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.     

Textural and electronic characteristics of mechanochemically activated composites with nanosilica and activated carbon

Nanosilicas (A-50, A-300, A-500)/activated carbon (AC, S_BET = 1520 m²/g) composites were prepared using short-term (5 min) mechanochemical activation (MCA) of powder mixtures in a microbreaker. Smaller silica nanoparticles of A-500 (average diameter d_av = 5.5 nm) can more easily penetrate into broad mesopores and macropores of AC microparticles than larger nanoparticles of A-50 (d_av = 52.4 nm) or A-300 (d_av = 8.1 nm). After MCA of silica/AC, nanopores of non-broken AC nanoparticles remained accessible for adsorbed N₂ molecules. According to ultra-soft X-ray emission spectra (USXES), MCA of silica/AC caused formation of chemical bonds Si-O-C; however, Si-C and Si-Si bonds were practically not formed. A decrease in intensity of OK_α band in respect to CK_α band of silica/AC composites with diminishing sizes of silica nanoparticles is due to both changes in the surface structure of particles and penetration of a greater number of silica nanoparticles into broad pores of AC microparticles and restriction of penetration depth of exciting electron beam into the AC particles.     

Pulsed plasma ion source to create Si nanocrystals in SiO2 substrates

A pulsed KrF excimer laser of irradiance of about 10⁸ W/cm² was utilized to synthesize Si nanocrystals on SiO₂/Si substrates. The results were compared with that ones obtained by applying low bias voltage to Si(1 0 0) target in order to control the kinetic energy of plasma ions. Glancing incidence X-ray diffraction spectra indicate the presence of silicon crystalline phases, i.e. (1 1 1) and (2 2 0), on SiO₂/Si substrates. The average Si nanocrystal size was estimated to be about 45 nm by using the Debye-Scherrer formula. Scanning electron microscopy and atomic force microscopy images showed the presence of nanoparticles of different size and shape. Their distribution exhibits a maximum concentration at 49 nm and a fraction of 14% at 15 nm.     

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.     

ZnO nanoparticles produced by novel reactive physical deposition process

This paper reports the deposition of ZnO nanoparticles with controlled sizes and different particle densities and their structural, composition and optical properties. They were deposited by means of a DC magnetron based vacuum nanoparticle source onto different substrates (GaAs, Si and Ti/SiO₂/Si). We believe that this is the first time that such nanoparticles have been produced using this unique technique. Zinc was used as sputtering target to produce zinc nanoparticles which were oxidized in-line using molecular oxygen. The structural properties and chemistry of the ZnO were studied by transmission electron microscopy. An average particle size of 6(±2) nm was produced with uniform size distribution. The particle density was controlled using a quartz crystal monitor. Surface densities of 2.3 × 10¹¹/cm², 1.1 × 10¹³/cm² and 3.9 × 10¹³/cm² were measured for three different deposition runs. The ZnO particles were found to be single crystalline having hexagonal structure. Photoluminescence measurements of all samples were performed at room temperature using a cw He-Cd laser at 325 nm excitation. The UV emission around 375 nm at room temperature is due to excitonic recombination and the broad emission centered at 520 nm may be attributed to intrinsic point defects such as oxygen interstitials.     

Characterization of the laser ablation plasma used for the deposition of amorphous carbon

The plasma produced by laser ablation of a graphite target was studied by means of optical emission spectroscopy and a Langmuir planar probe. Laser ablation was performed using a Nd:YAG laser with emission at the fundamental line with pulse length of 28 ns. In this work, we report the behavior of the mean kinetic energy of plasma ions and the plasma density, as a function of the laser fluence (J/cm²), and the target to probe (substrate) distance. The characterized regimes were employed to deposit amorphous carbon at different values of kinetic energy of the ions and plasma density. The mean kinetic energy of the ions could be changed from 40 to 300 eV, and the plasma density could be varied from 1 × 10¹² to 7 × 10¹³ cm⁻³. The main emitting species were C⁺ (283.66, 290.6, 299.2 and 426.65 nm) and C⁺⁺ (406.89 and 418.66 nm) with the C⁺ (426.65 nm) being the most intense and that which persisted for the longest times. Different combinations of the plasma parameters yield amorphous carbon with different structures. Low levels (about 40 eV) of ion energy produce graphitic materials, while medium levels (about 200 eV) required the highest plasma densities in order to increase the CC sp³ bonding content and therefore the hardness of the films. The structure of the material was studied by means of Raman spectroscopy, and the hardness and elastic modulus by depth sensitive nanoindentation.     

