Laser-assisted shape selective fragmentation of nanoparticles

Experimental results are presented on laser-assisted fragmentation of gold-containing nanoparticles suspended in liquids (either ethanol or water). Two kinds of nanoparticles are considered: (i) elongated Au nanorods synthesized by laser ablation of a gold target immersed in liquid phase; (ii) gold-covered NiCo nanorods with high aspect ratio (θ ∼ 10) synthesized by wet chemistry processes. The shape selectivity induced by laser fragmentation of these nanorods is gained via tuning the wavelength of laser radiation into different parts of the spectrum of their plasmon resonance corresponding to different aspect ratios θ. Fragmentation is performed using three laser wavelengths, involving a Cu vapour laser (510 and 578 nm) and a Nd:YAG (1064 nm). Nanoparticles are characterized by UV-vis spectrometry, Transmission Electron Microscopy (TEM). The effect of laser pulse duration (nanosecond against picosecond range) is also studied in the case of fragmentation with an IR laser radiation.     

Influence of Silver and Gold Nanoparticles and Thin Layers on Charge Carrier Generation in InGaN/GaN Multiple Quantum Well Structures and Crystalline Zinc Oxide Films

It has been shown that Ag and Au nanoparticles and thin layers influence charge carrier generation in InGaN/GaN multiple quantum well structures and crystalline ZnO films owing to the surface morphology heterogeneity of the semiconductors. When nanoparticles 10 < d < 20 nm in size are applied on InGaN/GaN multiple quantum well structures with surface morphology less nonuniform than that of ZnO films, the radiation intensity has turned out to grow considerably because of a plasmon resonance with the participation of localized plasmons. The application of Ag or Au layers on the surface of the structures strongly attenuates the radiation. When Ag and Au nanoparticles are applied on crystalline ZnO films obtained by rf magnetron sputtering, the radiation intensity in the short-wavelength part of the spectrum increases insignificantly because of their highly heterogeneous surface morphology.     

Laser ablation of silver and gold in liquid ammonia

Laser ablation of a silver (Ag) and/or gold (Au) target was performed in liquid ammonia (l-NH₃) at 233 K using nanosecond laser pulses of 1064, 532 and 355 nm wavelengths. An “in situ” monitoring of the ablation process by UV/vis/NIR spectroscopy has shown the evolution of the surface plasmon extinction band of silver or gold nanoparticles and thus confirmed their formation. While sols of Au nanoparticles in l-NH₃ are quite stable in air, those of Ag nanoparticles undergo oxidation to Ag(I) complexes with NH₃ ligands. On the other hand, formation of solvated electrons, namely of the (e⁻)NH₃ solvates, has not been unequivocally confirmed under the conditions of our laser ablation/nanoparticle fragmentation experiment, since only very weak vis/NIR spectral features of these solvates were observed with a low reproducibility. Reference experiments have shown that the well-known chemical production of these solvates is hindered by the presence of Ag and Au plates. Ag and Au targets can thus possibly act as electron scavengers in our ablation experiments.     

Nanoparticles produced by laser ablation of solids in liquid environment

A review of results on nanoparticles formation is presented under laser ablation of Ag, Au, and Ti solids targets in liquid environments (H₂O, C₂H₅OH, C₂H₄Cl₂, etc.). X-ray diffractometry (XRD), UV-Vis optical transmission spectrometry, and high-resolution transmission electron microscopy (HRTEM) characterise the nanoparticles. The morphology of nanoparticles is studied as a function of both laser fluence and nature of the liquid. The evidence of an intermediate phase of Au-Ag alloy is presented under exposure of a mixture of individual nanoparticles to laser radiation. Self-influence of the beam of a femtosecond laser is discussed under the ablation of the Ag target in liquids under Ti:sapphire laser. The factors are discussed that determine the distribution function of particle size under laser ablation. The influence of laser parameters as well as the nature on the liquid on the properties of nanoparticles is elucidated. PACS 42.62.-b; 61.46.+w; 78.66.-w     

Generation of nanospikes via laser ablation of metals in liquid environment and their activity in surface-enhanced Raman scattering of organic molecules

The formation of dense arrays of nanospikes occurs under laser ablation of bulk targets (Ag, Au, Ta, Ti) immersed in liquids such as water or ethanol. The average height of spikes is 50 nm and their density on the target amounts to 10¹⁰ cm⁻². The effect is observed with sufficiently short laser pulses. In particular, either a 350 ps or a 90 ps Nd:YAG lasers are used in their fundamental harmonics. The nanospikes are characterized by UV-Visible reflection spectrometry and atomic force microscopy. The oscillations of electrons within nanospikes result in a permanent coloration of the surface and a modification of the optical reflection spectra of the metal. Scanning the laser beam along the metal surface allows its nanostructuring over extended areas (∼1 cm²). The nanostructured Ag surface shows enhanced Raman scattering of acridine molecules at a concentration of 10⁻⁵ M/l, whereas the initial Ag targets do not show any signal within the accuracy of measurements.     

