZnS quantum dots (QDs) nanocomposite film was obtained to be 2.29×10² cm/Gw from a standard Z-scan setup with femtosecond laser pusles at 790 nm wavelength. Results show the novel biomacromolecule/QDs nanocomposite film has large third-order optical nonlinear absorption, the mechanism responsible for which was discussed.     

Optical Properties of CdS–PVA Nanocomposites

Semiconductor–polymer nanocomposites, with good control over the nanoparticle size and their dispersion within the polymer matrix, can have applications in many optical and luminescent display devices. Cadmium sulphide (CdS) is the most popular semiconductor nanoparticle exhibiting size dependent properties due to its large exciton binding energy and its suitability for large scale production. The nanoparticles need to be passivated against aggregation with suitable capping agents, without sacrificing the desirable properties like transparency and flexibility of the polymer. Cadmium sulphide nanoparticles capped with polyvinyl pyrrolidone (PVP) are synthesized using cadmium nitrate (Cd(NO₃)₂) and hydrogen sulphide (H₂S) as Cd²⁺ and S^2– sources, respectively. CdS particles with sizes in the range of 5–6 nm are prepared in methanol and the solvent is removed using a rotary evaporator. CdS powder is dispersed in polyvinyl alcohol (PVA) solution with dimethyl formamide (DMF) as solvent to get (PVP–CdS)–PVA nanocomposite film of about 0.2 mm thickness. This has been characterized by powder X-ray diffraction (XRD), optical absorption studies, transmission electron microscopy (TEM), differential scanning calorimetry (DSC) and photoluminescence (PL). Particle size does not change due to incorporation in the polymer matrix and the polymer retains its transparency and flexibility. The nanocomposite shows good photoluminescence property with stronger band edge emission than defect related emission. The latter could be quenched completely by optimizing the PVP content. Irradiation of the nanocomposite with 8 MeV electrons at a dose of 100 kGy could effectively quench the defect related emission.     

Novel chemical synthetic route and characterization of zinc selenide thin films

Zinc selenide (ZnSe) thin film have been deposited using chemical bath method on non-conducting glass substrate in a tartarate bath containing zinc sulfate, ammonia, hydrazine hydrate, sodium selenosulfate in an aqueous alkaline medium at 333 K. The deposition parameter of the ZnSe thin film is interpreted in the present investigation. The films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), optical absorption, electrical measurements, atomic absorption spectroscopy (AAS). The ZnSe thin layers grown with polycrystalline zinc blende system along with some amorphous phase present in ZnSe film. The direct optical band gap ‘E_g’ for the film was found to be 2.81 eV and electrical conductivity in the order of 10⁻⁸(Ω cm)⁻¹ with n-type conduction mechanism.     

Structure and photochromic properties of poly(vinylalcohol)/phosphotungstic acid nanocomposite films

Poly(vinylalcohol)/phosphotungstic acid (PVA/PWA) nanocomposite films were studied using Fourier-transform infrared and electron absorption spectroscopy. It was found that entrapping PWA into PVA leads to the formation of hydrogen bonds between OH groups of PVA and bridging oxygen atoms of PWA. Terminal oxygen atoms of PWA do not participate in hydrogen-bonding interactions with the polymer. Exposure of the nanocomposite film to UV radiation results both in the photo-induced transfer of protons from PVA to PWA with their attachment to the bridging oxygen atoms of PWA and in the formation of a PVA–PWA complex with the participation of deprotonated oxygen atoms of PVA and the terminal oxygen atoms of PWA. The UV irradiation causes the films to turn blue and a band of d–d transitions of W⁵⁺ ions (480 nm) and two bands of intervalence W⁵⁺ → W6+ charge-transfer transitions (740 and 1250 nm) to appear in their electronic spectrum.     

Influence of lithium potassium zirconate nanoparticles on the electrical properties and structural characteristics of poly(vinyl alcohol) films

We investigated the influence of lithium potassium zirconate (LiKZrO₃) nanoparticles on the electrical properties and structural characteristics of poly(vinyl alcohol) (PVA) films. PVA/LiKZrO₃ nanocomposite films were prepared by casting of aqueous solutions with varying LiKZrO₃ content (0.5, 1.0, and 2.0 wt.%). The dielectric constant (ε′), dielectric loss (ε″), AC conductivity (σ_ac), dielectric loss tangent (tan δ), and electric modulus (M′ and M″) of the nanocomposite films were measured over a range of frequencies at ambient temperature. The results show increases in σ_ac and M′ with frequency, whereas ε′, ε″, and tan δ decreased with increasing frequency. The films were also characterized using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and X-ray diffraction (XRD) techniques. DSC and XRD revealed the nature of LiKZrO₃ nanoparticle interaction with the PVA matrix. TGA analysis revealed an increase in thermal stability of the nanocomposites with increasing nanoparticle concentration. Scanning electron microscopy confirmed uniform dispersion of LiKZrO₃ nanoparticles in the PVA matrix.     

