Intense infrared luminescence in transparent glass-ceramics containing beta-Ga2O3 : Ni2+ nanocrystals

Transparent glass-ceramics containing beta-Ga2O3:Ni2+ nanocrystals were synthesized and characterized by X-ray diffraction, transmission electron microscopy, and electron energy loss spectroscopy. Intense broad-band luminescence centering at 1200 nm was observed when the sample was excited by a diode laser at 980 nm. The room-temperature fluorescent lifetime was 665 mu s, which is longer than the Ni2+-doped ZnAl2O4 and LiGa5O8 glass-ceramics and is also comparable to the Ni2+-doped LiGa5O8 single crystal. The intense infrared luminescence with long fluorescent lifetime may be ascribed to the high crystal field hold by Ni2+ and the moderate lattice phonon energy of beta-Ga2O3. The excellent optical properties of this novel material indicate that it might be a promising candidate for broad-band amplifiers and room-temperature tunable lasers.

Precipitation of Ge nanoparticles from GeO2 glasses in transmission electron microscope

We show, using spatially resolved energy loss spectroscopy in a transmission electron microscopy (TEM), that GeO2 and GeO2-SiO2 glasses are extremely sensitive to high energy electrons. Ge nanoparticles can be precipitated in GeO2 glasses efficiently by the high-energy electron beam of a TEM. This is relevant to TEM characterization of luminescent Ge nanoparticles in silicate glasses, which may produce artificial results. (C) 2005 American Institute of Physics.

Optical and electronic properties of amorphous diamond

The optical and electronic properties of highly tetrahedral amorphous diamond-like carbon (amorphous diamond, a-D) films were investigated. The structure of the films grown on silicon and glass substrates, under similar deposition conditions using a compact filtered cathodic vacuum arc system, are compared using electron energy loss spectroscopy (EELS). Results from hydrogenation of the films are also reported. The hydrogenated films show two prominent IR absorption peaks centered at 2920 and 2840 cm-1, which are assigned to the stretch mode of the C-H bond in the sp3 configuration on the C-H3 and C-H sites respectively. The high loss EELS spectra show no reduction in the high sp3 content in the hydrogenated films. UV and visible transmission spectra of a-D thin films are also presented. The optical band gap of 2.0-2.2 eV for the a-D films is found to be consistent with the electronic bandgap. The relationship between the intrinsic compressive stress in the films and the refractive index is also presented. The space charge limited current flow is analyzed and coupled with the optical absorption data to give an estimate of 1018 cm-3 eV-1 for the valence band edge density of states.

Effect of deposition conditions on the chemical bonding in sputtered carbon nitride films

A balanced planar r.f. powered magnetron sputter source has been used to deposit carbon nitride films from a graphite target under various conditions. Sample temperature, bias voltage and nitrogen content in the gas mixture were varied. The effects of oxygen, methane and ammonia on the film growth were also studied. Special attention was paid to the effects of the deposition parameters on the structure of the films, in particular the hybridisation of the carbon and nitrogen bonding. The chemical bonding of the carbon and nitrogen atoms was studied by electron energy loss spectroscopy (EELS). The chemical composition was evaluated by Rutherford back-scattering. The intensity of transitions to π antibonding orbitals, as revealed by EELS, was found to increase with the nitrogen content in the films. Ion bombardment of the films during growth and the addition of oxygen or hydrogen-rich gases further increased the proportion of π bonds of both the carbon and nitrogen atoms. It is suggested that the increase in the transitions to μ antibond orbitals is to be explained by increased sp2 or possibly sp hybridisation of the carbon and nitrogen. Also, the effect of annealing on the bonding of nitrogen rich films after deposition was tested. The changes caused by nitrogen and deposition conditions are consistent with previous reports on the formation of paracyanogen structures.

Preparation of tetrahedral amorphous carbon films by filtered cathodic vacuum arc deposition

Tetrahedrally bonded amorphous carbon (ta-C) and nitrogen doped (ta-C:N) films were obtained at room temperature in a filtered cathodic vacuum arc (FCVA) system incorporating an off-plane double bend (S-bend) magnetic filter. The influence of the negative bias voltage applied to substrates (from -20 to -350 V) and the nitrogen background pressure (up to 10-3 Torr) on film properties was studied by scanning electron microscopy (SEM), electron energy loss spectroscopy (EELS), Raman spectroscopy, X-ray photoemission spectroscopy (XPS), secondary ion mass spectroscopy (SIMS) and X-ray reflectivity (XRR). The ta-C films showed sp3 fractions between 84% and 88%, and mass densities around 3.2 g/cm3 in the wide range of bias voltage studied. In contrast, the compressive stress showed a maximum value of 11 GPa for bias voltages around -90 V, whereas for lower and higher bias voltages the stress decreased to 6 GPa. As for the ta-C:N films grown at bias voltages below -200 V and with N contents up to 7%, it has been found that the N atoms were preferentially sp3 bonded to the carbon network with a reduction in stress below 8 GPa. Further increase in bias voltage or N content increased the sp2 fraction, leading to a reduction in film density to 2.7 g/cm3.