Periodic surface structures on crystalline silicon created by 532 nm picosecond Nd:YAG laser pulses

Creation of laser-induced morphology features, particularly laser-induced periodic surface structures (LIPSS), by a 532 nm picosecond Nd:YAG laser on crystalline silicon is reported. The LIPSS, often termed ripples, were produced at average laser irradiation fluences of 0.7, 1.6, and 7.9 J cm⁻². Two types of ripples were registered: micro-ripples (at micrometer scale) in the form of straight parallel lines extending over the entire irradiated spot, and nano-ripples (at nanometer scale), apparently concentric, registered only at the rim of the spot, with the periodicity dependent on laser fluence. There are indications that the parallel ripples are a consequence of the partial periodicity contained in the diffraction modulated laser beam, and the nano-ripples are very likely frozen capillary waves. The damage threshold fluence was estimated at 0.6 J cm⁻².     

Morphology and composition on Al surface irradiated by femtosecond laser pulses

We study the surface chemicals and structures of aluminum plates irradiated by scanning femtosecond laser pulses in air for a wide range of laser fluence from 0.38 to 33.6 J/cm². X-ray photoelectron spectroscopy and X-ray diffraction analyses indicate clearly that crystalline anorthic Al(OH)₃ is formed under femtosecond laser pulse irradiation. Besides aluminum hydroxide, crystalline Al₂O₃ is also found in the samples irradiated at high laser fluence. Field emission scanning electron microscopy demonstrates that the surfaces of the samples irradiated with low laser fluence are colloidal-like and that nanoparticles with a few nanometers in size are embedded in glue-like substances. For high laser fluence irradiated samples, the surfaces are highly porous and covered by nanoparticles with uniform size of less than 20 nm.     

1064-nm laser fragmentation of thin Au and Ag flakes in acetone for highly productive pathway to stable metal nanoparticles

The laser-induced fragmentation of thin Au and Ag flakes in acetone by 1064-nm nanosecond laser (with the fluence typically ∼2 J/cm²) potentially offers a highly productive pathway to stable metal nanoparticles in liquid. Acetone serves as a superior liquid medium that keeps fine metal nanoparticles free from precipitation even in such concentrated nanoparticle solutions exceeding ∼0.1 M. Thin metal flakes have good capability to absorb the 1064-nm laser energy as efficiently as in the visible region. A part of the thus laser-heated molten flakes explosively split into submicroparticles, and some other significant part directly into fine nanoparticles. Both kinds of product particles have minor absorption cross-sections for subsequent laser pulses at 1064 nm, and thus no longer fragment further. One of the two kinds of Ag flakes studied in this work yielded fine Ag nanoparticles at a remarkable high production rate of 1.1 mg/min for the input laser power of only ∼0.65 W.     

Self-Q-switched and mode-locked Nd,Cr:YAG laser with 6.52-W average output power

Simultaneous self-Q-switched and mode-locked have been demonstrated in a diode-pumped Nd,Cr:YAG laser. For the first time as we know, almost 100% modulation depth has been achieved at an intracavity intensity of 5.6 × 10⁵ W/cm². The maximum average output power of 6.52 W corresponding to a slope efficiency of 30% is obtained at 1064 nm. The laser produces high-quality pulses in a TEM₀₀-mode at the pump power of 16.5 W. The pulse duration of the mode-locked pulses is about 600 ps with 136 MHz repetition rate.     

Influence of ordering change on the optical and thermal properties of inflation polyethylene films

Changes of thermal diffusivity inside femtosecond laser-structured volumes as small as few percent were reliably determined (with standard deviation less than 1%) with miniaturized sensors. An increase of thermal diffusivity of a crystalline high-density polyethylene (HDPE) inflation films by 10-20% from the measured (1.16 ± 0.01) × 10⁻⁷ m² s⁻¹ value in regions not structured by femtosecond laser pulses is considerably larger than that of non-crystalline polymers, 0-3%. The origin of the change of thermal diffusivity are interplay between the laser induced disordering, voids’ formation, compaction, and changes in molecular orientation. It is shown that laser structuring can be used to modify thermal and optical properties. The birefringence and infrared spectroscopy with thermal imaging of CH₂ vibrations are confirming inter-relation between structural, optical, and thermal properties of the laser-structured crystalline HDPE inflation films. Birefringence modulation as high as Δn ∼ ± 1 × 10⁻³ is achieved with grating structures.     