Laser-assisted generation of gold nanoparticles and nanostructures in liquid and their plasmonic luminescence

Nanoparticles (NPs) and surface nanostructures (NS) are produced via laser ablation of a bulk gold target in liquid using second harmonics of 10 ps Nd:YAG laser (532 nm) with repetition rate of 50 kHz. The morphology and plasmon photoluminescence (PL) properties of obtained nanoscale objects are described. Transmission electron microscopy and field emission scanning electron microscopy are used for morphology characterization of NPs and NS, respectively. Plasmon PL of both gold NPs and NS is experimentally studied using the third harmonics of the Nd:YAG picosecond laser (355 nm) as a pump. The wavelength of intensity maximum of PL of Au NPs colloidal solution virtually coincides with the position of Au NPs plasmon absorption peak. Real-time excitation of both plasmon PL and Raman scattering of surrounding liquid by picosecond laser pulses in aqueous colloidal solution is also investigated. The efficient cross section of plasmon PL of Au NPs colloid is evaluated using Raman scattering of water as a comparative parameter. The results are in good agreement with values obtained in previous works. Plasmon PL from self-organized NS on the Au surface produced via laser ablation is observed for the first time. Its spectrum is compared to PL spectra of both aqueous colloidal solutions of NPs and of NPs deposited on a Si wafer. The obtained experimental data are discussed with reference to the band structure of bulk Au.     

High probability of single molecule junction formation with Ag electrodes

We use a scanning tunneling microscope-based break-junction technique to compare the probability of the formation of a single-molecule junction for a series of amine-terminated oligophenyl and alkane species using either Ag or Au as electrodes. For all molecules, we find that there is a significantly higher probability of junction formation when using Ag electrodes than with Au electrodes. We also find that longer molecules have a higher probability than shorter molecules to form a junction for both Ag and Au electrodes. For all molecules, the measured molecular junction length that is formed with the Ag electrodes was longer than that formed with Au electrodes. Furthermore, we can make a single atomic oxygen junction and can measure its conductance using Ag electrodes. These observations are attributed to a narrower gap of the Ag electrodes compared to that of the Au electrodes after the metal contact ruptures. Since there is a high probability of a molecular junction forming when using Ag electrodes, we can therefore perform a statistical analysis within the context of the material properties that are suitable for future molecular electronics.     

Experimental characterization of bi-directional terahertz emission from gold-coated nanogratings

The THz radiation emission of Au-coated nanogratings (fused silica substrate, 30?nm Au layer thickness, 500?nm grating constant) upon fs laser irradiation (785?nm, 150?fs, 1?kHz,???1?mJ/pulse) is observed in both directions along the laser beam axis (forward and backward) and for both, illumination of the Au/air or the Au/silica interface. THz radiation along the laser beam propagation is emitted in a narrow solid angle of about 15°?fwhm independent on the laser pulse fluence, the angle of incidence and the nanograting profile. The bar width and groove depth of the nanograting as well as the angle of laser beam incidence strongly affect the THz radiation yield. The energy of single THz light pulses is measured absolutely (2?fJ in the 0.3?C0.38?THz range) using a highly sensitive and fast superconducting transition edge sensor. The bi-directional emission of THz radiation is in agreement with the model assumption of surface plasmon polaritons propagating simultaneously on both Au layer interfaces (Au/air and Au/silica).     

New surface structure analysis of Ag-Si phase by quantitative auger electron spectroscopy method

Ag or Au was deposited on a clean Si substrate at room temperature. These systems, Ag/Si and Au/Si, were annealed at various temperatures or various heating times. Due to the annealing, Ag or Au diffused into Si and/or Si diffused into the metal. The changes of the surface composition are analyzed by a quantitative Auger Electron Spectroscopy (AES) method which is newly developed as a non-destructive method. In the case of Ag/Si, Ag migrated into the Si substrate and/or Si diffused into Ag. Then, Ag-Si solid solution was produced. After the annealing, the Ag/Si system is changed into Ag/(Ag-Si)/Si of the three-phase structure. In the case of Au/Si (Au film thickness < 15 Å), the Au film thickness became thinner by annealing. The Au/Si system always keeps the Au/Si phase after annealing, while there was no Au-Si solution area. The difference between the Ag/(Ag-Si)/Si and the Au/Si structure is attributed to the reason that Au diffuses more quickly than Ag into the Si substrate. AES results after annealing cannot be explained by the model of the formation of the three-dimensional island structure which is commonly referenced.     