Properties of tetrahedral amorphous carbon prepared by vacuum arc deposition

The structural, optical, electrical and physical properties of amorphous carbon deposited from the filtered plasma stream of a vacuum arc were investigated. The structure was determined by electron diffraction, neutron diffraction and energy loss spectroscopy and the tetrahedral coordination of the material was confirmed. The measurements gave a nearest neighbour distance of 1.53 Å, a bond angle of 110 and a coordination number of four. A model is proposed in which the compressive stress generated in the film by energetic ion impact produces pressure and temperature conditions lying well inside the region of the carbon phase diagram within which diamond is stable. The model is confirmed by measurements of stress and plasmon energy as a function of ion energy. The model also predicts the formation of sp2-rich materials on the surface owing to stress relaxation and this is confirmed by a study of the surface plasmon energy. Some nuclear magnetic resonance, infrared and optical properties are reported and the behaviour of diodes using tetrahedral amorphous carbon is discussed. © 1991.

Microstructural evolution of SiOx films and its effect on the luminescence of Si nanoclusters

In this paper we demonstrate that the structural and optical properties of Si nanoclusters (Si ncs) formed by thermal annealing of SiOx films prepared by plasma enhanced chemical vapor deposition (PECVD) and magnetron sputtering are very different. In fact, at a fixed Si excess and annealing temperature, photoluminescence (PL) spectra of sputtered samples are redshifted with respect to PECVD samples, denoting a larger Si ncs size. In addition, PL intensity reaches a maximum in sputtered films at annealing temperatures much lower than those needed in PECVD films. These data are correlated with structural properties obtained by energy filtered transmission electron microscopy and electron energy loss spectroscopy. It is shown that in PECVD films only around 30% of the Si excess agglomerates in clusters while an almost complete agglomeration occurs in sputtered films. These data are explained on the basis of the different initial structural properties of the as-deposited films that become crucial for the subsequent evolution. © 2008 American Institute of Physics.

Microstructural and compositional characteristics of GaN films grown on a ZnO-buffered Si(111) wafer

Polycrystalline GaN thin films have been deposited epitaxially on a ZnO-buffered (111)-oriented Si substrate by molecular beam epitaxy. The microstructural and compositional characteristics of the films were studied by analytical transmission electron microscopy (TEM). A SiO2 amorphous layer about 3.5 nm in thickness between the Si/ZnO interface has been identified by means of spatially resolved electron energy loss spectroscopy. Cross-sectional and plan-view TEM investigations reveal (GaN/ZnO/SiO2/Si) layers exhibiting definite a crystallographic relationship: [111](Si)//[111](ZnO)//[0001](GaN) along the epitaxy direction. GaN films are polycrystalline with nanoscale grains (similar to100 nm in size) grown along [0001] direction with about 20degrees between the (1 (1) over bar 00) planes of adjacent grains. A three-dimensional growth mode for the buffer layer and the film is proposed to explain the formation of the as-grown polycrystalline GaN films and the functionality of the buffer layer. (C) 2004 Elsevier Ltd. All rights reserved.

Nucleation of diamond by pure carbon ion bombardment - a transmission electron microscopy study

A cross-sectional high-resolution transmission electron microscopy (HRTEM) study of a film deposited by a 1 keV mass-selected carbon ion beam onto silicon held at 800 degrees C is presented. Initially, a graphitic film with its basal planes perpendicular to the substrate is evolving. The precipitation of nanodiamond crystallites in upper layers is confirmed by HRTEM, selected area electron diffraction, and electron energy loss spectroscopy. The nucleation of diamond on graphitic edges as predicted by Lambrecht [W. R. L. Lambrecht, C. H. Lee, B. Segall, J. C. Angus, Z. Li, and M. Sunkara, Nature, 364 607 (1993)] is experimentally confirmed. The results are discussed in terms of our recent subplantation-based diamond nucleation model. (c) 2005 American Institute of Physics.

Diamond nucleation by energetic pure carbon bombardment

Deposition of 1000 eV pure carbon ions onto Si(001) held at 800 degrees C led to direct nucleation of diamond crystallites, as proven by high-resolution transmission electron microscopy and electron energy loss spectroscopy. Molecular dynamic simulations show that diamond nucleation in the absence of hydrogen can occur by precipitation of diamond clusters in a dense amorphous carbon matrix generated by subplantation. Once the diamond clusters are formed, they can grow by thermal annealing consuming carbon atoms from the amorphous matrix. The results are applicable to other materials as well.

