Target-plane deposition of diamond-like carbon in pulsed laser ablation of graphite

In pulsed Nd:YAG laser ablation of highly oriented pyrolytic graphite (HOPG) at 10⁻⁶ Torr, diamond-like carbon (DLC) are deposited at laser wavelengths of 1064, 532, and 355 nm on substrates placed in the target-plane. These target-plane samples are found to contain varying sp³ content and composed of nanostructures of 40-200 nm in size depending on the laser wavelength and laser fluence. The material and origin of sp³ in the target-plane samples is closely correlated to that in the laser-modified HOPG surface layer, and hardly from the backward deposition of ablated carbon plume. The surface morphology of the target-plane samples shows the columnar growth and with a tendency for agglomeration between nanograins, in particular for long laser wavelength at 1064 nm. It is also proposed that DLC formation mechanism at the laser-ablated HOPG is possibly via the laser-induced subsurface melting and resolidification.     

Synthesis of cation-exchanged laponite suspensions by laser ablation of microsized-metal particles in liquid

Laser ablation in the liquid technique has been used to synthesize cation-exchanged laponite suspensions. In summary, laser ablation of the microsize-metal powder (Co, Al, and Cu) dispersed in an aqueous solution containing deionized water laponite crystals was carried out using laser beam generated by a single-mode, Q-switched Nd-Yag laser operating at 532 nm with a pulse duration of 5.5 ns and 10 Hz repetition rate. Laser fluence was 0.265 J/cm² for all tests. For all samples, the mass fraction of laponite was 1%. General observations of the prepared samples indicated that an aqueous suspension of 1 wt% laponite retained its free flowing liquid phase characteristics even after aging for several weeks. When bivalent cationic metals (Cu, Co, Al) were ablated in it for about 1 h, even with a small amount of the metal (0.025% and 0.050%) were generated, the suspension became highly viscous and behaved as a shear-thinning and thixotropic material. That is, the suspension gelled strongly when it was allowed to rest. The gels, however, could easily be reverted to a low viscosity liquid with simple shaking. Information from TEM and XRD analysis indicated that such a sol-gel transformation might be due to the charge exchange between the cationic species produced during the laser ablation and the sodium ions in the interlayers of the clay sheets.     

Preparation of silver nanoparticles by laser ablation in polyvinylpyrrolidone solutions

We performed laser ablation of a silver plate in polyvinylpyrrolidone (PVP) aqueous solutions to prepare silver nanoparticles. Secondary laser irradiation onto the prepared colloidal solutions was also carried out. It was revealed that the formation efficiency was increased by addition of PVP as well as the stability of nanoparticles. The result of shadowgraph measurements suggested that the increased ablation efficiency by PVP is attributable to increased secondary etching efficiency by the solvent-confined plasma toward the silver plate. On the other hand, the size decrease of the nanoparticles by addition of PVP was more remarkable during the secondary irradiation process than in the laser ablation (nanoparticle preparation) process. This result indicates that emitted materials interact less sufficiently with PVP molecules in the laser ablation process than in the secondary laser irradiation process.     

Spectroscopic characterization approach to study surfactants effect on ZnO2 nanoparticles synthesis by laser ablation process

Zinc peroxide nanoparticles having grain size less than 5 nm were synthesized using pulsed laser ablation in aqueous solution in the presence of different surfactants and solid zinc target in 3% H₂O₂. The effect of surfactants on the optical and structure of ZnO₂ was studied by applying different spectroscopic techniques. Structural properties and grain size of the synthesized nanoparticles were studied using XRD method. The presence of the cubic phase of zinc peroxide in all samples was confirmed with XRD, and the grain sizes were 4.7, 3.7, 3.3 and 2.8 nm in pure H₂O₂, and H₂O₂ mixed with SDS, CTAB and OGM respectively. For optical characterization, FTIR transmittance spectra of ZnO₂ nanoparticles prepared with and without surfactants show a characteristic ZnO₂ absorption at 435-445 cm⁻¹. FTIR spectrum revealed that the adsorbed surfactants on zinc peroxide disappeared in case of CTAB and OGM while it appears in case of SDS. This could be due to high critical micelles SDS concentration comparing with others which is attributed to the adsorption anionic nature of this surfactant. Both FTIR and UV-vis spectra show a red shift in the presence of SDS and blue shift in the presence of CTAB and OGM. The blue shift in the absorption edge indicates the quantum confinement property of nanoparticles. The zinc peroxide nanoparticles prepared in additives-free media was also characterized by Raman spectra which show the characteristic peaks at 830-840 and 420-440 cm⁻¹.     

