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.     

Formation of surface stabilized Si nanocrystal by pulsed laser ablation in hydrogen gas

We prepared silicon nanocrystallites by pulsed laser ablation (PLA) of a Si target in hydrogen background gas. A mixture of hydrogen and helium was used as a background gas and the hydrogen partial pressure was varied. The deposited nanocrystal-film system shows a hierarchical structure composed of surface hydrogenated silicon nanocrystallites as the primary structure and aggregates of the nanocrystallites as the secondary structure. The size of the primary particles was not sensitive to the hydrogen partial pressure, while the porosity of the secondary structure constituted by the aggregation of the primary particles increased with increasing hydrogen partial pressure. This indicates that the surface is stabilized and that aggregation of the primary structure is depressed by surface hydrogenation. The optical gap energy of the deposits shifted to higher energy with increasing hydrogen partial pressure due to the formation of well-isolated nanocrystallites by surface stabilization. These results indicate that PLA in hydrogen gas is a promising technique to prepare surface stabilized and controlled silicon nanocrystallites.     

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.     

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.     

CdSe &; ZnS core/shell nanoparticles generated by laser ablation of microparticles

Laser Ablation of Microparticles (LAM) is a process of nanoparticle formation in which microparticles in a flowing aerosol are continuously ablated by high-power laser pulses. For the first time, we have produced CdSe/ZnS core/shell nanoparticles using a double ablation apparatus, designed to undergo a two-step LAM process. This process can be inverted to produce ZnS/CdSe core/shell nanoparticles. The present work focuses on the range around ∼15 nm radius heterostructures and uses high-resolution transmission electron microscopy (HRTEM) to image core and shells. For smaller particles, core shell structures have been detected with energy dispersive spectroscopy (EDS) 5 nm spot size beam and fast Fourier transform (FFT) spectra. Differences in the ablation behavior were measured between the two IIB–VIA type semiconductors.     

Zinc oxide nanostructures grown by pulsed laser deposition

We report the use of PLD to grow different ZnO nanostructures. Very different film morphologies have been observed using different laser wavelengths to ablate the target. The influence of substrate temperature and oxygen background pressure on the film morphology has been investigated too. Smooth and rough films, hexagonal pyramids and columns have been obtained by using a KrF excimer laser (248 nm) for the target ablation, while hexagonal hierarchical structures and pencils have been obtained by using ArF (193 nm). Photoluminescence and X-ray diffraction measurements revealed the good quality of the samples, in particular of those deposited using the ArF laser beam.     

Electroluminescence from ZnO nanowire-based p-GaN/n-ZnO heterojunction light-emitting diodes

Vertically aligned ZnO nanowires were successfully grown on the sapphire substrate by nanoparticle-assisted pulsed laser deposition (NAPLD), which were employed in fabricating the ZnO nanowire-based heterojunction structures. p-GaN/n-ZnO heterojunction light-emitting diodes (LEDs) with embedded ZnO nanowires were obtained by fabricating p-GaN:Mg film/ZnO nanowire/n-ZnO film structures. The current–voltage measurements showed a typical diode characteristic with a threshold voltage of about 2.5 V. Electroluminescence (EL) emission having the wavelength of about 380 nm was observed under forward bias in the heterojunction diodes and was intensified by increasing the applied voltage up to 30 V.     

Anatase TiO2 films fabricated by pulsed laser deposition using Ti target

TiO₂ films were prepared by pulsed laser deposition using a metallic Ti target in an O₂ gas ambient. The microstructure along with optical and photocatalytic properties of the deposited films were systematically studied by changing the deposition parameters and substrates. It was found that TiO₂ films having nearly pure anatase phase grew effectively in O₂ atmosphere. When the films were fabricated at a substrate temperature of 400°C, their phase structures were greatly affected by the O₂ gas pressure, and nearly pure anatase phase with typical (101) and (004) peaks can be obtained under an O₂ pressure of 15 Pa. For the deposition at 700°C, the crystal structure of the TiO₂ films exhibited a strong anatase (004) peak and was inert to the oxygen pressures. Two modes, namely a substrate-temperature-controlled mode and an oxygen-pressure-controlled mode, were considered for the growth of the anatase TiO₂ films under different substrate temperatures. In addition, the optical and photocatalytic properties were found to be sensitive to both the microstructure and grain size of the TiO₂ films.     

