Femtosecond-laser nanofabrication onto silicon surface with near-field localization generated by plasmon polaritons in gold nanoparticles with oblique irradiation

Nanohole fabrication process with gold nanoparticles irradiated by femtosecond laser at different incident angles is investigated. Nanoparticles with diameter of 200 nm and laser irradiation with center wavelength of 800 nm are used in the present study. The analysis of the electromagnetic field distribution in the near-field zone of the particle is made by simulations based on finite-differential time domain (FDTD) method. It is shown that when gold nanoparticle is irradiated by laser pulse surface plasmon excitation can be induced, and associated with it, high-intensity near field is produced in a limited area around the particle. It is found that the change of the irradiation conditions by means of irradiation from various incident directions gives a possibility of laser nanoprocessing with tunable characteristics. Our results show that enhanced optical intensity is able to be induced on the substrate surface regardless of incident direction of the laser due to the image charge interaction with the substrate. Furthermore, the use of p-polarized laser irradiation at a certain angle gives a minimum of the spatial dimensions of the enhanced zone on the substrate which is about two times smaller than that obtained at normal incidence.     

Preparation of conventional thermoelectric nanopowders by pulsed laser fracture in water: application to the fabrication of a pn hetero-junction

The technique of laser fracture in a liquid medium has been applied to the synthesis of n-type (Bi_0.95Sb_0.05)₂ (Te_0.95Se_0.05)₃ and p-type (Bi_0.2Sb_0.8)₂Te₃ semiconducting nanopowders which are the best conventional materials currently used for thermoelectric applications at ambient temperature. The nanopowders have been prepared with a high yield in an especially built-up cell. Laser fracture in water of micronsized powders has been applied, using a nanosecond Nd:YAG laser working at 532 nm. The obtained powders have been characterized by scanning and transmission electron microscopy and by X-ray diffraction. The mean diameter is about 10 nm and the phase of the initial powders is kept. To test the potentiality of these nanosized materials, we have shown the feasibility to produce a pn hetero-junction.     

Highly effective three-dimensional large-scale microfabrication using a continuous scanning method

Effective scanning is an important issue in two-photon induced stereolithography (TPS) for the reduction of the processing time required to fabricate three-dimensional (3D) nano/microstructures. In large-scale TPS based on a stage-scanning system, the large processing time due to the intrinsic slow response in the stage scanning system is a major obstacle to its use as a practical nanofabrication process. To overcome this drawback, we propose a continuous scanning method (CSM) for a stage-scanning system. In CSM, a pattern is generated with continuous movement of the stage during laser beam exposure. A stable fabrication window (SFW), which enables uniform motion of the stage without errors considering the stage characteristics, was obtained from fundamental experiments. Within the condition of a SFW, 2D and 3D microstructures having nanoscale details were fabricated with a whole scale range of several hundred micrometers using CSM.     

Geometrical dependence of optical negative index meta-materials at 1.55 μm

We have studied the geometry dependency of fishnet-like negative refractive index meta-materials (NIMs), and developed a process to fabricate such NIMs using nanoimprint lithography (NIL) in a controlled way for it to achieve negative refractive index in the desired frequency range. As an example, we fabricated a fishnet structure with a minimum negative refractive index of −1.7 at 1560 nm, which was only 10 nm off the targeted wavelength of 1550 nm.     

Large scale highly organized single-walled carbon nanotube networks for electrical devices

Large-scale room-temperature liquid-phase directed assembly of highly organized single-walled carbon nanotubes (SWNT) over large areas is demonstrated. The presented process utilizes lithographically patterned template to guide the fluidic self-assembly of SWNTs on a silicon-dioxide substrate. The width of these highly organized SWNT structures are in the micron range while their heights are in orders of nanometers. Room temperature electrical I–V characterization of these fabricated high coverage SWNT wires show linear ohmic behavior. The resistivity of these assembled SWNT network is in the order of 10⁻⁶ Ω m demonstrating their metallic characteristics during conductance. Scaling of the assembly processes on a wafer level with high yield is demonstrated. Our developed assembly process is compatible with complimentary metal oxide semiconductor (CMOS) processes and provides a simple and flexible way of building SWNT nanotube-based electronics in a large scale.     

