Laser ablation of silver in different liquids: Optical and nonlinear optical properties of silver nanoparticles

The optical, structural, and nonlinear optical properties of silver nanoparticles prepared using the method of laser ablation in various liquids at wavelengths of 397, 532, and 795 nm with laser pulses of different duration are studied. An analysis of the dimensional and spectral characteristics of the silver nanoparticles revealed a time dynamics of the nanoparticle size distribution in solutions. It is shown that thermal self-defocusing is observed for the case of nanosecond or shorter pulses generated with a high repetition rate. For picosecond and femtosecond pulses with a low repetition rate, the effects of self-focusing (γ = 3 × 10^?13 cm² W^?1) and saturated absorption (β = ?1.5 × 10^?9 cm W^?1) were observed in the solutions under study. The third-order nonlinear susceptibility of the silver nanoparticles was found to be 5 × 10^?8 esu at a wavelength of 397 nm.     

Pulse laser-induced particle separation from polymethyl methacrylate: a mechanistic study

The separation mechanism of opaque and transparent model micro-particles, graphite and polystyrene copolymer spheres, respectively, from polymethyl methacrylate (PMMA) substrates were investigated employing a ns-pulse laser radiating at 532 nm. The particles transparent in the visible wavelength range could be removed from PMMA efficiently in a very narrow fluence range between 1 and 2 J/cm² according to a simple 1D thermal expansion model. Above this fluence region, with single pulses, the transparent microspheres caused local ablation of the PMMA substrate in the optical microlens nearfield. This process led to removal of the particles themselves due to the expansion of the ablation plasma. The irregularly shaped graphite particles shaded the underlying substrate from the incoming radiation so that no optical nearfield damage mechanism could be observed. Therefore, a substantial cleaning window between 0.5 and more than 16 J/cm² was provided. The graphite data suggest an ablation mechanism of the particulates themselves due to a high optical absorption coefficient.     

Synthesis and optical properties of silver nanoparticles in ORMOCER

Experimental results on synthesis of metal nanoparticles in ORMOCER by ion implantation are presented. Silver ions were implanted into organic/inorganic matrix at an accelerating energy of 30?keV and doses in the range of 0.25?10¹⁷ to 0.75?10¹⁷?ion/cm². The silver ions form metal nanoparticles, which demonstrate surface plasmon absorption at the wavelength of 425?C580?nm. The nonlinear absorption of new composite materials is measured by Z-scan technique using 150?fs laser pulses at 780?nm wavelength. ORMOCER matrix shows two-photon nonlinear absorption, whereas ORMOCER with silver nanoparticles demonstrates saturated absorption. Some optical applications of these composite materials are discussed.     

Effect of laser fluence on the size of copper oxide nanoparticles produced by the ablation of Cu target in double distilled water

Copper oxide nanoparticles produced in double distilled water at room temperature by laser ablation of the Cu target have been investigated using TEM, SEM, AFM, X-ray diffraction, photo-spectrometry and PIXE. Q-switched Nd:YAG laser operating at 1064 nm with a pulse duration of 5–6 ns was used to conduct the experiments in the fluence range of 5.73–9.87 J/cm². In each experiment, 12,000 laser pulses were used to ablate the target placed in double distilled water. Different diagnostic techniques reveal that the nanoparticles have a size between 2–55 nm and their mean size as well as the width of particle distribution increases with the laser fluence. Since no surface active material (surfactant) was added to water, the nanoparticles aggregated and settled down at the bottom of the container within a week. In addition to stable Cu₂O, the XRD spectrum also shows the presence of suboxide Cu₆₄O in the colloidal solution of nanoparticles produced in the present study.     

Effects of green laser fluence on the characteristics of graphene nanosheets synthesized by laser ablation method in liquid nitrogen medium

We have studied the effects of laser fluence on the characteristics of graphene nanosheets produced by pulsed laser ablation technique. In this work, The second harmonic of a Q-switched Nd:YAG laser at 532 nm wavelength and 5 Hz repetition rate with different laser fluences in the range of 0.5–1.8 J/cm² was used to irradiate the graphite target in liquid nitrogen medium. The products of ablation were characterized using Fourier transform infrared spectroscopy, field emission scanning electron microscopy, X-ray diffraction pattern, UV–Vis absorption spectroscopy, Raman spectrum and transmission electron microscopy. The Raman spectroscopy indicates that the quality of the graphene nanosheets was decreased while their structure defects were increased as the laser fluence was increased from 0.5 to 1.4 J/cm². Our results suggest that the amount of defects and the number of layers in graphene nanosheets can be changed by adjusting the laser fluence. This study could be a useful guidance for producing of high quality of graphene nanosheets by laser ablation method.     

