J.R. Morante

The complete Raman spectrum of nanometric SnO2 particles

14 and space group P4 2 /mnm. The unit cell consists of two metal atoms and four oxygen atoms. Each metal atom is situated amidst six oxygen atoms which approximately form the corners of a regular octahedron. Oxygen atoms are surrounded by three tin atoms which approximate the corners of an equilateral triangle. The lattice parameters are a5b 54.737 A, and c53.186 A. The ionic radii for O 22 and Sn 41 are 1.40 and 0.71 A, respectively. 1 The 6 unit cell atoms give a total of 18 branches for the vibrational modes in the first Brillouin zone. The mechanical representation of the normal vibration modes at the center of the Brillouin zone is given by 2,3 G5G 1 ~ A1g!1G 2 ~ A2g!1G 3 ~ B1g!1G 4 ~ B2g! 1G 5 ~ Eg!12G 1 ~ A2u!12G 4 ~ B1u!14G 5 ~ Eu!, ~1! using the Koster notation with the commonly used symmetry designations listed in parenthesis. The latter will be used throughout this article. Of these 18 modes, 2 are active in infrared ~the single A2u and the triply degenerate Eu), 4 are Raman active ~three nondegenerated modes, A1g , B1g , B2g , and a doubly degenerate Eg), and two are silent ( A2g , and B1u). One A2u and two Eu modes are acoustic. In the Raman active modes oxygen atoms vibrate while Sn atoms are at rest ~see Fig. 1 in Ref. 4!. The nondegenerate mode, A1g , B1g , and B2g , vibrate in the plane perpendicular to the c axis while the doubly degenerated E g mode vibrates in the direction of the c axis. The B 1g mode consists of rotation of the oxygen atoms around the c axis, with all six oxygen atoms of the octahedra participating in the vibration. In the A2g infrared active mode, Sn and oxygen atoms vibrate in the c axis direction, and in the Eu mode both Sn and O atoms vibrate in the plane perpendicular to the c axis. The silent modes correspond to vibrations of the Sn and O atoms in the direction of the c axis (B1u) or in the plane perpendicular to this direction ( A2g). According to the literature, the corresponding calculated or observed frequencies of the optical modes are presented in Table I. When the size of the SnO2 crystal is reduced, the infrared spectrum is modified because the interaction between electromagnetic radiation and the particles depends on the crystal’s size, shape, and state of aggregation. 8‐1 0 Experiments using Raman spectroscopy have also reported spectrum modification, at least partially. Low frequency bands have been observed previously in SnO2, 11 and several authors have reported the existence of bands not observed in single-crystal or polycrystalline SnO 2 which have been found to be closely related to grain size. 12‐15 However, some of these reports do not adequately explain the origin of the abnormal spectrum. The aim of this article is to present a complete Raman spectrum of SnO2 nanoparticles. The analysis comprises ~i! modification of the normal vibration modes active in Raman when the spectra are obtained from nanocrystals of SnO2 ~‘‘classical modes’’ !, ~ii! the disorder activated surface modes in the region around 475‐775 cm 21 , and ~iii! the appearance of the acoustic modes in the low-frequency region of the spectra.

Structural and optical properties of high quality zinc-blende/wurtzite GaAs nanowire heterostructures

The structural and optical properties of three different kinds of GaAs nanowires with 100% zinc-blende structure and with an average of 30% and 70% wurtzite are presented. A variety of shorter and longer segments of zinc-blende or wurtzite crystal phases are observed by transmission electron microscopy in the nanowires. Sharp photoluminescence lines are observed with emission energies tuned from 1.515 eV down to 1.43 eV when the percentage of wurtzite is increased. The downward shift of the emission peaks can be understood by carrier confinement at the interfaces, in quantum wells and in random short period superlattices existent in these nanowires, assuming a staggered band offset between wurtzite and zinc-blende GaAs. The latter is confirmed also by time-resolved measurements. The extremely local nature of these optical transitions is evidenced also by cathodoluminescence measurements. Raman spectroscopy on single wires shows different strain conditions, depending on the wurtzite content which affects also the band alignments. Finally, the occurrence of the two crystallographic phases is discussed in thermodynamic terms.

In-depth resolved Raman scattering analysis for the identification of secondary phases: Characterization of Cu2ZnSnS4 layers for solar cell applications

This work reports the in-depth resolved Raman scattering analysis with different excitation wavelengths of Cu2ZnSnS4 layers. Secondary phases constitute a central problem in this material, particularly since they cannot be distinguished by x-ray diffraction. Raman spectra measured with 325 nm excitation light after sputtering the layers to different depths show peaks that are not detectable by excitation in the visible. These are identified with Cu3SnS4 modes at the surface region while spectra measured close to the back region show peaks from ZnS and MoS2. Observation of ZnS is enhanced by resonant excitation conditions achieved when working with UV excitation.

Effects of Nb doping on the TiO2 anatase-to-rutile phase transition

We study the influence of Nb doping on the TiO2 anatase-to-rutile phase transition, using combined transmission electron microscopy, Raman spectroscopy, x-ray diffraction and selected area electron diffraction analysis. This approach enabled anatase-to-rutile phase transition hindering to be clearly observed for low Nb-doped TiO2 samples. Moreover, there was clear grain growth inhibition in the samples containing Nb. The use of high resolution transmission electron microscopy with our samples provides an innovative perspective compared with previous research on this issue. Our analysis shows that niobium is segregated from the anatase structure before and during the phase transformation, leading to the formation of NbO nanoclusters on the surface of the TiO2 rutile nanoparticles.