Laser transfer of diamond nanopowder induced by metal film blistering

Blister-based laser induced forward transfer (BB-LIFT) is a promising technique to produce surface microstructures of various advanced materials including inorganic and organic micro/nanopowders, suspensions and biological micro-objects embedded in life sustaining medium. The transferred material is spread over a thin metal film irradiated from the far side by single laser pulses through a transparent support. Interaction of the laser pulse with the metal–support interface under optimized conditions causes formation of a quickly expanding blister. Fast movement of the free metal surface provides efficient material transfer, which has been investigated for the case of diamond nanopowder and diamond-containing suspension. The unique features of the given technique are universality, simplicity and efficient isolation of the transferred material from the ablation products and laser heating.     

Synthesis of 3-dimensional periodic nanostructures in an interference field of UV laser light

In 2000, Campbell et al. (Nature 404:53, 2000) have shown that three-dimensional periodic nanostructures can be obtained from UV laser interference irradiation of photoresist for 6 nanosecond single pulse. We have developed a similar experiment for photolytic gas phase decomposition and for photopatternable organic–inorganic hybrid resins. Different steps in results, presently reported, were first to determine the characteristics of both the 3D interference pattern and interferometer to be associated to a CVD reactor and second to verify the mechanical stability of the set up confirmed with the structuration of a siloxane based methacrylic resins by UV polymerization and finally to grow periodic nanostructures by photolytic gas phase decomposition of chromyl chloride. The experimental results obtained so far indicate that, depending on the electromagnetic energy density, a vapor phase decomposition of chromyl chloride leads to periodic arrays of either Cr–O amorphous or Cr₂O₃ particles on glass and (001)TiO₂ substrates at room temperature.     

ZnO–CuO core–shell nanorods and CuO-nanoparticle–ZnO-nanorod integrated structures

ZnO–CuO core–shell nanorods and CuO-nanoparticle–ZnO-nanorod integrated structures were synthesized for the first time by a two-stage solution process. Scanning electron microscopy and high-resolution transmission electron microscopy show that the diameter and the length of the nanorods are around 60 and 800 nm, respectively. The morphologies of outer CuO could be varied from nanoparticles to nanoshells by adjusting the solvent and dipping processes of copper (II) nitrate solution. The CuO nanoparticles are single-crystalline or highly textured structures with size of around 30 nm. The CuO shell with thickness of around 10 nm is constructed of nanocrystals with sizes in the range of 3–10 nm embedded in an amorphous matrix. Room-temperature cathodoluminescence measurements of the CuO–ZnO nanocomposites exhibit relatively sharp ultraviolet emissions at 380 nm as well as broad green and yellow emissions at 500 and 585 nm. The p-CuO/n-ZnO one-dimensional nanocomposites are promising for optoelectronic nanodevice applications.     

Fabrication of nanowires and nanostructures: combining template synthesis with patterning methods

We report on different approaches that we have adopted and developed for the fabrication of nanowires and nanostructures. Methods based on template synthesis and on self organization seem to be the most promising for the fabrication of nanomaterials and nanostructures due to their easiness and low cost. The development of a supported nanoporous alumina template and the possibility of using this template to combine electrochemical synthesis with lithographic methods open new ways for the fabrication of complex nanostructures. The numerous advantages of the supported template and its compatibility with microelectronic processes make it an ideal candidate for further integration into large-scale fabrication of various nanowire-based devices.     

Efficient synthesis of ZnO nanoparticles,nanowalls, and nanowires by thermal decomposition of zinc acetate at a low temperature

ZnO nanoparticles, nanowires, and nanowalls were synthesized rapidly on Si via thermal decomposition of zinc acetate by a modified chemical vapor deposition at a low substrate temperature of 200–250°C for the first time. The diameters of the synthesized nanoparticles and nanowires are around 100 and 30 nm, respectively, and the thickness of nanowalls is around 20 nm. High-resolution transmission electron microscopy shows that the nanowires as well as nanowalls are single-crystalline, and the nanoparticles are highly-textured poly-crystalline structures. Room-temperature photoluminescence spectra of the nanostructures show strong ultraviolet emissions centered at 368–383 nm and weak violet emissions at around 425 nm, indicating good crystal quality. The study provides a simple and efficient route to synthesize ZnO diverse nanostructures at low temperature.     