Determination of the mid-IR femtosecond surface-damage threshold of germanium

To assess the potential uses of germanium as a nonlinear material in the mid IR we have measured the surface-damage threshold of germanium optical windows using femtosecond pulses at a wavelength of 3.9 μm. By working with a wavelength corresponding to a photon energy of less than half the band-gap energy, free-carrier generation due to one- and two-photon absorption was eliminated. The laser pulses had an energy of 5.5 μJ, a duration of 255 fs, and were focused to a waist size of approximately 100 μm. The multi-shot damage threshold of the germanium windows was estimated to be approximately 94 GW/cm². The data should be of immediate benefit to industrial laser researchers and applications engineers working in the mid-IR region.     

Fabrication of composite based on GeSi with Ag nanoparticles using ion implantation

Comparative analysis of the structural and optical properties of composite layers fabricated with the aid of implantation of single-crystalline silicon (c-Si) using Ge⁺ (40 keV/1 × 10¹⁷ ions/cm²) and Ag⁺ (30 keV/1.5 × 10¹⁷ ions/cm²) ions and sequential irradiation using Ge⁺ and Ag⁺ ions is presented. The implantation of the Ge⁺ ions leads to the formation of Ge: Si fine-grain amorphous surface layer with a thickness of 60 nm and a grain size of 20–40 nm. The implantation of c-Si using Ag⁺ ions results in the formation of submicron porous amorphous a-Si structure with a thickness of about 50 nm containing ion-synthesized Ag nanoparticles. The penetration of the Ag⁺ ions in the Ge: Si layer stimulates the formation of pores with Ag nanoparticles with more uniform size distribution. The reflection spectra of the implanted Ag: Si and Ag: GeSi layers exhibit a sharp decrease in the intensity in the UV (220–420 nm) spectral interval relative to the intensity of c-Si by more than 50% owing to the amorphization and structuring of surface. The formation of Ag nanoparticles in the implanted layers gives rise to a selective band of the plasmon resonance at a wavelength of about 820 nm in the optical spectra. Technological methods for fabrication of a composite based on GeSi with Ag nanoparticles are demonstrated in practice.     

Cavity-enhanced optical feedback-assisted photo-acoustic spectroscopy with a 10.4 μm external cavity quantum cascade laser

An ultra-sensitive photo-acoustic spectrometer using a 10.4 μm broadly tunable mid-IR external cavity quantum cascade laser (EC-QCL) coupled with optical feedback to an optical power buildup cavity with high reflectivity mirrors was developed and tested. A laser optical power buildup factor of 181 was achieved, which corresponds to an intra-cavity power of 9.6 W at a wavelength of 10.4 μm. With a photo-acoustic resonance cell placed inside the cavity this resulted in the noise-equivalent absorption coefficient of 1.9 × 10^?10 cm^?1 Hz^?1/2, and a normalized noise-equivalent absorption of 1.1 × 10^?11 cm^?1 W Hz^?1/2. A novel photo-acoustic signal normalization technique makes the photo-acoustic spectrometer’s response immune to changes and drifts in the EC-QCL excitation power, EC-QCL to cavity coupling efficiency and cavity mirrors aging and contamination. An automatic lock of the EC-QCL to the cavity and optical feedback phase optimization permitted long wavelength scans within the entire EC-QCL spectral tuning range.     