Synthesis of nanoparticles and suspensions by pulsed laser ablation of microparticles in liquid

Recent studies demonstrated that the process to produce metal and oxide nanoparticles by laser ablation of consolidated microparticles is a convenient and energy-efficient way to prepare nanoparticles. In this work, the novel process is applied to nanoparticle synthesis in the liquid environment and the results are compared with those by the gas-phase process. Metal and oxide nanoparticles are synthesized by pulsed laser ablation of the compacted metal microparticles using a Q-switched Nd:YAG laser in water. It is shown that the process is effective for preparing nanoparticle suspensions having relatively uniform size distributions. While the laser fluence and the degree of compaction strongly influence the size of the produced nanoparticle in air, the sedimentation time is shown to be the most critical factor to determine the mean size of the suspended particles.     

Impact of open de-ionized water thin film laminar immersion on the liquid-immersed ablation threshold and ablation rate of features machined by KrF excimer laser ablation of bisphenol A polycarbonate

Debris control and surface quality are potential major benefits of sample liquid immersion when laser micromachining; however, the use of an immersion technique potentially modifies the ablation mechanism when compared to an ambient air interaction. To investigate the machining characteristics, bisphenol A polycarbonate has been laser machined in air and under a controllable open liquid film. To provide quantitative analysis, ablation threshold, ablation rate and the attenuation coefficient of the immersing de-ionized (DI) water fluid were measured. In ambient air the threshold fluence was measured to be 37 mJ cm⁻². Thin film immersion displayed two trends: threshold fluences of 58.6 and 83.9 mJ cm⁻². The attenuation of DI water was found to be negligible; thus, the change in ablation rate resulted from increased confinement of the vapour plume by the liquid medium, generating higher Bremsstrahlung attenuation of the beam, lowering the laser etch rate. Simultaneously, splashing motivated by the confined ablation plume allowed release of plume pressure before plume etching commenced. This contributed to the loss of total etching efficiency. Two interaction scenarios were obsereved as a result of splashing: (i) intermediate threshold fluence, where splashing occured after every pulse in a mode that interrupted the flow entirely, leaving an ambient air interaction for the following pulse; (ii) high threshold fluence, where splashing occured for every pulse in a mode that allowed the flow to recommence over the image before the next pulse causing every pulse to experience Bremsstrahlung attenuation. Since attenuation of the immersion liquid was negligible, it is the action of the constrained ablation plume within a thin flowing immersion liquid, the resultant Bremsstrahlung attenuation and splashing events that are the critical mechanisms that modify the primary ablation characteristics.     

Nano-ionic thin films of gadolinia-doped ceria prepared by pulsed laser ablation

Microstructural properties of nano-ionic thin films of gadolinia-doped ceria (GDC) prepared by pulsed laser ablation from sintered targets of gadolinia (5–20 mol%) doped ceria are investigated. The ionic conductivity measurements of the sintered pellets showed a decrease in the activation energy from 1.1 to 0.65 eV for 5 and 30 mol% gadolinia-doped ceria, respectively. The microstructural properties of the GDC films as a function of substrate temperature, oxygen partial pressure, and laser energy show that the films are polycrystalline in the entire range of substrate temperature. The grain size is found to increase with increasing temperature up to 873 K. Further improved crystallinity is noticed for the films grown with oxygen partial pressure of 0.1–0.2 mbar. X-ray diffraction and transmission electron microscopy (TEM) reveal nanocrystalline grains with textured growth along <111> orientation in these films at low substrate temperature and at lower oxygen partial pressure. TEM study shows a uniform distribution of nanocrystal of 8–10 nm for energies ≤200 mJ/pulse, and nanocrystals embedded in a large crystalline matrix of doped ceria for energies in the range 400–600 mJ/pulse. Raman spectroscopy also confirms the defects in these films. The study also reveals that the substrate temperature and oxygen partial pressure could influence preferred orientation, while the laser energy could significantly influence defect concentration in these films. Invited paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, Dec. 7–9, 2006.     