Phase diagrams of laser-processed nanoparticles of brass

Nanoparticles of brass are prepared by ablation of a brass target in ethanol using radiation of a copper-vapor laser at various laser fluences. The nanoparticles are characterized by TEM and optical spectroscopy. The multipulse laser irradiation leads to formation both the nanoparticles in liquid and well-ordered micro-structures on a surface of a target. It is revealed that both the morphology and absorption spectra of brass nanoparticles depend on presence of the micro-structures. Nanoparticles with the various phase diagrams are formed from a flat brass surface and from the same surface with micro-structures. The results are compared with a model of phase diagrams, in which size and composition effects are taken into account.     

Synthesis of nanoparticles by pulsed laser ablation of consolidated metal microparticles

This paper describes a novel process of nanoparticle synthesis by pulsed laser ablation of consolidated microparticles. Metal microparticles, including Cu, Al and Ag, are consolidated by a cold isobaric press with pressures up to a few hundred MPa before laser irradiation. Nanoparticles are then synthesized in air by high-power pulsed laser ablation of the microparticles using a Q-switched Nd:YAG laser. It is shown that the degree of compaction plays a significant role in determining the size of the produced nanoparticles. The effect of laser fluence and collector position on the distribution of particle size is examined. Photoacoustic deflection probing and nanosecond time-resolved visualization indicate that the novel process attains increased efficiency of laser-energy coupling with the target. PACS 81.07.-b; 81.07.Wx; 42.62.Cf     

Migration-coalescence of Nanoparticles During Deposition of Au,Ag, Cu,and GaAs on Amorphous SiO2

Nanoparticles formed during the initial period of film growth can migrate, coalesce, and may also melt. Nanoparticles of Au, Ag, Cu, and GaAs ranging from 1 to 15nm in diameter were sputter-deposited on amorphous SiO₂ (a-SiO₂). Transmission electron microscopy was used to analyze the time-dependent change of the dispersion of particles on a thin film. The number density of nanoparticles was nearly constant during the deposition of Ag. For Au, Cu, and GaAs, however, the number density decreased with time during the early deposition period. For example, for Au the number density decreased from 2.8×10¹⁶m^–2 (surface coverage ratio of 0.08) to 1.8×10¹⁶m^–2 (surface coverage ratio of 0.14). The surface coverage increased because the particle size increased as the number density decreased. This decrease suggests that migration followed by coalescence occurred. For Au, although we found evidence of migration of 2-nm particles at 500°C, the migration rate was too slow to account for the results from the deposition experiments. These observations indicate an autocatalytic mechanism that migration followed by coalescence liberates energy by the formation of chemical bonds, heats the coalesced particles, and enhances further migration. The strong dependence of the structure of nanoparticle dispersions on the deposition rate is a direct consequence of the deposition mechanism, which is a nonlinear, kinetically-controlled process.     

The work function and electronic structure of coherent Ag–Au interfaces

First-principles calculations reveal that coherent Ag–Au interfaces are energetically favorable with negative interface energies, signifying an intermixing tendency of Ag and Au. Calculations also show that for each Ag–Au interface two overlayers are needed to get a relatively stable work function and the interface dipole is formed due to an unequal loss of electrons from Ag and Au atoms. Moreover, the densities of states suggest that a stronger chemical bonding is formed in the Ag–Au interface than in the corresponding Ag or Au bulks.     

A study of the thermal-induced nonlinearity of Au and Ag colloids prepared by the chemical reaction method

The nonlinear optical properties of metal Au and Ag colloidal solutions prepared by the chemical reaction method were investigated by a single beam Z-scan technique. Under CW 633 nm excitation, the Au and Ag colloidal solutions exhibited a large thermal-induced refractive index n₂. At the same time, the thermo-optic coefficients dn/dT of the Au and Ag colloidal solutions were obtained. The mechanism responsible for the process of nonlinear refraction was discussed in term of laser heating effect.     

