Synthesis and photoluminescence of aligned SiO<Subscript>x</Subscript> nanowire arrays

Aligned SiO_x nanowire arrays standing on a Si substrate were successfully synthesized using a simple method by heating a single-crystalline Si slice covered with SiO₂ nanoparticles at 1000 °C in a flowing Ar atmosphere. The SiO_x nanowire arrays were characterized by scanning electron microscopy and transmission electron microscopy. The SiO_x nanowires become progressively thinner from bottom to top. The formation process of the SiO_x nanowire arrays is closely related to a vapor–solid mechanism. Room-temperature photoluminescence measurements under excitation at 260 nm showed that the SiO_x nanowire arrays had a strong blue–green emission at 500 nm (about 2.5 eV), which may be related to oxygen defects. Received: 29 April 2002 / Accepted: 30 April 2002 / Published online: 10 September 2002 RID="*" ID="*"Corresponding author. Fax: +86-551-559-1434, E-mail: gwmeng@mail.issp.ac.cn     

Study of the third order nonlinear optical properties of Zn<Subscript>1−x</Subscript>Mg<Subscript>x</Subscript>Se and Cd<Subscript>1−x</Subscript>Mg<Subscript>x</Subscript>Se crystals

Third order nonlinear optical susceptibilities χ^<3> of ternary Zn_1−xMg_xSe and Cd_1−xMg_xSe crystals have been measured using standard degenerate four-wave mixing (DFWM) method at 532 nm. The nonlinear transmission technique has been applied to check if our crystals exhibit two-photon absorption. The studied Zn_1−xMg_xSe and Cd_1−xMg_xSe solid solutions were grown from the melt by the modified high-pressure Bridgman method. For both crystals the energy gap increases with increasing Mg content. In the case of Zn_1−xMg_xSe, it was found that the value of third order nonlinear optical susceptibility χ^<3> decreases with increasing Mg content. An explanation of this behaviour results from the dependence of optical nonlinearities on the energy band gap E_g of the studied crystals. In the case of Cd_1txMg_xSe with low content of Mg, no response was observed for the studied wavelength since the energy gap in such crystals is smaller than the photon energy of the used laser radiation. It was also found that the value of third order nonlinear optical susceptibility χ^<3> for Cd_0.70Mg_0.30Se is higher than for Zn_0.67Mg_0.33Se. This behaviour can be understood if one take into consideration that the free carrier concentration in Cd_1−xMg_xSe samples is about four orders of magnitude higher than that in Zn_1txMg_xSe ones with comparable Mg content respectively. It is commonly known that when the electric conductivity increases, the values of nonlinear optical properties increase. From the performed measurements one can conclude that the incorporation of Mg as constituent into ZnSe and CdSe crystals leads to a change of the third order nonlinear optical susceptibilities.     

Short-range magnetic order,irreversibility and giant magnetoresistance near the triple points in the (x,T) magnetic phase diagram of ZrMn<Subscript>6</Subscript>Sn<Subscript>6-x</Subscript>Ga<Subscript>x</Subscript>

We have studied pseudo-layered ZrMn₆Sn_6-xGa_x intermetallics (0.55 ≤ x ≤ 0.81) using magnetic, magnetoresistivity and powder neutron diffraction measurements. All the alloys studied have magnetic ordering temperatures in the 450-490 K temperature range. They present complex temperature-dependent partially disordered magnetic structures whose ferromagnetic component develops upon increasing the Ga content. ZrMn₆Sn_6-xGa_x alloys with x ≤ 0.69 are essentially collinear antiferromagnets at high-temperature and adopt antifan-like arrangements at low temperature. For x ≥ 0.75, the alloys order ferromagnetically and evolve to a fan-like structure upon cooling. The intermediate compositions (x = 0.71 and 0.73) present a canted fan-like order at high temperature and another kind of antifan-like arrangement at low temperature. The degree of short-range order tends to increase upon approaching the intermediate compositions. The (x, T) phase diagram contains two triple points (x ~ 0.70; T ~ 460 K and x ~ 0.74; T ~ 455 K), where the paramagnetic, an incommensurate and a commensurate phases meet, which possess some of the features of Lifshitz point. Irreversibilities manifest in the low-temperature magnetization curves at the antifan-fan or fan-ferromagnetic boundaries as well as inside the fan region. Giant magnetoresistance is observed, even above room temperature.     