Incubation in the UV irradiation of condensed CHCl<Subscript>3</Subscript> solids

Matrix-Assisted-Pulsed-Laser-Evaporation (MAPLE) has emerged as a very promising technique for the deposition of polymers and biopolymers in intact and functional form. However, our understanding of the mechanism of the procedure is still limited. Here, we examine laser-induced (248 nm) desorption from condensed CHCl₃ solid, which has been employed as a potential matrix in MAPLE. We find that the absorption of the condensed halocarbon increases significantly with successive laser pulses, as a result of the formation and accumulation of strongly absorbing products. This results in a significant increase of the ejection efficiency in the irradiation with successive laser pulses. Thus, in studies employing multi-pulse irradiation protocols, the attained laser-induced temperatures are considerably higher than what is estimated on the basis of the absorption coefficient of CHCl₃. Thus, contrary to previous suggestions, ablation of CHCl₃ frozen solid at 248 nm may be due to explosive boiling. A number of additional implications are also discussed.     

Thin SiC<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> layers prepared by hybrid laser–magnetron deposition

Thin SiC _x films were fabricated by hybrid laser–magnetron deposition system. KrF excimer laser was used for deposition of carbon and magnetron at the same time for sputtering of Si species. Films were fabricated in argon/hydrogen ambient with and without additional RF discharge. The substrate temperature was changed up to 700°C. Films topology, crystallinity, composition, chemical bonds and optical emission spectra were studied. Films were smooth and amorphous. Films of thickness 400–1000 nm were fabricated. Adhesion moved from 8 to 14 N, depending on deposition conditions.     

Thickness distribution of thin amorphous chalcogenide films prepared by pulsed laser deposition

Amorphous chalcogenide thin films were prepared from As₂Se₃, As₃Se₂ and InSe bulk glasses by pulsed laser deposition using a KrF excimer laser. Thickness profiles of the films were determined using variable angle spectroscopic ellipsometry. The influence of the laser beam scanning process during the deposition on the thickness distribution of the prepared thin films was evaluated and the corresponding equations suggested. The results were compared with experimental data.     

Growth of ZnO nanoparticles and nanorods with ultrafast pulsed laser deposition

In this work, we study the application of ultrafast pulsed laser deposition (PLD) in ZnO nanomaterial synthesis, including nanoparticles and nanorods. PLD using long pulse (nanosecond) lasers has been widely used as a method for growing prototype materials. The recently-emerged ultrafast PLD is expected to be able to overcome the problem of large liquid droplet formation. Using near infrared and femtosecond laser pulses in ablation, we first characterize the ablation plume using a Langmuir probe and plasma optical emission spectroscopy. We then examine the structural properties of the nanoparticles generated during low-fluence ablation. Finally, we demonstrate that using nanoparticle aggregates as templates, assisted by plume-excited nitrogen radicals at a high fluence, high quality ZnO nanorods can be grown free of metal catalysts.     

Improvement of electrical properties of silicon-based thin-film transistors by modifying technological fabrication processes

This paper is a review of technological process evolution associated to electrical performance improvement of silicon-based thin-film transistors (TFTs) that were performed mainly in the GM/IETR laboratory. The main objective in agreement with the fields of applications is to fabricate TFTs at a temperature low enough to be compatible with the substrates, glass substrates in a first place and flexible substrates in a second one, which implies several approaches. In fact, the electrical properties of the TFTs, mainly field-effect mobility of carriers in the channel, I _on/I _off drain current ratio, and subthreshold slope, are strongly dependent on the quality and the nature of the channel material, on the material quality and thus on the density of states at the interface with the gate insulator, and on the quality of the gate insulator itself. All the improvements are directly linked to all these aspects, which means an actual combination of the efforts. For the glass substrate, compatible technology processes such as deposition techniques, or solid phase, or laser crystallizations of active layers were studied and compared. The paper details all these approaches and electrical performances. In addition, some results about the use of a silicon–germanium compound as channel active layer and airgap transistors for which the insulator is released, complete the presentation of the evolution of the silicon-based TFTs during the last twenty years.     

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.     