Cross patterning on MgO based on dislocations using femtosecond laser irradiation

We show a unique technique to form dense dislocations locally inside a MgO single crystal with a rock-salt type structure using femtosecond (fs) laser irradiation. Cross-shaped patterns of micrometer size, originating from densely introduced dislocations, are formed spontaneously around the focal point. We controlled the three-dimensional propagation of the dislocations by adjusting the pulse energy of the fs laser and NA of objective lens. The technique may open up a new field of dislocation technology for optical applications.     

Nanoscale laser processing and diagnostics

The article summarizes research activities of the Laser Thermal Laboratory on pulsed nanosecond and femtosecond laser-based processing of materials and diagnostics at the nanoscale using optical-near-field processing. Both apertureless and apertured near-field probes can deliver highly confined irradiation at sufficiently high intensities to impart morphological and structural changes in materials at the nanometric level. Processing examples include nanoscale selective subtractive (ablation), additive (chemical vapor deposition), crystallization, and electric, magnetic activation. In the context of nanoscale diagnostics, optical-near-field-ablation-induced plasma emission was utilized for chemical species analysis by laser-induced breakdown spectroscopy. Furthermore, optical-near-field irradiation greatly improved sensitivity and reliability of electrical conductance atomic force microscopy enabling characterization of electron tunneling through the oxide shell on silicon nanowires. Efficient in-situ monitoring greatly benefits optical-near-field processing. Due to close proximity of the probe tip with respect to the sample under processing, frequent degradation of the probe end occurs leading to unstable processing conditions. Optical-fiber-based probes have been coupled to a dual-beam (scanning electron microscopy and focused ion beam) system in order to achieve in-situ monitoring and probe repair.     

Modulating the diameter of carbon nanotubes in array form via floating catalyst chemical vapor deposition

Based on the analysis of catalyst particle formation and carbon nanotube (CNT) array growth process in floating catalyst chemical vapor deposition (CVD), delicately controlled gaseous carbon sources and catalyst precursors were introduced into the reactor for the controllable growth of CNT array. The low feeding rate of ferrocene was realized through low-temperature sublimation. With less ferrocene introduced into the reactor, the collision among the in situ formed iron atoms decreased, which led to the formation of smaller catalyst particles. The mean diameter of the CNT array, grown at 800^oC, decreased from 41 to 31 nm when the ferrocene-sublimed temperature reduced from 80 to 60^oC. Furthermore, low growth temperature was adopted in synthesis, through the modulation of the CNT diameter, by controlling the sintering of catalyst particles and the collision frequency. When the growth temperature was 600^oC, the as-grown CNTs in the array were with a mean diameter of 10.2 nm. If propylene was used as carbon source, the diameter can be modulated in similar trends. The diameter of CNT can be modulated by the parameter of the operation using the same substrate and catalyst precursor without other equipment or previous treatment. Those results provide the possibility for delicately controllable synthesis of CNT array via simple floating catalyst CVD.     

Fabrication of Step-and-Flash Imprint Lithography (S-FIL) templates using XeF<Subscript>2</Subscript> enhanced focused ion-beam etching

The fabrication of Step-and-Flash Imprint Lithography (S-FIL) templates with line widths of 50 nm is described in this work. The structures have been patterned using a Ga⁺ focused ion beam (FIB) in a quartz template. FIB milling is generally accompanied with re-deposition effects, which represent a hindrance to densely patterned nanostructures required in most NIL applications. To reduce these re-deposition effects, in this research, xenon difluoride (XeF₂) enhanced FIB etching was applied that also increases the material removal rates in comparison to pure kinetic ion sputtering. To optimise the process when using XeF₂ gas the following ion scanning parameters have been examined: ion dose, beam current, dwell time and beam overlap (step size). It has been found that the assisting gases at very low doses do not bring significant etching enhancements whilst the sputtering rates have increased at high doses. Using the XeF₂ gas-assisted etching, FIB structuring has been used to fabricate <100 nm structures onto quartz S-FIL templates. The presence of XeF₂ considerably enhances the etching rate of quartz without any significant negative effects on the spatial resolution of the FIB lithographic process and reduces the template processing time.     