Coarsening-resistant Ag nanoparticles stabilized on amorphous TiO<Subscript>x</Subscript> nanoparticles

Bare Ag nanoparticles (～10 nm) and Ag nanoparticles (1–20 nm) on the surfaces of larger TiO_x nanoparticles were prepared by laser ablation of microparticle aerosols (LAMA). The behaviors of the nanoparticles during high temperature annealing were then studied with ex situ and in situ transmission electron microscopy. For the ex situ heating experiments, Ag and Ag-on-TiO_x NPs were collected onto gold TEM grids and subjected to annealing treatments at 500 °C in argon, vacuum, and air. At this temperature, bare Ag NPs on carbon TEM supports coarsened rapidly in both air and argon atmospheres. In contrast, Ag-on-TiO_x NPs that were heated to 500 °C in flowing argon or in a vacuum did not coarsen significantly and were remarkably stable. Ag-on-TiO_x NPs that were heated to 500 °C in air, however, behaved quite differently. The TiO_x crystallized upon heating and a significant loss of Ag were observed from the surfaces of the TiO_x, likely due to sublimation. These results demonstrate that the surface defect structure and chemistry of the oxide support strongly influence the thermal stability of Ag NPs produced by LAMA.     

Preparation,characterization and photoluminescence properties of ultra long SiC/SiO<Subscript>x</Subscript> nanocables

SiC core and SiO_x shell nanocables of a few millimeters long have been prepared by pyrolysis of SiO₂ nanopowder added poly(dimethyl siloxane) without catalyst in a tube furnace at 1050 °C in Ar. The influence of the synthesis conditions (synthesis temperature and cooling time) on the products is studied. The products obtained from different conditions are characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, high-resolution electron microscopy equipped with energy dispersive X-ray spectroscopy, and photoluminescence spectroscopy. The results show that the cores and the shells are crystalline and amorphous, respectively, and that the addition of SiO₂ nanopowder and prolongation of cooling time both increase the diameter of the cores. The growth process of the nanocables is discussed. The photoluminescence emission bands of the nanocables are mainly from their shells. PACS 68.37.Hk; 68.37.Lp; 78.67.n; 81.07.b; 81.16.Be     

Large-scale potential fluctuations caused by SiO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> compositional inhomogeneity

The short-range order in amorphous SiO _x (0 ≤ x ≤ 2) films has been studied by high-resolution X-ray photoelectron spectroscopy. Both the random bonding and random mixture models do not describe experimental photoelectron spectra of SiO _x (x ≤ 2). An intermediate model of the SiO _x structure has been proposed. The measured photoelectron spectra of the SiO _x (x ≤ 2) valence band indicate the presence of the silicon phase and silicon oxide.     

a-Si/SiN<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> multilayered light absorber for solar cell

40 alternate a-Si/SiN _x multilayer are incorporated as an absorber layer in a p–i–n solar cell. The device is fabricated using hot-wire chemical vapor deposition (HWCVD) technique. The structure of the multilayer film is examined by high resolution transmission electron microscopy (HR-TEM) which shows distinct formation of alternate a-Si and SiN _x layers. The a-Si and SiN _x layers have thickness of ~3.5 and 4 nm, respectively. The photoluminescence (PL) of multilayer film shows bandgap energy of ~2.52 eV, is larger than that of the c-Si and a-Si. Dark and illuminated current–voltage (I–V) characterization of the ML films shows that these ML are photosensitive. In the present work, it is seen that the p–i–n structure with i-layer as ML quantum well (QW) structures show photovoltaic effect with relatively high open-circuit voltage (V _OC). The increment of bandgap energy in PL and high V _OC of the device is attributed to the quantum confinement effect (QCE).     