Resonantly enhanced three-photon excitation spectra of lithium

We present the first measurement on the resonantly enhanced three-photon excitation spectra of natural lithium using a Nd:YAG laser pumped dye laser in conjunction with a thermionic diode ion detector. Exploiting the linear and circular polarizations, the np ²P_3/2(8 ? n ? 11) and nf  ²F_7/2 (8 ? n ? 38) series have been observed via three-photon excitation from the ground state. The measured level energies reveal a dynamic shift from calculated values, which increases with an increase of the principal quantum number n. The ac stark shift and line broadening mechanisms are studied as a function of laser intensity. It is noted that the width increases and the line center shifts towards the higher energy side as the laser intensity is increased. The maximum observed shift for the 12f ²F_7/2 line is 0.33 cm⁻¹ corresponding to the laser intensity variation from 1.34 × 10¹² W/m² to 1.03 × 10¹³ W/m², whereas its width increases from 0.36 cm⁻¹ to 0.82 cm⁻¹.     

Formation of TiN-Ir particle films using pulsed-laser deposition and their electrolytic properties in producing hypochlorous acid

Using sintered TiN and TiN-Ir (Ir contents: 5.9-14.2 at.%) targets, pulsed-laser deposition (PLD) was carried out to produce thin films composed of nanoparticles and particulates in the presence of nitrogen gas. The size (2-100 nm) of the produced crystalline TiN nanoparticles increased as nitrogen pressure was increased in the range from 1.33 to 1.33 × 10² Pa. At a pressure of 1.33 × 10³ Pa, amorphous TiN nanoparticles combined in the form of chains. Large Ir particulates with diameters of up to 2 μm were particularly prominent in TiN-Ir films. Size distributions of the Ir particulates were dependent on ablation laser wavelength; that is, the diameter decreased at laser wavelength shortened. The TiN-Ir films with different Ir contents and morphologies on Ti substrates were evaluated as electrolysis electrodes for water disinfection. The highest current efficiency was 0.45%, which is comparable to that of conventional Ti-Pt electrodes, for a chloride-ion concentration of 9 mg dm⁻³.     

Effects of electron relaxation on multiple harmonic generation from metal surfaces with femtosecond laser pulses

Calculations are presented for the first four (odd and even) harmonics of an 800 nm laser from a gold surface, with pulse widths ranging from 100 down to 14 fs. For peak laser intensities above 1 GW/cm² the harmonics are enhanced because of a partial depletion of the initial electron states. At 10¹¹ W/cm² of peak laser intensity the calculated conversion efficiency for 2nd-harmonic generation is 3 × 10⁻⁹, while for the 5th-harmonic it is 10⁻¹⁰. The generated harmonic pulses are broadened and delayed relative to the laser pulse because of the finite relaxation times of the excited electronic states. The finite electron relaxation times cause also the broadening of the autocorrelations of the laser pulses obtained from surface harmonic generation by two time-delayed identical pulses. Comparison with recent experimental results shows that the response time of an autocorrelator using nonlinear optical processes in a gold surface is shorter than the electron relaxation times. This seems to indicate that for laser pulses shorter than ∼30 fs, the fast nonresonant channel for multiphoton excitation via continuum-continuum transitions in metals becomes important as the resonant channel becomes slow (relative to the laser pulse) and less efficient.     

3D periodic structures grown on silicon by radiation of a pulsed Nd:YAG laser and their field emission properties

Periodic three-dimensional structures were successfully grown on single crystal Si wafers either bare or Au-covered under their exposure to a pulsed radiation of a Nd:YAG laser in vacuum. The structures protrude above the initial wafer surface for 10 μm while their spatial period is about 70 μm. The coupling of the laser radiation to Si surface is related to the thermal non-linear absorption of the near band gap radiation. The structures exhibit an efficient field emission with an average emission current of 5 mA/cm² and is sensitive to the post-treatment of samples. The drawbacks of the emission current densities are discussed.     

Partial crystallization of silicon by high intensity laser irradiation

Commercial single crystal silicon wafers and amorphous silicon films piled on single crystal silicon wafers were irradiated with a femtosecond pulsed laser and a nanosecond pulsed laser at irradiation intensities between 10¹⁷ W/cm² and 10⁹ W/cm². In the single crystal silicon substrate, the irradiated area was changed to polycrystalline silicon and the piled silicon around the irradiated area has spindly column structures constructed of polycrystalline and amorphous silicon. In particular, in the case of the higher irradiation intensity of 10¹⁶ W/cm², the irradiated area was oriented to the same crystal direction as the substrate. In the case of the lower irradiation intensity of 10⁸ W/cm², only amorphous silicon was observed around the irradiated area, even when the target was single crystal silicon. In contrast, only amorphous silicon particles were found to be piled on the amorphous silicon film, irrespective of the intensity and pulse duration.Three-dimensional thermal diffusion equation for the piled particles on the substrate was solved by using the finite difference methods. The results of our heat-flow simulation of the piled particles almost agree with the experimental results.     