Tentative analysis of Swirl defects in silicon crystals

Swirl defects in dislocation-free Czochralski (CZ) silicon crystals have been investigated by preferential etching, transmission electron microscopy (TER I) and electron energy loss spectroscopy (EELS) mode of a scanning transmission electron microscope (STEM). Two kinds of Swirl defects have been found with a good correspondence between striated pattern consisting of hillocks and the buried micro-defects. The Swirl defects were identified as perfect dislocation loop cluster and tetrahedral precipitate, respectively. In addition, a kind of tiny micro-defects is found to be distributed preferentially in the vicinity of the Swirl pattern although there is no detectable correspondence between hillocks and the micro-defects. The energy-filtered images have been obtained by the plasma peaks at different parts of a coherent precipitate with the Si matrix. The experimental results show some indications of the existence of oxygen and carbon in the core of the precipitate and suggest that oxygen and carbon may play important roles in the formation of Swirl defect. (C) 2000 Elsevier Science B.V. All rights reserved.

Void-like defects in annealed Czochralski silicon

Void-like defects of octahedron structure having {111} facets were observed in annealed Czochralski silicon. The amorphous coverage of SiOx and SiCx on the inner surface of the defects was identified using transmission electron microscopy and electron energy-loss spectroscopy. It is suggested that these defects are a kind of amorphous precipitate origin. A mechanism for the generation of these defects and the previously reported solid amorphous precipitates is proposed. (C) 1998 American Institute of Physics. [S0003-6951(98)02842-3].

Microstructural and compositional characteristics of GaN films grown on a ZnO-buffered Si(111) wafer

Polycrystalline GaN thin films have been deposited epitaxially on a ZnO-buffered (111)-oriented Si substrate by molecular beam epitaxy. The microstructural and compositional characteristics of the films were studied by analytical transmission electron microscopy (TEM). A SiO2 amorphous layer about 3.5 nm in thickness between the Si/ZnO interface has been identified by means of spatially resolved electron energy loss spectroscopy. Cross-sectional and plan-view TEM investigations reveal (GaN/ZnO/SiO2/Si) layers exhibiting definite a crystallographic relationship: [111](Si)//[111](ZnO)//[0001](GaN) along the epitaxy direction. GaN films are polycrystalline with nanoscale grains (similar to100 nm in size) grown along [0001] direction with about 20degrees between the (1 (1) over bar 00) planes of adjacent grains. A three-dimensional growth mode for the buffer layer and the film is proposed to explain the formation of the as-grown polycrystalline GaN films and the functionality of the buffer layer. (C) 2004 Elsevier Ltd. All rights reserved.

Chemisorption and reaction characteristics of methyl radicals on Cu(110)

Methyl radicals are generated by pyrolysis of azomethane, and the condition for achieving neat adsorption on Cu(110) is described for studying their chemisorption and reaction characteristics. The radical-surface system is examined by X-ray photoemission spectroscopy, ultraviolet photoemission spectroscopy, temperature-programmed desorption, low-energy electron diffraction (LEED), and high-resolution electron energy loss spectroscopy under ultrahigh vacuum conditions. It is observed that a small fraction of impinging CH3 radicals decompose into methylene possibly on surface defect sites. This type of CH2 radical has no apparent effect on CH3(ads) surface chemistry initiated by dehydrogenation to form active CH2(ads) followed by chain reactions to yield high-mass alkyl products. All thermal desorption products, such as H-2, CH4, C2H4, C2H6, and C3H6, are detected with a single desorption peak near 475 K. The product yields increase with surface coverage until saturation corresponding to 0.50 monolayer of CH3(ads). The mass distribution is, however, invariant with initial CH3(ads) coverage, and all desorbed species exhibit first-order reaction kinetics. LEED measurement reveals a c(2 x 2) adsorbate structure independent of the amount of gaseous exposure. This strongly suggests that the radicals aggregate into close-packed two-dimensional islands at any exposure. The islanding behavior can be correlated with the reaction kinetics and is deemed to be essential for the chain propagation reactions. Some relevant aspects of the CH3/Cu(111) system are also presented. The new results are compared with those of prior studies employing methyl halides as radical sources. Major differences are found in the product distribution and desorption kinetics, and these are attributed to the influence of surface halogen atoms present in those earlier investigations.

Evidence for perimeter sites over SmOx-modified Rh(100) surface by CO chemisorption

SmOx modified Rh(l 0 0) surfaces have been in-situ prepared by depositing metallic Sin and subsequently oxidizing under controlled conditions, and the interaction between the lanthanide oxide and transition metal has been characterized by means of X-ray photoelectron spectroscopy (XPS) and high-resolution electron-energy-loss spectroscopy (HREELS) as well as thermal desorption spectroscopy (TDS). As evidenced, the adsorption of CO on the modified surfaces shows some different features to the original surface of Rh(l 00). The covering of SmOx blocks some sites on the surface and consequently suppresses adsorption of the typical CO species with an uptake at about 500 K, while a novel desorption peak centered at 260 K emerges in the CO TDS. Correspondingly, the XP spectrum exhibits a new C Is peak at 287.9 eV and 0 Is peak at 532.6 eV. The intensity of the low temperature peak varies with the coverage of SmOx, which shows an actual correlation to the perimeter sites of SmOx particles on the surface. (C) 2004 Elsevier B.V. All rights reserved.