Anomalous thermal expansion in La<Subscript>2−x</Subscript>Sr<Subscript>x</Subscript>CuO<Subscript>4</Subscript> system

It was found that thermal expansion Δl/l was anomalous in a wide temperature interval for single-and polycrystals of the La_2?xSr_xCuO₄ system with various doping levels: the samples with small Sr content contracted with heating. This effect was observed up to x=0.2. Anisotropy of thermal expansion was revealed, for different crystal directions. The Δl/l anomaly was sensitive, to the oxygen content. These results are consistent with the local bosons model.     

Glass-forming ability and thermal stability of Fe<Subscript>62</Subscript>Nb<Subscript>8−x</Subscript>Zr<Subscript>x</Subscript>B<Subscript>30</Subscript> and Fe<Subscript>72</Subscript>Zr<Subscript>8</Subscript>B<Subscript>20</Subscript> amorphous alloys?

Glass-forming ability (GFA) and thermal stability of Fe₆₂Nb₈B₃₀, Fe₆₂Nb₆Zr₂B₃₀ and Fe₇₂Zr₈B₂₀ at % amorphous alloys were investigated by calorimetric (DSC and DTA) measurements. The crystallization kinetics was studied by DSC in the mode of continuous versus linear heating and it was found that both the glass transition temperature, T _g , and the crystallization peak temperature, T _p , display strong dependence on the heating rate. The partial replacement of Nb by Zr leads to lower T _g and T _x temperatures and causes a decrease of the supercooled liquid region. JMA analysis of isothermal transformation data measured between T _g and T _x suggests that the crystallization of the Fe₆₂Nb₈B₃₀ and Fe₆₂Nb₆Zr₂B₃₀ amorphous alloys take place by three-dimensional growth with constant nucleation rate. Nb enhances the precipitation of the metastable Fe₂₃B₆ phase and stabilizes it up to the third crystallization stage. Zr addition increases the lattice constant of Fe₂₃B₆ and, at the same time, decreases the grain size.     

Temperature dependence of the fundamental band gap parameters in cadmium-rich Zn<Subscript>x</Subscript>Cd<Subscript>1-x</Subscript>Se using photoluminescence spectroscopy

Thin films of ternary Zn_xCd_1-xSe were deposited on GaAs (100) substrate using metalorganic-chemical-vapour-deposition (MOCVD) technique. Temperature dependence of the nearband-edge emission from these Cd-rich Zn_xCd_1-xSe (forx = 0025, 0.045) films has been studied using photoluminescence spectroscopy. Relevant parameters that describe temperature variation of the energy and broadening of the fundamental band gap have been evaluated using various models including the two-oscillator model, the Bose-Einstein model and the Varshni model. While all these models suffice to explain spectra at higher temperatures, the two-oscillator model not only explains low temperature spectra adequately but also provides additional information concerning phonon dispersion in these materials.     

The role of material microstructure in the magnetic behavior of amorphous and polycrystalline Co<Subscript>x</Subscript>Si<Subscript>1-x</Subscript> lines

The role of material microstructure in the magnetic anisotropy of real nanostructures has been studied by the comparison of the magnetic behavior of arrays of amorphous and polycrystalline Co_xSi_1-x lines. From the experimental measurements of angular dependences of remanences parallel and perpendicular to the applied field we determine the angular dispersion of effective local easy axis of anisotropy. We have proved that amorphous lines have a dispersion of effective anisotropy axis much smaller than the polycrystalline samples. As a consequence, amorphous lines have a better defined magnetic behaviour, pointing the interest of the fabrication of nanostructures made of amorphous materials.     

Short-range order in amorphous ferromagnetic Fe-B alloys

Amorphous and quenched crystalline Fe-B alloys in the composition range of 4–25 at % B were prepared by melt spinning and investigated by ⁵⁷Fe Mössbauer spectroscopy at T = 87 K. The states of iron atoms in the α-Fe phases, including iron atoms having boron atoms in the nearest coordination sphere, and in the orthorhombic (o) and tetragonal (T) Fe₂B phases are detected in the microcrystalline alloys. The short-range order and the local atomic structure of the amorphous Fe-B alloys are determined. The amorphous alloys consist of microregions (clusters) with short-range order of the t- and o-Fe₂B and α-Fe types. The dependence of the content of various types of clusters on the alloy composition is quantitatively estimated.     