Electrical and optical properties of ZnO films prepared by sputtering of ZnO targets containing AlN

ZnO films prepared from the ZnO target containing 2% AlN are transparent irrespective of radio frequency (RF) power. The obtained ZnO films have the carrier density of 3.8 × 10²⁰ cm⁻³ or less and the low mobility of 5.3-7.8 cm²/(V s). In the case of 5% AlN target, ZnO films prepared at 40, 60 and 80 W are transparent, whereas ZnO films prepared at 100 and 120 W are colored. As RF power increases from 40 to 120 W, the carrier density increases straightforwardly up to 5.5 × 10²⁰ cm⁻³ at 100 W and is oppositely reduced to 3.2 × 10²⁰ cm⁻³ at 120 W. In the case of 10% AlN target, ZnO films prepared at 60 W or more are colored, and have the carrier density of 4 × 10²⁰ cm⁻³ or less. The N-concentration in these colored films is estimated to be 1% or less. The Al-concentration in the ZnO films prepared from the 5 and 10% AlN targets is higher than 2%. The carrier density of the ZnO films containing Al and N atoms is nearly equal to that of ZnO films doped with Al atoms alone. There is no evidence in supporting the enhancement of the carrier density via the formation of N-Al_xZn_4−x clusters (4 ≥ x ≥ 2).     

Non-linear optical properties of silver nanoparticles prepared by hydrogen reduction method

Silver nanoparticles have been prepared using hydrogen gas as the reducing agent for silver nitrate and poly(vinyl pyrrolidone) as the capping agent; the reaction was carried out at 70 °C for 3 h. The size of the nanoparticles was found to be about 20 nm as analyzed using transmission electron micrographs. The X-ray diffraction pattern revealed the face-centered cubic (fcc) structure of silver nanoparticles. The linear absorption of Ag nanoparticles, α, is obtained about 3.71 cm⁻¹. The non-linear refractive indices of silver nanoparticles were defined by the z-scan technique using CW He-Ne laser (λ = 632.8 nm) at different incident intensities. The magnitude of non-linear refractive index (n₂) was measured to be in the order of 10⁻⁷ (cm²/W) with a negative sign. Therefore self-defocusing phenomena is taking placed for Ag nanoparticles.     

Femtosecond laser-induced dynamic alignment in Coulomb explosion of CO: Roles of laser wavelength, intensity and pulse duration

Dependences of dynamic alignment of CO molecules induced by intense femtosecond laser fields on laser wavelength, intensity and pulse duration are investigated by numerical simulations. A counting approach and a fourth-order Runge-Kutta algorithm are used to calculate the angular distribution and the time evolution of molecules. A two-step Coulomb explosion model of diatomic molecules in intense laser fields is used to determine the instant that CO molecular dynamic alignment is over. Our calculating results show that the linear polarizability and the damping force play an important role in the angular rotation of CO molecule in conditions of 800 nm laser wavelength and 10¹⁵ W/cm² laser intensity. The contributions of the second-order field-induced dipole moment and the higher-order correction term to molecular rotation acceleration comparing to the linear polarizability and damping force are negligible. The extent of dynamic alignment of CO molecules reduces with the increasing of laser intensity. The dynamic alignment time of CO molecules is tightly connected to the laser pulse duration. The angular distributions of CO molecules as the laser pulse length varied from 50 to 250 fs at laser intensity of 3×10¹⁴ W/cm² are shown and discussed.     

Ionoluminescence and photoluminescence studies of Ag ion irradiated kyanite

Ionoluminescence (IL) of kyanite single crystals bombarded with 100 MeV swift Ag⁸⁺ ions with fluences in the range 1.87-7.5×10¹¹ ions/cm² has been studied. A pair of sharp IL peaks at ∼689 and 706 nm along with broad emission in the region 710-800 nm are recorded in both crystalline and pelletized samples. Similar results are recorded in Photoluminescence (PL) of pelletized kyanite bombarded with same ions and energy with fluences in the range 1×10¹¹-5×10¹³ ions/cm² with an excitation of 442 nm laser beam. The characteristic pair of sharp emission peaks at 689 and 706 nm in both IL and PL is attributed to luminescence centers activated by Fe²⁺ and Fe³⁺ ions. The reduction in IL and PL bands intensity with increase of ion fluence might be attributed to degradation of Si-O (2ν₃) bonds, present on the surface of the sample.