Enhancement of organic nanoparticle preparation by laser ablation in aqueous solution using surfactants

Nanoparticle and metal phthalocyanine (MPc) transparent colloidal aqueous solutions were directly obtained by 355 nm YAG laser ablation. We found that too long an irradiation time does not contribute to producing nanoparticles and their generation efficiency increases with a low solution temperature. We believe this due to nanoparticle reassociation which is caused by hydrophobicity. To prevent generated nanoparticles from reassociating we performed experiments adding two kinds of ionic and nonionic surfactants into solution. We found five characteristics of nanoparticle generation from adding surfactants to a solution regardless of the type of surfactant used. These characteristics are that: (1) production efficiency increases; (2) stability is better after irradiation; (3) irradiation intensity needed to induce nanoparticle generation becomes lower; (4) mean size of the generated nanoparticles becomes smaller; and (5) crystalline structures of oxo(phthalocyaninato) vanadium (IV) (VOPc) are controllable by changing the surfactant concentration.     

Morphological and chemical modifications and plume ejection following UV laser ablation of doped polymers: Dependence on polymer molecular weight

This work investigates the effect of polymer molecular weight (M_W) on the morphological and chemical modifications and on the plume ejection of doped polymethyl methacrylate (PMMA), and polystyrene (PS) films following irradiation at 248 nm. Micro-bubbles develop in the irradiated films of the low absorbing PMMA-based substrates. The extent and kinetics of the observed morphological changes are respectively larger and last longer in the low M_W polymer, as evidenced by optical microscopy and real-time monitoring of transmission of a CW laser. The changes observed in the Raman spectra upon irradiation indicate that degradation occurs to a higher extent in larger M_W polymers. Laser induced fluorescence (LIF) probing of the plume reveals the presence of NapH and PhenH products from, respectively, NapI- and PhenI-doped films and a slower ejection process in the plume of low M_W polymer. For highly absorbing PS, a less dramatic dependence on M_W is observed. Results are discussed in the framework of the bulk photothermal model, according to which ejection requires a critical number of bonds to be broken.     

Synthesis of ZnO nanoparticles using nanosecond pulsed laser ablation in aqueous media and their self-assembly towards spindle-like ZnO aggregates

ZnO nanoparticles were fabricated by pulsed laser ablation (PLA) of a Zn metal in aqueous media, and aging effects on the morphology and photoluminescence properties of ZnO nanoparticles were investigated. The crystalline phase and particle morphology were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). It was found that small, well-defined ZnO nanoparticles were obtained by PLA of a Zn plate in aqueous media, and subsequent aging of the obtained ZnO nanoparticle suspension produced in cetyltrimethylammonium bromide (CTAB) solution led to the formation of spindle-like ZnO aggregates. However, in deionized water not the spindle-like ZnO aggregates but fluffy round aggregates were obtained. High-resolution transmission electron microscopic (HRTEM) observation indicated that the spindle-like ZnO aggregates were composed of many well-defined nanoparticles. Spindle-like aggregates exhibited strong exciton emission, while green emission could be suppressed via an aging process in the presence of CTAB. Moreover, thin films prepared by electrophoretic deposition (EPD) of ZnO nanoparticles after PLA in the presence of CTAB also possessed highly elongated aggregate structures that were possibly formed by surrounding the ZnO nanoparticles with double layers of CTAB molecules.     

The effect of liquid environment on size and aggregation of gold nanoparticles prepared by pulsed laser ablation

The effects of liquid environment on nucleation, growth and aggregation of gold nanoparticles were studied. Gold nanoparticles were prepared by pulsed laser ablation in deionised water with various concentrations of ethanol and also in pure ethanol. UV/visible extinction and TEM observations were employed for characterization of optical properties and particle sizes respectively. Preparation in water results in smaller size, shorter wavelength of maximum extinction and stable solution with an average size of 6 nm. Nanoparticles in solution with low concentration ethanol up to 20 vol% are very similar to those prepared in water. In the mixture of deionised water and 40 up to 80 vol% ethanol, wavelength of maximum extinction shows a red shift and mean size of nanoparticles was increased to 8.2 nm. Meanwhile, in this case, nanoparticles cross-linked each other and formed string type structures. In ethanol, TEM experiments show a mean size of 18 nm and strong aggregation of nanoparticles. The data were discussed qualitatively by considering effects of polarity of surrounding molecules on growth mechanism and aggregation. This study provided a technique to control size, cross-linking and aggregation of gold nanoparticles via changing the nature of liquid carrier medium.     

