Large-scale synthesis of In2O3 nanowires

In₂O₃ nanowires have been successfully fabricated on a large scale from indium particles by thermal evaporation at 1030 °C. The as-synthesized products were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). SEM and TEM images show that these nanowires are uniform with diameters of about 60–120 nm and lengths of about 15–25 μm. XRD and selected-area electron diffraction analysis together indicate that these In₂O₃ nanowires crystallize in a cubic structure of the bixbyite Mn₂O₃ (I) type (also called the C-type rare-earth oxide structure). The growth mechanism of these nanowires is also discussed. Received: 29 June 2001 / Accepted: 28 September 2001 / Published online: 20 December 2001     

Large-scale synthesis of SnO2 nanobelts

Tin dioxide (SnO₂) nanobelts have been successfully synthesized in bulk quantity by a simple and low-cost process based on the thermal evaporation of tin powders at 800 °C. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations reveal that the nanobelts are uniform, with lengths from several-hundred micrometers to a few millimeters, widths of 60 to 250 nm and thicknesses of 10 to 30 nm. X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX) and selected-area electron diffraction analysis (SAED) indicate that the nanobelts are tetragonal rutile structure of SnO₂. The SnO₂ nanobelts grow via a vapor–solid (VS) process. Received: 3 June 2002 / Accepted: 10 June 2002 / Published online: 10 September 2002 RID="*" ID="*"Corresponding author. Fax: +86-551/559-1434, E-mail: gwmeng@mail.issp.ac.cn     

Optical extinction resonance of Au and Ag clusters formed by ion irradiation in SiO2 and Al2O3

Three methods based on ion-beam irradiation were used to fabricate Ag and Au colloids in silica and alumina. Their surface-plasmon resonance in the visible was characterised by transmittance measurements and interpreted on the basis of transmission electron microscope observations. Despite their bimodal size distribution, particles formed by ion-beam mixing of sandwich layers exhibit much narrower resonances than those obtained by ion implantation. This unusual effect of an inhomogeneity in cluster size is ascribed to the spatial organisation of these clusters. Irradiation of supersaturated solid solutions at much lower ion fluences produces colloids with more uniform size and spatial distributions, and equally strong resonances. Received: 17 March 2001 / Accepted: 31 July 2001 / Published online: 11 February 2002     

Synthesis and photoluminescence characteristics of doped ZnS nanoparticles

Free-standing powders of doped ZnS nanoparticles have been synthesized by using a chemical co-precipitation of Zn²⁺, Mn²⁺, Cu²⁺ and Cd²⁺ with sulfur ions in aqueous solution. X-ray diffraction analysis shows that the diameter of the particles is ∼2–3 nm. The unique luminescence properties, such as the strength (its intensity is about 12 times that of ZnS nanoparticles) and stability of the visible-light emission, were observed from ZnS nanoparticles co-doped with Cu²⁺ and Mn²⁺. The nanoparticles could be doped with copper and manganese during the synthesis without altering the X-ray diffraction pattern. However, doping shifts the luminescence to 520–540 nm in the case of co-doping with Cu²⁺ and Mn²⁺. Doping also results in a blue shift on the excitation wavelength. In Cd²⁺-doped ZnS nanometer-scale particles, the fluorescence spectra show a red shift in the emission wavelength (ranging from 450 nm to 620 nm). Also a relatively broad emission (ranging from blue to yellow) has been observed. The results strongly suggest that doped ZnS nanocrystals, especially two kinds of transition metal-activated ZnS nanoparticles, form a new class of luminescent materials. Received: 16 October 2000 / Accepted: 17 October 2000 / Published online: 23 May 2001     

Formation of Cu nanoparticles in GaAs using MeV ion implantation followed by thermal annealing

Analytical electron microscopy, high-resolution X-ray diffraction and combined Rutherford backscattering spectrometry and channeling experiments have been used to investigate the radiation damage and the effect of post-implantation annealing on the microstructure of GaAs(100) single crystals implanted with 1.00 MeV Cu⁺ ions to a dose of ≈ 3×10¹⁶ cm^-2 at room temperature. The experiments reveal the formation of a thick and continuous amorphous layer in the as-implanted state. Annealing up to 600 °C for 60 min does not result in the complete recovery of the lattice order. The residual disorder in GaAs has been found to be mostly microtwins and stacking fault bundles. The redistribution of implanted atoms during annealing results in the formation of nano-sized Cu particles in the GaAs matrix. The X-ray diffraction result shows a cube-on-cube orientation of the Cu particles with the GaAs lattice. The depth distribution and size of the Cu particles have been determined from the experimental data. A tentative explanation for these results is presented. Received: 15 February 1999 / Accepted: 18 February 1999 / Published online: 28 April 1999     