Short-range order in the Fe-B-Sn amorphous system

Melt quenched FeBSn samples of different compositions were prepared with three different quenching rates and analyzed by Mössbauer spectroscopy and X-ray diffraction. In a previous work, the glass-forming tendency in this system was analyzed, In the present work, the short-range order is studied and an improvement in the determination of the glass-forming composition range is achieved. Mössbauer spectra were fit using hyperfine field distributions.     

Anomalous temperature dependence of photoluminescence in GeO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> films and GeO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>/SiO<Subscript>2</Subscript> nano-heterostructures

The optical properties of GeO _x film and GeO _x /SiO₂ multilayer heterostructures (with thickness of GeO _x layers down to 1 nm) were studied with the use of Raman scattering and infrared spectroscopy, ellipsometry and photoluminescence spectroscopy including temperature dependence of photoluminescence. The observed photoluminescence is related to defect (dangling bonds) in GeO _x and interface defects for the case of GeO _x /SiO₂ multilayer heterostructures. From analysis of temperature dependence of photoluminescence intensity, it was found that rate of nonradiative transitions in GeO _x film has Berthelot type, but anomalous deviations from Berthelot type temperature dependence were observed in temperature dependences of photoluminescence intensities for GeO _x /SiO₂ multilayer heterostructures.     

Intensely emitting CdTe nanocrystals retained initial photoluminescence efficiency in sol–gel derived Si<Subscript>1-x</Subscript>Zr<Subscript>x</Subscript>O<Subscript>2</Subscript> glass

Emitting CdTe nanocrystals (NCs) were embedded in pure glass matrices (Si_1-xZr_xO₂, x≤0.15) using a controlled sol–gel method, where the pre-hydrolyzed condition, the molar ratio of Zr/Si, the gelation time, the pH, and the amount of alcohol were judiciously optimized considering the surface condition of the NCs and the mechanism of the glass formation. As a result, the prepared glass phosphor exhibited high photoluminescence efficiencies (40% for green and 60% for red when Zr/Si was 5–10%) by retaining their initial values as in CdTe colloidal solution. To our knowledge, these values are the highest among those ever obtained for any solid matrices containing NCs. Because of the existence of Zr, the prepared glasses exhibit much better resistance against the ambient atmosphere, heat-treatment, and boiling water compared with pure silica glass (x=0) or the glass prepared from our other methods using a silane coupling agent. Thus, the obtained glass is promising for applications such as optical devices. PACS 78.67.Bf; 78.55.Qr; 78.55.Et     

Magnetic phases in Mn<Subscript>1</Subscript>_<Subscript>x</Subscript>Fe<Subscript>x</Subscript>WO<Subscript>4</Subscript> studied by neutron powder diffraction

The magnetic structures of Mn_1-xFe_xWO₄ with x = 0.0, 0.16, 0.21, 0.225, 0.232, 0.24, 0.27, 0.29, and 1.0 were refined from neutron powder diffraction data. The magnetic phase diagram could be completed in the coexistence range of different magnetic structures up to x = 0.29. For the magnetic state at 1.5 K a commensurate antiferromagnetic structure with a propagation vector = (±1/4, 1/2, 1/2) was found for x ⩽ 0.22 while the magnetic spins order with = (1/2, 0, 0) for x ≥ 0.22. In the latter phase, additionally, weak magnetic reflections indexed to an incommensurate ordering with = (- 0.214, 1/2, 0.457) occur in the diffraction pattern up to x = 0.29 indicating the occurence of a reentrant phase. For 0.12 ⩽ x ⩽ 0.29 the low temperature phases are separated from a magnetic high temperature phase showing only magnetic reflections indexed to a spin arrangement with = (1/2, 0, 0). The magnetic phase diagram is discussed qualitatively considering random superexchange between the statistically distributed Mn²⁺- and Fe²⁺-ions in the coexistence range 0.12 ⩽ x ⩽ 0.29 of different magnetic structures related to those of pure MnWO₄ and FeWO₄. Received 9 October 2002 Published online 14 March 2003     

Raman scattering and electrical properties of Tl<Subscript>x</Subscript>Cu<Subscript>1−x</Subscript>GaSe<Subscript>2</Subscript> solid solutions

The results of the study of Raman scattering and photo-emf in Tl _x Cu_1−x GaSe₂ single crystals are presented. The objective of this work was to reveal some features of optical and phonon spectra, to study regularities of their variation with composition and, on this basis, to create prerequisites to extend the possibilities of their practical applications.     