Microstructure and electrical conductivity of YSZ thin films prepared by pulsed laser deposition

Yttria-stabilized zirconia (YSZ) is the most common solid electrolyte material used e.g. in ceramic fuel cells. Thin films of YSZ were deposited on c-cut sapphire single crystals by pulsed laser deposition using a KrF excimer laser focused on a polycrystalline 8 mol% Y₂O₃-stabilized ZrO₂ target. Depending on the substrate temperature and the oxygen background pressure during deposition, different microstructures are obtained. XRD and high-resolution SEM revealed the formation of dense amorphous films at room temperature. At 600°C preferentially (111) oriented polycrystalline films consisting of densely agglomerated nm-sized grains of the cubic phase resulted. Grain size and surface roughness could be controlled by varying the oxygen background pressure. RBS and PIXE evidenced congruent transfer only for a low number of pulses, indicating a dynamical change of the target stoichiometry during laser irradiation. The in-plane ionic conductivity of the as-deposited crystalline films was comparable to bulk YSZ. The conductivity of initially amorphous YSZ passes a maximum during the crystallization process. However, the relative changes remain small, i.e. no significant enhancement of ionic conductivity related to the formation of a nanocrystalline microstructure is found.     

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.     

SBN thin films growth by RF plasma beam assisted pulsed laser deposition

SBN thin films were grown on MgO and Silicon substrates by PLD and RF-PLD (radiofrequency assisted PLD) starting from single crystal Sr_0.6Ba_0.4Nb₂O₆ and ceramic Sr_0.5Ba_0.5Nb₂O₆ stoichiometric targets. Morphological and structural analyses were performed on the SBN layers by AFM and XRD and optical properties were measured by spectroellipsometry. The films composition was determined by Rutherford Backscattering Spectrometry. The best set of experimental conditions for obtaining crystalline, c-axis preferential texture and with dominant 31° in-plane orientation relative to the MgO (100) axis is identified.     

Characteristics of ZnO epilayer on the post-annealed buffer layer on GaN/sapphire substrate by pulsed laser deposition

We employed epi-GaN substrates for ZnO film growth, and studied the deposition and post-annealing effects. ZnO films were grown by pulsed laser deposition (PLD) method. The as-grown films were annealed for one hour under atmospheric pressure air. ZnO morphologies after annealing were investigated and the post-annealed ZnO films grown at T _g =700^oC have very smooth surfaces and the rms with roughness is about 0.5 nm. Finally, ZnO post-annealed buffer layer was inserted between ZnO epilayer and GaN/sapphire substrates. It is confirmed by AFM that growth temperature of 700^oC helps the films grow in step-flow growth mode. It is observed by cathode luminescence spectrum that the ZnO film grown at 700^oC has very low visible luminescence, indicating the decrease of the deep level defects. It is also revealed by Hall measurements that carrier concentration is decreased by increasing the growth temperatures. It is suggested that low temperature buffer layer growth and post-annealing technique can be used to fabricate ZnO hetero-epitaxy.     

Growth regimes in pulsed laser deposition of aluminum oxide films

Alumina is technologically exploited in several forms, ranging from compact hard films as protective coatings to open microstructures of high specific area as supports for catalysts. Currently, various production processes are used to deposit the different forms. PLD has the potential of obtaining not only the different forms, but also a continuous modulation of properties, by tuning of the process parameters. This work investigates the relationship between the process parameters and the resulting film morphology, structure and properties for PLD performed with an alumina target in a background oxygen atmosphere. Three distinct growth regimes are found, leading, respectively, to compact homogeneous films, columnar structures and open microstructures. These structures are quantitatively characterized, and the ranges of the process parameters corresponding to the three regimes are identified. An empirical scaling law is proposed, which can be exploited as a guide for the design of growth processes aimed at obtaining specific film properties.     

Pulsed laser CVD investigations of single-wall carbon nanotube growth dynamics

The nucleation and rapid growth of single-wall carbon nanotubes (SWNTs) were explored by pulsed-laser assisted chemical vapor deposition (PLA-CVD). A special high-power, Nd:YAG laser system with tunable pulse width (>0.5 ms) was implemented to rapidly heat (>3×10⁴°C/s) metal catalyst-covered substrates to different growth temperatures for very brief (sub-second) and controlled time periods as measured by in situ optical pyrometry. Utilizing growth directly on transmission electron microscopy grids, exclusively SWNTs were found to grow under rapid heating conditions, with a minimum nucleation time of >0.1 s. By measuring the length of nanotubes grown by single laser pulses, extremely fast growth rates (up to 100 microns/s) were found to result from the rapid heating and cooling induced by the laser treatment. Subsequent laser pulses were found not to incrementally continue the growth of these nanotubes, but instead activate previously inactive catalyst nanoparticles to grow new nanotubes. Localized growth of nanotubes with variable density was demonstrated through this process and was applied for the reliable direct-write synthesis of SWNTs onto pre-patterned, catalyst-covered metal electrodes for the synthesis of SWNT field-effect transistors.