PPV/PVA/ZnO nanocomposite prepared by complex precursor method and its photovoltaic application

In this article, we describe a new method to prepare a ZnO and conjugated polymer nanocomposite and its application in bulk-heterojunction solar cells. The composite was composed of zinc oxide (ZnO) and poly(phenylene vinylene)/poly(vinyl alcohol) (PPV/PVA). For the preparation, the composite was prepared first through the complex reaction between Zn²⁺ ion and –OH of the PVA–PPV precursor by simply mixing zinc salts and a PVA–PPV precursor aqueous solution at 70 °C. By addition of a concentrated aqueous ammonia into the system, highly regular Zn(OH)₂ nanodots were formed and dispersed in the PVA/PPV precusor mixed solution. The PVA/PPV precursor can well bind Zn²⁺ ion through complex interaction, so act as a template to direct the distribution of ZnO in the process. The nanocomposite films were finally obtained by solution casting and subsequently treated by heating samples at 160 °C for 6 h. TEM observations showed that ZnO nanodots uniformly dispersed in PVA–PPV mixtures. The resulting nanocomposite films possess a large interfacial area between the electron donor and acceptor of the bulk-heterojunction. Improved charge seperation and collection are evidenced by the large photoluminescence intensity difference between pure PPV and composites films, which result in the increase in both open circuit voltage and short circuit current of the hybrid solar cells.     

Determination of optical constants and nonlinear optical coefficients of Violet 1-doped polyvinyl alcohol thin film

The optical properties of Violet 1-doped polyvinyl alcohol (PVA) have been investigated using Wemble and Didomenico (WD) method. The optical constants such as refractive index n, the dispersion energy E _d, the oscillation energy E ₀, the lattice dielectric constant \(\varepsilon _{\infty } \), light frequency dielectric constant ε ₀ and the ratio of carrier concentration to the effective mass N/m* have been determined using reflection spectra in the wavelength range 300–900 nm. The single- beam Z-scan technique was used to determine the nonlinear optical properties of Violet 1:polyvinylalcohol (PVA) thin film. The experiments were performed using continuous wave (cw) laser with a wavelength of 635 nm. The calculated nonlinear refractive index of the film, n ₂ = ?2.79×10^?7 cm²/W and nonlinear absorption coefficient, β = 6.31×10^?3 cm /W. Optical limiting characteristics of the dye-doped polymer film was studied. The result reveals that Violet 1 can be a promising material for optical limiting applications.     

The roles of zinc selenide sandwiched between organic layers and its applications in white light-emitting diodes

In this paper, the roles of zinc selenide (ZnSe) sandwiched between organic layers, i.e. organic/ZnSe/aluminum quinoline (Alq₃), have been studied by varying device structure. A broad band emission was observed from ITO/poly(N-vinylcarbazole)(PVK)(80 nm)/ZnSe(120 nm)/ Alq₃(15 nm)/Al under electric fields and it combined the emissions from the bulk of PVK, ZnSe and Alq₃, however, emission from only Alq₃ was observed from trilayer device ITO/N,N^′-bis-(1-naphthyl)-N,N^′-diphenyl-1, 1^′-biphenyl-4, 4^′-diamine (NPB) (40 nm)/ZnSe(120 nm)/ Alq₃(15 nm)/Al. Consequently the luminescence mechanism in the ZnSe layer is suggested to be charge carrier injection and recombination. By thermal co-evaporating Alq₃ and 4-(dicyanomethylene)-2-t-butyl-6-(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB), we get white light emission with a Commission Internationale de l’E clairage (C.I.E) co-ordinates of (0.32, 0.38) from device ITO/PVK(80 nm)/ZnSe(120 nm)/ Alq₃:DCJTB(0.5 wt% DCJTB)(15 nm)/Al at 15 V and the device performs stably with increasing applied voltages.     

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.     

Optical absorption and linear/nonlinear parameters of polyvinyl alcohol films doped by fullerene

New polymeric films were developed for optoelectronic devices by an interaction between Fullerene (C60) and polyvinyl alcohol (PVALC) via the casting method. The structure analysis was studied by Gaussian fitting of XRD patterns and SAED (Selected area electron diffraction). Using HRTEM and SEM, the particle shape and the nanocomposite surface on PVALC are investigated. The change in the functional group of the composites was observed via FT-IR and Raman spectroscopy. In this work, we calculated the bandgap and localized state's width, in the forbidden band, via the absorption coefficient obtained from the Beer-Lambert relation. The bandgap of nanocomposite films was reduced to 4.05 eV. Moreover, due to the surface plasmon absorption in nanocomposite films, k (Extinction index) increases with the doping concentration. The bandgap and refractive index (n) relations were studied via various empirical formulas to calculate the average value of n. The linear optical parameters, such as 1^st-order susceptibility (χ⁽¹⁾), high-frequency dielectric (e_∞), and static dielectric (e_o) constants, were calculated. The nonlinear susceptibility χ⁽³⁾ raised from 0.928 × 10⁻¹² esu to 1.779 × 10⁻¹² esu. Also, the refractive index (n₂) enhanced from 1.665 × 10⁻¹¹ esu to 2.993 × 10⁻¹¹ esu. The optical limiting performance and the ability of nanocomposite to absorb laser beams were tested. The result suggests that C60 has a considerable effect on the PVALC matrix, and the samples have the necessary guidance for laser CUT-OFF and photonic applications.