On the interpretation of the phase diagram of La<Subscript>2−x</Subscript>M<Subscript>x</Subscript>CuO<Subscript>4</Subscript>

The difference between the phase diagrams of La_2?x(Ba,Sr)_xCuO₄ and Nd_2?xCe_xCuO₄ is discussed. It is proposed that the discrepancy of x-values corresponding to the transition from antiferromagnetic dielectric state to conducting one (respectively, x≈0.06 in La_2?x(Ba,Sr)_xCuO₄ and x≈0.125 in Nd_2?xCe_xCuO₄) results from non-homogeneous doping of La_2?x(Ba,Sr)_xCuO₄ over the range 0.06<x<0.125, when localized holes are added to each second CuO₂ layer. Therefore the actual phase diagram of the “holedoped” superconductor La_2?x(Ba,Sr)_xCuO₄ coincides with one for the “electron-doped” superconductor Nd_2?xCe_xCuO₄. It is shown that all features observed in La_2?x(Ba,Sr)_xCuO₄ around x=0.125 are clarified on this basis.     

Electrical switching studies on As<Subscript>40</Subscript>Te<Subscript>60-x</Subscript>Se<Subscript>x</Subscript> and As<Subscript>35</Subscript>Te<Subscript>65-x</Subscript>Se<Subscript>x</Subscript> glasses

The I–V characteristics of bulk As₄₀Te_60-xSe_x and As₃₅Te_65-xSe_x glasses have been studied with a current sweep of 0–18 mA-0, over a wide range of compositions (4≤x≤22). All the glasses studied showed a threshold electrical switching behaviour. The number of switching cycles withstood by the samples has been found to depend on the ON-state current. It is seen that the switching voltages increase with increase in selenium content. Further, the switching voltages are found to be almost independent of the thickness of the sample (d), in the range 0.18–0.3 mm. Also, the switching voltages and the number of switching cycles withstood by the samples are found to decrease with temperature. Received: 6 November 2002 / Accepted: 8 November 2002 / Published online: 29 January 2003 RID="*" ID="*"Corresponding author. Fax: +91-80/360-0135, E-mail: sasokan@isu.iisc.ernet.in     

Structure,transport and magnetic properties of the double perovskite (Ca<Subscript>2-2x</Subscript>Sr<Subscript>2x</Subscript>)FeMoO<Subscript>6</Subscript>

In this paper we report the results of a detailed investigation of the double perovskite (Ca_2-2xSr_2x)FeMoO₆ system. Chemical size effects on structural, electrical, and magnetic properties caused by the substitution of isovalent, larger Sr ions into the smaller Ca sites, resulting in (Ca_2-2xSr_2x)FeMoO₆, have been examined. The compounds crystallize in the monoclinic space group P2₁/n for 0.0x<0.2, the orthorhombic space group Pbnm for 0.2x<0.4, and the tetragonal space group I4/m and I4/mmm for x0.4. Examination of the resistivity of all compounds reveals a metallic behavior which is well described by a Tⁿ dependence except for x=1.0. These n values change from 1 to 2 as T decreases lower than T_c. This is indicative of a variation in the transport mechanism at T_c. The ferrimagnetic transition temperature T_c increases with increasing x from 318 (x=0.0) to 393 K (x=1.0). For all samples, the saturation magnetization at 82 K obeys M_s3.5_B/(formula unit), compared to a theoretical spin-only moment of 4_B/(formula unit) for a perfectly ordered compound. PACS 74.25.Fy; 74.25.Ha