Characterization of optical and nonlinear optical properties of silver nanoparticles prepared by laser ablation in various liquids

The optical, structural, and nonlinear optical properties of silver nanoparticles prepared by laser ablation in various liquids were investigated at 397.5, 532, and 795 nm. The TEM and spectral measurements have shown temporal dynamics of size distribution of Ag nanoparticles in solutions. The thermal-induced self-defocusing dominated in the case of high pulse repetition rate as well as in the case of nanosecond pulses. In the case of low pulse repetition rate, the self-focusing (γ = 3 × 10⁻¹³ cm² W⁻¹) and saturated absorption (β = −1.5 × 10⁻⁹ cm W⁻¹) of picosecond and femtosecond radiation were observed in these colloidal solutions. The nonlinear susceptibility of Ag nanoparticles ablated in water was measured to be 5 × 10⁻⁸ esu (at λ = 397.5 nm).     

Fabrication of transparent double-walled carbon nanotubes flexible matrix touch panel by laser ablation technique

This study reports on the fabrication of transparent double-walled carbon nanotubes (DWNTs) flexible matrix touch panel using the method of laser ablation. We employed an Nd:YAG laser (1064 nm) to pattern transparent DWNT thin film pre-coated on a PET substrate and successfully fabricated a flexible matrix touch panel. By increasing the laser energy, the ablation depth of transparent DWNT flexible thin film is increased but the sheet resistance (Ω/sq) is decreased. When the laser energy intensity reaches 117 mJ/cm², the DWNTs can be completely ablated from transparent DWNT flexible thin film. This method is rapid, simple, applicable to large-area processing and thus is potential for mass production.     

Investigation of metal nanoparticles produced by laser ablation and their catalytic activity

Polydiphenylsilylenemethylene (PDPhSM) thin films, which are difficult to fabricate by conventional methods because of their insolubility and high melting point, have been synthesized by using laser-ablated metal nanoparticles for the thermal ring-opening polymerization of 1,1,3,3-tetraphenyl-1,3-disilacyclobutane (TPDC) in this paper. TPDC was first evaporated on silicon substrates and then exposed to metal (Pt, Cu and Ag) nanoparticles deposition by laser ablation prior to heat treatment. The catalytic activity of Pt, Cu and Ag nanoparticles has been studied. The results showed that the mean diameter of Pt nanoparticles was the smallest, Cu nanoparticles the moderate and Ag nanoparticles the biggest, while the polymerization efficiency for Pt nanoparticles was the highest, Cu nanoparticles the moderate and Ag nanoparticles the lowest. In addition, the penetration behaviours of Pt, Cu and Ag nanoparticles into the TPDC monomer films during laser ablation were different due to the particle size or the chemical interaction between metal nanoparticles and TPDC molecules.     

Enhancement of ablation rate and production of colloidal nanoparticles by irradiation of metals with nanosecond pulsed laser in presence of external electric field

This paper presents the results of experimental study on the effect of electric field on the ablation rate during the nanosecond pulsed laser ablation of aluminum and copper in deionized water. The effect of electric field strength on the material removal rate and its mechanisms were investigated both in the electric field parallel and perpendicular to the laser beam path schemes. The ablation rate was estimated by measuring the dimensions of craters on the target induced by laser. The crater dimensions and optical properties of the produced colloidal nanoparticles were characterized by means of optical microscopy and UV–Vis absorption spectroscopy, respectively. The results indicate that pulsed laser ablation in the presence of an electric field significantly leads to higher material removal rate. The experimental results also confirm that the crater geometry extremely depends on the direction of the electric field with respect to the laser beam direction. The UV–Vis spectra show that the nanoparticles production efficiency increases with increasing the electric field strength.     

Synthesis and characterization of permalloy nanostructured films by deposition of laser ablated nanoparticles

A permalloy (Ni₈₁Fe₁₉; at%) microparticle (MP) aerosol was ablated to produce a nanoparticle (NP) aerosol that was then impacted at high velocity onto a substrate to produce porous thick films. The structure of the NPs was analyzed by transmission electron microscopy and the morphologies of the NPs and the nanostructured films were studied using high-resolution transmission electron microscopy and scanning electron microscopy. These analyses showed that the original composition and structure of the MPs were preserved in the NPs and films. The majority of NPs that were produced ranged in size between 2 and 15 nm with some larger particles present. Magnetization-temperature curves showed that the films consisted of a mixture of small superparamagnetic NPs and larger ferromagnetic NPs. A high saturation magnetization of 62.3 emu/g at 300 K was retained in the films indicating that they remained free of significant oxidation.