Characterization of Ag and Au nanoparticles created by nanosecond pulsed laser ablation in double distilled water

Pulsed laser ablation of Ag and Au targets, immersed in double-distilled water is used to synthesize metallic nanoparticles (NPs). The targets are irradiated for 20 min by laser pulses at different wavelengths—the fundamental and the second harmonic (SHG) (λ = 1064 and 532 nm, respectively) of a Nd:YAG laser system. The ablation process is performed at a repetition rate of 10 Hz and with pulse duration of 15 ns. Two boundary values of the laser fluence for each wavelength under the experimental conditions chosen were used—it varied from several J/cm² to tens of J/cm². Only as-prepared samples were measured not later than two hours after fabrication. The NPs shape and size distribution were evaluated from transmission electron microscopy (TEM) images. The suspensions obtained were investigated by optical transmission spectroscopy in the near UV and in the visible region in order to get information about these parameters. Spherical shape of the NPs at the low laser fluence and appearance of aggregation and building of nanowires at the SHG and high laser fluence was seen. Dependence of the mean particle size at the SHG on the laser fluence was established. Comments on the results obtained have been also presented.     

Diffraction patterns and nonlinear optical properties of gold nanoparticles

Stable gold nanoparticles have been prepared by using soluble starch as both the reducing and stabilizing agents; this reaction was carried out at 40 °C for 5 h. The obtained gold nanoparticles were characterized by UV–Vis absorption spectroscopy, transmission electron microscopy (TEM) and z-scan technique. The size of these nanoparticles was found to be in the range of 12–22 nm as analyzed using transmission electron micrographs. The optical properties of gold nanoparticles have been measured showing the surface plasmon resonance. The second-order nonlinear optical (NLO) properties were investigated by using a continuous-wave (CW) He–Ne laser beam with a wavelength of 632.8 nm at three different incident intensities by means of single beam techniques. The nonlinear refractive indices of gold nanoparticles were obtained from close aperture z-scan in order of 10^?7 cm²/W. Then, they were compared with diffraction patterns observed in far-field. The nonlinear absorption of these nanoparticles was obtained from open aperture z-scan technique. The values of nonlinear absorption coefficient are obtained in order of 10^?1 cm/W.     

Ag离子注入非晶SiO2的光学吸收、拉曼谱和透射电镜研究

能量为200keV的Ag离子，以1×10¹⁶，5×10¹⁶，1×10¹⁷ cm^-2的剂量分别注入到非晶SiO₂玻璃，光学吸收谱显示：注入剂量为1×10¹⁶ cm^-2的样品的光吸收谱为洛伦兹曲线，与Mie理论模拟的曲线形状一致；注入剂量较大的5×10¹⁶，1×10¹⁷ cm^-2的谱线共振吸收增强，峰位红移并出现伴峰. 透射电镜观察分析表明，注入剂量不同的样品中形成的纳米颗粒的大小、形状、分布都不同，注入剂量较大的还会产生明显的表面溅射效应，这些因素都会影响共振吸收的峰形、峰位和峰强. 当注入剂量达到1×10¹⁷ cm^-2时，Ag纳米颗粒内部可能还形成了杂质团簇. 关键词： 离子注入 纳米颗粒 共振吸收 红移     

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.     

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.     

表面层对1 064 nm高反射镜损伤阈值影响

 采用电子束蒸发的方法制备了３种具有不同表面层材料及结构的中心波长为1 064 nm的零度高反镜,３种膜系表面层分别为1/4波长光学厚度的HfO₂,1/2波长光学厚度的SiO₂,以及1/4波长光学厚度的SiO₂。光谱测试表明：三者在1 064 nm处均有较高的反射率（高于99.8%）,利用热透镜的方法测量得到３个膜系辐照激光正入射情况下,薄膜对光的吸收比例分别为3.0×10^-6,5.0×10^-6和6.5×10^-6,其损伤阈值分别为32.5,45.2和28.4 J/cm²。并在膜层内部电场分布和膜层材料物理特性的基础上分析了３种不同表面层膜系吸收和损伤阈值差别的原因。     

Pulsed laser deposition of nanostructured Ag films

Ultra-thin (0.5-5 nm) films of Ag have been prepared by pulsed laser deposition in vacuum using a 26 ns KrF excimer laser at 1 J cm⁻². The deposition was controlled using a Langmuir ion probe and a quartz crystal thickness monitor. Transmission electron microscopy showed that the films are not continuous, but are structured on nanometer size scales. Optical absorption spectra showed the expected surface plasmon resonance feature, which shifted to longer wavelength and increased in strength as the equivalent film thickness was increased. It is shown that Maxwell Garnett effective medium theory can be used to calculate the main features of optical absorption spectra.     