Photoinduced transformations and holographic recording in nanolayered a-Se/As2S3 and AsSe/As2S3 films

Received: 13 October 1998 / Accepted: 9 December 1998 / Published online: 24 February 1999     

Excimer laser ablation of gold-loaded inverse polystyrene-block-poly (2-vinylpyridine) micelles

Diblock-copolymers (PS(1700)-b-P2VP(450) or PS(1350)-b-P2VP(400)) forming spherical micelles, can be loaded with a Au-salt and deposited on top of various substrates. Such polymer films have been exposed to a pulsed ArF excimer laser in order to remove the polymer matrix and, in parallel, to chemically reduce the salt into metallic Au nanodots. To analyze this process in detail, it was subdivided into three steps: (a) laser ablation of thick and thin diblock-copolymer films; (b) laser irradiation of Au-salt loaded diblock-copolymer films; and (c) laser irradiation of arrays of metallic Au nanodots. In (a) it was found that a complete removal of the polymer by laser ablation is only possible in air under ambient conditions while identical laser irradiations under vacuum result in a residual layer of approximately 14 nm. Substep (b) revealed a nucleation process of the resulting metallic Au within the micellar core leading to clusters of small Au dots. Furthermore, this substep provided evidence for an asymmetric interplay between the macroscopic temperature of a polymer film during laser treatment and the energy density per laser pulse. In (c) it could be demonstrated that metallic Au nanodots on mica are stable against laser irradiation under conditions leading to a polymer removal. Received: 7 August 2000 / Accepted: 2 November 2000 / Published online: 3 April 2001     

Artificially nanostructured Cu:Al2O3 films produced by pulsed laser deposition

The processes leading to the formation of Cu:Al₂O₃ composite films on Si (001) with a well defined nanostructure by alternate pulsed laser deposition (a-PLD) in vacuum are investigated. Alternately amorphous Al₂O₃ layers and Cu nanocrystals nucleated on the Al₂O₃ surface are formed, according to the PLD sequence. The Al₂O₃ deposited on the Cu nanocrystals fills in the space between them until they are completely buried, and subsequently, a continuous dense layer with a very flat surface (within 1 nm) is developed. The nucleation process of the nanocrystals and their resulting oblate ellipsoidal shape are discussed in terms of the role of the energetic species involved in the PLD process and the metal–oxide interface energy. Received: 4 July 2000 / Accepted: 5 July 2000 / Published online: 13 September 2000     

Photoluminescence characteristics of ZnS nanocrystallites doped with Ti3+and Ti4+

Direct synthesis of ZnS nanocrystallites doped with Ti³⁺ or Ti⁴⁺ by precipitation has led to novel photoluminescence properties. Detailed X-ray diffraction (XRD), fluorescence spectrophotometry, UV–vis spectrophotometry and X-ray photoelectron spectroscopy (XPS) analysis reveal the crystal lattice structure, average size, emission spectra, absorption spectra and composition. The average crystallite size doped with different mole ratios, estimated from the Debye–Scherrer formula, is about 2.6±0.2 nm. The nanoparticles can be doped with Ti³⁺ and Ti⁴⁺ during the synthesis without the X-ray diffraction pattern being altered. The strong and stable visible-light emission has been observed from ZnS nanocrystallites doped with Ti³⁺ (its maximum fluorescence intensity is about twice that of undoped ZnS nanoparticles). However, the fluorescence intensity of the ZnS nanocrystallites doped with Ti⁴⁺ is almost the same as that of the undoped ZnS nanoparticles. The emission peak of the undoped sample is at 440–450 nm. The emission spectrum of the doped sample consists of two emission peaks, one at 420–430 nm and the other at 510 nm. Received: 27 April 2001 / Accepted: 16 August 2001 / Published online: 17 October 2001     

Fabrication and characterization of In2O3 nanowires

In₂O₃ nanowires were successfully fabricated through a simple gas-reaction route in argon atmosphere. These nanowires have diameters ranging from 20 nm to 50 nm and lengths up to tens of micrometers. High-resolution transmission electron microscopy observations and the electron-diffraction (ED) pattern reveal that the In₂O₃ nanowires are formed by the stacking of (2) planes along the [1] direction, which is parallel to the wire axis. A strong and wide ultraviolet (UV) emission band centered at around 392 nm is observed for the first time in the room-temperature photoluminescence measurement in addition to the usual blue emission (468 nm). Moreover, five discrete fine peaks (372 nm, 383 nm, 406 nm, 392 nm and 413 nm) are further identified in this broad UV band. Received: 10 April 2002 / Accepted: 12 April 2002 / Published online: 19 July 2002     