Influence of average size and interface passivation on the spectral emission of Si nanocrystals embedded in SiO2

The correlation between the structural (average size and density) and optoelectronic properties [band gap and photoluminescence (PL)] of Si nanocrystals embedded in SiO2 is among the essential factors in understanding their emission mechanism. This correlation has been difficult to establish in the past due to the lack of reliable methods for measuring the size distribution of nanocrystals from electron microscopy, mainly because of the insufficient contrast between Si and SiO2. With this aim, we have recently developed a successful method for imaging Si nanocrystals in SiO2 matrices. This is done by using high-resolution electron microscopy in conjunction with conventional electron microscopy in dark field conditions. Then, by varying the time of annealing in a large time scale we have been able to track the nucleation, pure growth, and ripening stages of the nanocrystal population. The nucleation and pure growth stages are almost completed after a few minutes of annealing time at 1100 °C in N2 and after...

Analysis of the noble metal catalytic additives introduced by impregnation of as obtained SnO2 sol–gel nanocrystals for gas sensors

In order to clarify the role of the noble metal additives in the gas sensing mechanisms, three of the most common catalytic additives, such as Pd, Pt and Au, have been introduced in a sol–gel obtained tin oxide base material. The additives nominal weight concentrations used were 0.2% and 2%, and they were introduced in the precipitated tin oxide. A posterior calcination treatment was carried out, during 8 h, at the temperatures of 250°C, 400°C, 450°C, 600°C, 800°C and 1000°C. Structural and surface analysis of these nanopowders have been performed. Identification and localisation of metallic, 2+ and 4+ oxidised states of the used noble metals are discussed, and experimental evidences about their effects on the sensor performance are presented. Likewise, effects of their presence on the nanoparticle characteristics, and also on the material sensitivity to CO and CH4, are analysed and discussed.

Nucleation mechanism of gallium-assisted molecular beam epitaxy growth of gallium arsenide nanowires

Molecular beam epitaxy Ga-assisted synthesis of GaAs nanowires is demonstrated. The nucleation and growth are seen to be related to the presence of a SiO2 layer previously deposited on the GaAs wafer. The interaction of the reactive gallium with the SiO2 pinholes induces the formation of nanocraters, found to be the key for the nucleation of the nanowires. With SiO2 thicknesses up to 30nm, nanocraters reach the underlying substrate, resulting into a preferential growth orientation of the nanowires. Possibly related to the formation of nanocraters, we observe an incubation period of 258s before the nanowires growth is initiated.

Self-assembled quantum dots in a nanowire system for quantum photonics

Quantum dots embedded within nanowires represent one of the most promising technologies for applications in quantum photonics. Whereas the top-down fabrication of such structures remains a technological challenge, their bottom-up fabrication through self-assembly is a potentially more powerful strategy. However, present approaches often yield quantum dots with large optical linewidths, making reproducibility of their physical properties difficult. We present a versatile quantum-dot-in-nanowire system that reproducibly self-assembles in core-shell GaAs/AlGaAs nanowires. The quantum dots form at the apex of a GaAs/AlGaAs interface, are highly stable, and can be positioned with nanometre precision relative to the nanowire centre. Unusually, their emission is blue-shifted relative to the lowest energy continuum states of the GaAs core. Large-scale electronic structure calculations show that the origin of the optical transitions lies in quantum confinement due to Al-rich barriers. By emitting in the red and self-assembling on silicon substrates, these quantum dots could therefore become building blocks for solid-state lighting devices and third-generation solar cells.

High mobility indium free amorphous oxide thin film transistors

High mobility bottom gate thin film transistors (TFTs) with an amorphous gallium tin zinc oxide (a-GSZO) channel layer have been produced by rf magnetron cosputtering using a gallium zinc oxide (GZO) and tin (Sn) targets. The effect of postannealing temperatures (200, 250, and 300°C) was evaluated and compared with two series of TFTs produced at room temperature (S1) and 150°C (S2) during the channel deposition. From the results, it was observed that the effect of postannealing is crucial for both series of TFTs either for stability as well as for improving the electrical characteristics. The a-GSZO TFTs (W∕L=50∕50μm) operate in the enhancement mode (n-type), present a high saturation mobility of 24.6cm2∕Vs, a subthreshold gate swing voltage of 0.38V/decade, a turn-on voltage of −0.5V, a threshold voltage of 4.6V, and an Ion∕Ioff ratio of 8×107, satisfying all the requirements to be used as active-matrix backplane.

Crystalline structure, defects and gas sensor response to NO2 and H2S of tungsten trioxide nanopowders

AbstractStructural and NO 2 and H 2 S gas-sensing properties of nanocrystalline WO 3 powders are analysed in this work. Sensor response of thick-film gas sensors was studied in dry and humid air. Interesting differences were found on the sensor response between sensors based on 400 and700 8C-annealed WO 3 , what motivated a structural study of these materials. Crystalline structure and defects were characterised by X-raydiffraction (XRD), Raman spectroscopy and transmission electron microscopy (TEM). Experimental results showed that both triclinic andmonoclinic structures are present in the analysed materials, although their amount depends on the annealing treatment. Crystalline shearplanes, which are defects associated to oxygen deficient tungsten trioxide, were found in 400 8C-annealed WO 3 and their influence on XRDspectra was analysed by XRD simulations. Moreover, XRD and Raman spectra were also acquired at normal metal oxide-based gas sensorworking temperatures in order to relate both crystalline structure and sensor response.# 2003 Elsevier Science B.V. All rights reserved.