Surface modulation of silicon surface by excimer laser at laser fluence below ablation threshold

Controlled single step fabrication of silicon conical surface modulations on [311] silicon surface is reported utilizing KrF excimer laser [λ=248 nm] at laser fluence below ablation threshold laser fluence. When laser fluence was increased gradually from 0 to 0.2 J/cm² for fixed 200 numbers of shots; first nanopores are observed to form at 0.1 J/cm², then very shallow nanocones evolve as a function of laser fluence. At 0.2 J/cm², nanoparticles are observed to form. Up to 0.15 J/cm² the very shallow nanocone volume is smaller but increases at a fast rate with laser fluence thereafter. It is observed that the net material volume before and after the laser irradiation remains the same, a sign of the melting and resolidification without any ablation.     

The optical properties and energy transition process in nanocomposite of polyvinyl-pyrrolidone polymer and Mn-doped ZnS

This study has been carried out on the optical properties of polyvinyl-pyrrolidone (PVP), the energy transition process in nanocomposite of PVP capped ZnS:Mn nanocrystalline and the influence of the PVP concentration on the optical properties of the PVP capped ZnS:Mn nanocrystalline thin films synthesized by the wet chemical method. The microstructures of the samples were investigated by X-ray diffraction, the atomic absorption spectroscopy, and transmission electron microscopy. The results showed that the prepared samples belonged to the sphalerite structure with the average particle size of about 2–3 nm. The optical properties of samples are studied by measuring absorption, photoluminescence (PL) spectra and time-resolved PL spectra in the wavelength range from 200 to 700 nm at 300 K. From data of the absorption spectra, the absorption edge of PVP polymer was found about of 230 nm. The absorption edge of PVP capped ZnS:Mn nanoparticles shifted from 322 to 305 nm when the PVP concentration increases. The luminescence spectra of PVP showed a blue emission with peak maximum at 394 nm. The luminescence spectra of ZnS:Mn–PVP exhibits a blue emission with peak maximum at 437 nm and an orange–yellow emission of ion Mn²⁺ with peak maximum at 600 nm. While the PVP coating did not affect the microstructure of ZnS:Mn nanomaterial, the PL spectra of the PVP capped ZnS:Mn samples were found to be affected strongly by the PVP concentration.     

Raman investigation of femtosecond laser-induced graphitic columns in single-crystal diamond

We report on the fabrication of graphitic columns induced in single-crystal diamond plates using 100 fs laser pulses at 800 nm wavelength. Different values of laser fluence (0.6–1.2 J/cm²) and graphitization speed (1–100 μm/s) were used for the laser treatment. A Raman investigation was performed aimed at evaluating the structural properties of the fabricated columns, showing that a lower laser fluence and a proper choice of graphitization speed may improve the degree of graphite crystallinity, and suppress the residual diamond content.     

Biocompatible film deposition by using Nd:YAG pulsed laser

A Nd:YAG laser operating at the fundamental wavelength (1064 nm) and at the second harmonic (532 nm), with 9 ns pulse duration, 100–900 mJ pulse energy, and 30 Hz repetition rate mode, was employed to ablate in vacuum (10^?6 mbar) biomaterial targets and to deposit thin films on substrate backings. Titanium target was ablated at the fundamental frequency and deposited on near-Si substrates. The ablation yield increases with the laser fluence and at 40 J/cm ² the ablation yield for titanium is 1.2×10¹⁶ atoms/pulse. Thin film of titanium was deposited on silicon substrates placed at different distance and angles with respect to the target and analysed with different surface techniques (optical microscopy, scanning electron spectrosopy (SEM), and surface profile).

Hydroxyapatite (HA) target was ablated to the second harmonic and thin films were deposited on Ti and Si substrates. The ablation yield at a laser fluence of 10 J/cm ² is about 5×10¹⁴ HA molecules/pulse. Thin film of HA, deposited on silicon substrates placed at different distance and angles with respect to the target, was analysed with different surface techniques (optical microscopy, SEM, and Raman spectroscopy).

Metallic films show high uniformity and absence of grains, whereas the bio-ceramic film shows a large grain size distribution. Both films found special application in the field of biomaterial coverage.