Strong green luminescence of Ni2+-doped ZnS nanocrystals

ZnS nanoparticles doped with Ni²⁺ have been obtained by chemical co-precipitation from homogeneous solutions of zinc and nickel salt compounds, with S^2- as precipitating anion, formed by decomposition of thioacetamide (TAA). The average size of particles doped with different mole ratios, estimated from the Debye–Scherrer formula, is about 2–2.5 nm. The nanoparticles could be doped with nickel during synthesis without altering the X-ray diffraction pattern. A Hitachi M-850 fluorescence spectrophotometer reveals the emission spectra of samples. The absorption spectra show that the excitation spectra of Ni-doped ZnS nanocrystallites are almost the same as those of pure ZnS nanocrystallites (λ_ex=308–310 nm). Because a Ni²⁺ luminescent center is formed in ZnS nanocrystallites, the photoluminescence intensity increases with the amount of ZnS nanoparticles doped with Ni²⁺. Stronger and stable green-light emission (520 nm) (its intensity is about two times that of pure ZnS nanoparticles) has been observed from ZnS nanoparticles doped with Ni²⁺. Received: 18 December 2000 / Accepted: 17 March 2001 / Published online: 20 June 2001     

MeV Al+ and Al2+ ions implantation in Si(100): surface roughness and defects in the bulk

This paper deals with the implantation of high-energy (1.0–3.0 MeV) atomic and molecular Al⁺ ions in Si(100) to a fluence of 5×10¹⁴ Al atoms/cm² at room temperature. The molecular effect, i.e. the increase of the displacement yield compared with the sum of the atomic yields, and the damage formation as well as defect behaviour after annealing have been investigated. A detailed experimental study has been made of the evolution of extended secondary defects which form during thermal anneals of Al⁺ or Al₂ ⁺ irradiated silicon. The samples have been examined using combined Rutherford backscattering and channeling experiments together with transmission electron microscopy observations. The surface structure of the implanted wafers has been measured by atomic force microscopy. The results for the implantation-induced roughness at the Si surface, resulting from Al⁺ or Al₂ ⁺ irradiation at the same energy/atom, total atomic fluence, flux rate, and irradiation temperature, are presented and discussed. Received: 19 August 1999 / Accepted: 20 October 1999 / Published online: 23 February 2000     

Efficient submicron processing of metals with femtosecond UV pulses

The generation of submicron-sized holes on metal surfaces by applying femtosecond UV laser pulses was investigated. Different optical schemes based on a Schwarzschild-type reflective objective were used to reach optimized ablation quality and efficiency in different applications (hole ablation, through-hole drilling, generation of surface patterns consisting of holes, etc.). Submicron-sized holes and hole patterns were ablated onto metal surfaces and drilled through ∼5-μm-thick steel foils with 600-nm diameter on the output side. Using a special optical interferometric method, large-area surface processing of high-conductivity materials in the submicron regime was performed. Combining these techniques with the application of high-repetition-rate ultra-short UV laser sources, large-area sub-μm processing of all kinds of materials in industrial environments is possible. Received: 28 February 2002 / Accepted: 12 March 2002 / Published online: 25 October 2002 RID="*" ID="*"Corresponding author. Fax: +49-551/503599, E-mail: psimon@llg.gwdg.de     

Template synthesis of single-crystal Cu nanowire arrays by electrodeposition

Cu nanowire arrays have been synthesized using potentiostatic electrodeposition within the confined nanochannels of a porous anodic alumina membrane. The Cu nanowire arrays and the individual nanowires have been characterized using SEM, TEM, SAED, HREM and XRD. Investigation results reveal that the Cu nanowire arrays having high wire packing densities are highly ordered over large areas. The individual Cu nanowires (diameter ∼60 nm) were single-crystal and found to be dense and continuous with uniform diameters throughout their entire length. An optimum ECD condition (at lower overpotentials) for the synthesis of single-crystal Cu nanowires was also discussed. Received: 19 April 2001 / Accepted: 28 April 2001 / Published online: 20 June 2001     

Laser–MBE growth of high-quality ZnO thin films on Al2O3(0001) and SiO2/Si(100) using the third harmonics of a Nd:YAG laser

High-quality ZnO thin films were grown on single-crystalline Al₂O₃(0001) and amorphous SiO₂/Si(100) substrates at 400–640 °C using laser molecular beam epitaxy. For film growth, the third harmonics of a pulsed Nd:YAG laser were illuminated on a ZnO target. The ZnO films were epitaxially grown on Al₂O₃(0001) with the narrow X-ray diffraction full width at half maximum (FWHM) of 0.04° and the films on SiO₂/Si(100) exhibited a preferred c-axis orientation. Furthermore, the films exhibited excellent optical properties in photoluminescence (PL) measurements with very sharp excitonic and weak deep-level emission peaks. At 15 K, PL FWHM values of the films grown on Al₂O₃(0001) and SiO₂/Si(100) were 3 and 18 meV, respectively. Received: 8 May 2001 / Accepted: 18 September 2001 / Published online: 20 December 2001     