Reduction of the linewidths of deep luminescence centers in 28Si reveals fingerprints of the isotope constituents

Dramatic reductions of the linewidths of well-known deep centers in 28Si reveal "isotopic fingerprints" of the constituents. The approximately 1014 meV Cu center, thought to be either a Cu pair or an isolated Cu, is shown to contain four Cu atoms, and the approximately 780 meV Ag center is shown to contain four Ag. The approximately 944 meV ;{*}Cu center, thought to be a different configuration of a Cu pair, in fact contains three Cu and one Ag, and a new two-Cu two-Ag center is found. The approximately 735 meV center, previously assigned to Fe, actually contains Au and three Cu. This suggests a family of four-atom (Cu, Ag, Au) centers.     

Generation of higher harmonics of femtosecond radiation in clusters

The frequency conversion of laser radiation in cluster media is studied by the method of laser ablation of surfaces containing different nanoparticles (Cr₂O₃, In₂O₃, Ag, Sn, Au, and Cu). Using plasma that contains In₂O₃ nanoparticles as an example, it is shown that the resonant amplification of certain harmonics in the plateau-like distribution of harmonics, which is characteristic of the ablation of certain solid targets, is considerably modified in the case of targets that contain cluster formations. An increase in the conversion efficiency to harmonics in nanoparticle-containing media is discussed. In order to determine optimal characteristics of laser plasma with nanoparticles, their morphology is studied before and after laser ablation.     

High reflective p-GaN/Ni/Ag/Ti/Au Ohmic contacts for flip-chip light-emitting diode (FCLED) applications

The fabrication of high reflective Ni/Ag/(Ti, Mo)/Au Ohmic contacts for flip-chip light-emitting diode (FCLED) are proposed and considered, Ni/Ag/Au Ohmic contacts are also fabricated to compare their resulting reflectivities. From secondary ion mass spectrometry (SIMS) depth profiles, it indicates that the Au in-diffusion occurs in Ni/Ag/Au contacts after annealing. It is considered that Au in-diffusion, which is intermixed with Ag, Ni and GaN in Ni/Ag/Au contacts after annealing, is responsible for the resulting low reflectance (63% at the wavelength of 465 nm). To avoid Au in-diffusion and enhance the reflectivity, a diffusion barrier metal (Ti or Mo) between Ni/Ag and Au is fabricated and examined. It is demonstrated and found that an insertion of diffusion barrier metal of Ti enables to block Au diffusion effectively and also improve the reflectivity significantly, up to 93%.     

High-order harmonic generation in nanoparticle-containing laser-produced plasmas

Nanoparticle-containing media can be used for the efficient high-order harmonic generation (HHG) of laser radiation in the extreme ultraviolet range. We review the results of recent studies of the HHG in laser-produced plasmas containing Ag, Au, Pd, Pt, Ru, GaN, BaTiO₃, and SrTiO₃ nanoparticles. The harmonics of femtosecond radiation up to the 55th order were achieved using the nanoparticle-containing plumes, when the femtosecond radiation propagated through the preformed plasma. These results are compared with the high-order harmonics generated from the plasma produced on the surface of bulk targets at different delays between the subnanosecond heating prepulse and femtosecond pulse. We discuss a six-fold enhancement of the HHG yield, which was achieved in the case of nanoparticle-containing plumes with regard to the monoparticle-containing plasmas.     

Ligand-free gold–silver nanoparticle alloy polymer composites generated by picosecond laser ablation in liquid monomer

Polymer matrix nanocomposites filled with metallic and alloy nanoparticles add functionality in various applications such as optical devices and in the energy sector. However, matrix coupling agents or nanoparticle ligands may be unwanted additives, potentially inhibiting the resulting nanocomposite to be processed by injection molding. The generation of stabilizer-free Au, Ag, and AuAg alloy nanoparticle acrylate composites is achieved by picosecond-pulsed laser ablation of the respective metal target in the liquid monomer. Complementary to laser ablation of the solid alloy, we have alloyed nanoparticles by post-irradiation of Au and Ag colloids in the liquid monomer. The optical properties of the colloidal nanoparticles are successfully transferred to the solid poly(methyl methacrylate) matrix and characterized by their plasmon resonance that can be easily tuned between 400 and 600 nm by laser alloying in the liquid monomer.     

利用激光烧蚀法制备表面等离子体可调谐的金核银壳层纳米颗粒胶体

利用激光烧蚀方法在水中制备了金核银壳层纳米颗粒胶体,发现这种复合胶体的等离子体振动吸收峰频率会随着激光烧蚀时间的不同而发生改变。利用等离子杂化理论定性解释了共振吸收峰可调谐的物理机制.