Material processing of dielectrics with temporally asymmetric shaped femtosecond laser pulses on the nanometer scale

Laser material processing of dielectrics with temporally asymmetric femtosecond laser pulses of identical fluence, spectrum, and statistical pulse duration is investigated experimentally. To that end single shot structures at the surface of fused silica as a function of fluence and pulse shape are analyzed with the help of scanning electron microscopy. Structures for the bandwidth limited pulses show the known expansion in structure size with increasing laser fluence approaching the diffraction limit, which is 1.4 μm for the 0.5NA microscope objective used. In contrast, structures from the asymmetric pulses are remarkably stable with respect to variations in laser fluence and stay below 300 nm despite doubling the fluence. Different thresholds for surface material modification with respect to an asymmetric pulse and its time reversed counterpart are attributed to control of different ionization processes.     

Laser ablation of gadolinium targets in liquids for nanoparticle preparation

Tight focusing of a sub-picosecond laser pulse in a transparent dielectric provides a mean for localized deposition and plasma formation. A micro-explosion in a confined geometry results in a sub-micron cavity formation. Our numerical simulations show the cavity size is strongly dependent on the parameters of the equation of state such as the Grüneisen coefficient or the latent heat of sublimation. A comparison of numerical simulations with experimental data should allow a tuning of equations of state in the domain of extreme parameters     

Spatial characterization of the laser-induced plasma plumes generated by IR CO2 pulsed laser on carbon targets

We have used ferrocene and paraffin wax as novel precursor and solvent for the growth of iron oxide nanoparticles. The proposed method of growth has several advantages over existing methods of growth using iron pentacarbonyl a precursor. Highly crystalline and monodispersed particles are obtained which assemble in two- and three-dimensional hexagonal closed packed superlattices. Growth kinetics has been studied by varying concentration of the precursor and time of growth. A phenomenological model has been proposed to explain the growth kinetics.     

Submicrometer-MOS capacitor with ultra high capacitance biased by Au nanoelectrodes

The ultimate limits of size of the current metal-oxide-semiconductor capacitors can be overcome by preparation of three-dimensional devices that can vertically be biased using one-dimensional metal nanostructures. Here, we present a general and efficient approach to the assembly and integration of Au nanocrystals into functional nanoelectrodes of three-dimensional submicrometer-MOS (0.35 μm²) capacitors, presenting an ultra high capacitance (24±1 pF). The Au nanocrystals were directly produced into a nanoporous template of anodized aluminum oxide that was evaluated, and the electrical characterization of this device corroborates the formation of the MOS capacitor. Flat band voltage is independent of sweep voltage range, and negligible hysteresis of capacitance-voltage curves is observed when sweep voltage ranges from positive to negative and turned again to positive bias. In addition, experimental results match theoretical analysis and indicate the presence of free surface charges stored in the Au nanostructures. The demonstrated ability to control the assembling of the nanocrystals and the results of electrical characterization indicate that the embedded Au nanoelectrodes have a high potential for memory applications based on three-dimensional devices.     

Inverse pulsed laser deposition

Since the advent of pulsed laser deposition (PLD), several different target-substrate arrangements have been proposed. Besides the most common on-axis PLD, several off-axis geometries were studied, mainly to protect the substrate from the agglomerated species (clusters, droplets, particulates) of the plasma plume, which are detrimental to the homogeneity of films. Recently we introduced a novel geometry, termed inverse pulsed laser deposition (IPLD), in which the substrate is placed parallel to and slightly above the target plane. In this paper we summarize our results on this new geometry, and show how it can extend the perspectives of pulsed laser deposition, e.g., by improving the surface morphology of the films. Effects of ambient pressure are presented and exemplified on metallic and compound IPLD films, including Ti, CN _x , and Ti-oxides. AFM topographic images are used to prove that under optimized conditions IPLD is capable of growing compact and smooth films that are superior to PLD ones. A special—but easy-to-implement—IPLD arrangement is also introduced that considerably improves the homogeneity of IPLD films. In this geometry, the properties (e.g., deposition rate and roughness) of the films grown in the 1–25 Pa pressure domain are examined.     

Dye-sensitized solar cells based on TiO2 nanotube/porous layer mixed morphology

Titania porous layer has been fabricated on titania nanotubes for dye sensitized solar cells and the photovoltaic performance of solar cells with mixed morphology has been investigated. The porous layer results in a similar improvement in the short circuit current density to conventional TiCl₄ treatment, although the mechanisms responsible for the observed increase in the efficiency are different. This enables further improvements of the photovoltaic performance by combining the TiCl₄ treatment and porous layer deposition, so that the efficiency in the case of ∼5 μm long tubes increases on average from ∼1.6 to ∼2.2%.