Luminescence from copper nanoparticles

The presence of copper nanoparticles in alumina and silica modifies their luminescence, and the changes in spectra are influenced by variations in the nanoparticle size distributions. Luminescence signals are sensitive to the total defect population. Thus the luminescence not only reflects changes caused by thermal annealing, which can modify both intrinsic defects and the copper nanoparticles, but also responds to the method of preparation of thin film layers. Copper nanoparticle influence on luminescence is reported both for ion-implanted bulk silica and for copper in pulsed laser deposition within alumina. Luminescence thus potentially offers a non-destructive monitor of the layer quality, reproducibility and growth conditions, as well as the state and size of the copper nanoparticles. Received: 29 June 2001 / Published online: 10 October 2001     

Effects of excimer-laser irradiation of LaAlO3(100) single crystals: Influence on superconducting YBa2Cu3O7-x film growth

3 (100) single crystal substrates have been investigated. Poorly absorbed KrF irradiation leads to localized, deep, and unstable damage on the crystal surfaces. By contrast ArF has been found to induce well-localized roughness and microcracks on LaAlO₃(100) surfaces at fluences between 0.2 and 1.8 J/cm². The material emission threshold was estimated at around 0.5 J/cm² and cracks appeared above 1.4 J/cm². The substrate surface state determines YBa₂Cu₃O_7-x film growth, leading to morphological changes that have been related to a decrease in adatom mobility on the substrate. The most striking feature is the drastic reduction in YBa₂Cu₃O_7-x outgrowth density inside the irradiated areas. Irradiation has little effect on film crystalline properties. The main effect on the electrical properties can be restricted to a decrease of critical current density up to a factor of 10⁴, but such an important decrease is only observed in the most intensively irradiated substrates. Received: 18 November 1996/Accepted: 12 June 1997     

Microstructural analyses of the nanoparticles obtained after laser irradiation of Ti and W in ethanol

The laser ablation technique has been employed to prepare titanium (Ti) and tungsten (W) colloids from the elemental solids in ethanol using a copper-hydrogen bromide (CuHBr) vapour laser. The obtained nanoparticles were spherical with most diameters ranging from 0.05 to 0.5 μm. Some particles, notably when using Ti targets, are bigger than 0.9 μm, indicating resolidification of liquid droplets. The mechanism of material removal was characterized by photo-ablation where some particles were generated by rapid solidification from the melt. The W particles had tendency to coalescence, since small clusters merge to larger spheres. On the other hand, the Ti particles were coalescence-free, perhaps due to the thin high-resistant oxide layer at their surface.     

Study of UV laser interaction with gold nanoparticles embedded in silica

In order to resolve problems concerning the understanding and the control of laser-induced damage of silica optical elements, a collaboration between the CEA and different university laboratories has been undertaken. Ultra-pure silica model samples, seeded with gold nanoparticles whose diameter did not exceed 5 nm, were prepared. The aim in using these samples was to observe the mechanism of damage initiation that could be attributed to inclusions of nanometric size. This paper presents the different steps encountered during this study: preparation of the samples, the laser-induced damage tests, the Nomarski and atomic-force microscope observations of this damage and a series of experiments using a time-of-flight mass spectrometer at Argonne National Laboratory. The experimental data are then interpreted, and, in particular, compared to numerical simulations. A very encouraging result is the existence of a pre-damage phase at very low fluences that is not detectable by classical optical devices. The experimental means developed for such model samples should be transposable to the analysis of industrial glasses. Received: 19 July 2002 / Revised version: 23 September 2002 / Published online: 11 December 2002 RID="*" ID="*"Corresponding author. Fax: +33-1/6926-7106, E-mail: florian.bonneau@cea.fr     

Hydrothermal synthesis of novel sandwich-like structured ZnS/octylamine hybrid nanosheets

Novel sandwich-like structured zinc sulfide (ZnS)/octylamine (OA) hybrid nanosheets with exclusively sheet-like morphology were synthesized for the first time via a mild hydrothermal route using OA as structure-directing agent. The as-synthesized products were characterized by the X-ray diffraction, transmission electron microscopy, scan electron microscopy, energy dispersive analyses of X-rays, thermogravimetric analysis, and ultraviolet and visible absorption spectroscopy. The results showed that OA molecules were intercalated between wurtzite ZnS layers. As revealed from optical absorption measurements, the hybrid nanosheets exhibits strong quantum confinement effect with a great blue shift in the band gap.