Structural and sensing properties of nanocrystalline SnO<Subscript>2</Subscript> films deposited by spray pyrolysis from a SnCl<Subscript>2</Subscript> precursor

We report the fabrication and characterization of tin dioxide gas sensing layers. The tin dioxide layers were synthesized using a convenient, simple and low-cost technique of spray pyrolysis. The formation of stoichiometric SnO₂ layers with fine-grain structure is revealed by Rutherford backscattering spectroscopy. The microstructure, phase, nanoparticle size distribution and surface morphology were studied by transmission electron microscopy, electron diffraction and atomic force microscopy. Most of the grains were of 10–20 nm size; however, some particles were up to 100 nm in size and had a microtwin lamellae structure of SnO₂ phase (cassiterite) with lattice parameters a= 0.474 nm and c= 0.319 nm. The sensitivity of the layers with respect to 1000–10000 ppm CH₄ in air was obtained from both resistivity (S_R) and capacity (S_C) measurements at 330 °C and values of S_R=5–7 and S_C=22–31 were extracted. PACS 68.43.-h; 68.55.-a; 81.05.Hd; 81.07.-b; 81.15.Rs     

Ultra-sharp α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoflakes: growth mechanism and field-emission

We report the synthesis of single-crystalline α-Fe₂O₃ nanoflakes from a simple Fe–air reaction within the temperatures range of 260–400 °C. The nanoflakes synthesized at the lowest temperature (260 °C) in this work show an ultra-sharp morphology: 5–10 nm in thickness, 1–2 μm in length, 20 nm in base-width and around 5 nm at the tips; successfully demonstrate the promising electron field emission properties of a large-scaled α-Fe₂O₃ nanostructure film and exhibit the potential applications as future field-emission (FE) electron sources and displays (FEDs). The formation and growth of α-Fe₂O₃ nanostructures were discussed based on the surface diffusion mechanism. PACS 79.60.Jv; 79.70.+q; 77.84.Bw     

Structure of vacant electronic states of an oxidized germanium surface upon deposition of perylene tetracarboxylic dianhydride films

This paper presents the results of the investigation of the interface potential barrier and vacant electronic states in the energy range of 5 to 20 eV above the Fermi level (E_F) in the deposition of perylene tetracarboxylic dianhydride (PTCDA) films on the oxidized germanium surface ((GeO₂)Ge). The concentration of oxide on the (GeO₂)Ge surface was determined by X-ray photoelectron spectroscopy. In the experiments, we used the recording of the reflection of a test low-energy electron beam from the surface, implemented in the mode of total current spectroscopy. The theoretical analysis involves the calculation of the energy and spatial distribution of the orbitals of PTCDA molecules by the density functional theory (DFT) using B3LYP functional with the basis 6-31G(d), followed by the scaling of the calculated values of the orbital energy according to the procedure well-proven in the studies of small organic conjugated molecules. The pattern of changes in the fine structure of the total current spectra with increasing thickness of the PTCDA coating on the (GeO₂)Ge surface to 6 nm was studied. At energies below 9 eV above E_F, there is a maximum of the density of unoccupied electron states in the PTCDA film, formed mainly by π* molecular orbitals. The higher density maxima of unoccupied states are of σ* nature. The formation of the interface potential barrier in the deposition of PTCDA at the (GeO₂)Ge surface is accompanied by an increase in the work function of the surface, E_vac–E_F, from 4.6 ± 0.1 to 4.9 ± 0.1 eV. This occurs when the PTCDA coating thickness increases to 3 nm, and upon further deposition of PTCDA, the work function of the surface does not change, which corresponds to the model of formation of a limited polarization layer in the deposited organic film.     

Controlled synthesis of CeO<Subscript>2</Subscript> nanoparticles using novel amphiphilic cerium complex precursors

Maleic anhydride was grafted by long-chain alcohols (1-hexadecanol, 1-octadecanol) to amphiphilic mono-L cis-butene dicarboxylates (L = hexadecyl, octadecyl), i.e., MAH, MAO, respectively. Subsequently, corresponding amphiphilic cerium complexes with these two mono-L cis-butene dicarboxylate ligands (Ce(L')₃, L'= MAH, MAO) were synthesized and behaved as the precursors to prepare CeO₂ nanoparticles for both of which can form nanosized micelle-like aggregates by special self-assembly in the wet chemical process. The nanoparticles were further characterized by Fourier transform-infrared spectroscopy (FTIR), Diffuse reflectance ultraviolet-visible spectra (DRUVS), scanning electron microscope (SEM), transmission electron microscope (TEM), and x-ray diffraction (XRD). Both the CeO₂ nanoparticles are in a cubic fluorite structure and present regular and well-dispersion club-like morphology with average particle size in the range of 40–70 nm. Besides, the strong ultraviolet–visible absorption for these CeO₂ nanoparticles can be found at the long-wavelength ultraviolet to visible region of 200–500 nm.     

Synthesis and characterization of mono-dispersed Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>:Er<Superscript>3+</Superscript>-coated SiO<Subscript>2</Subscript> nanoparticles by co-precipitation process

In this paper, a facile co-precipitation process for preparing mono-dispersed core–shell structure nanoparticles is reported. The 110 nm SiO₂ cores coated with an yttrium aluminum garnet (Y₃Al₅O₁₂) layer doped with Er³⁺ were synthesized and the influence of the concentration ratio of [urea]/[metal ions] on the final product was investigated. The structure and morphology of samples were characterized by the X-ray powder diffraction, Fourier transform IR spectroscopy and transmission electron microscopy, respectively. The results indicate that a layer of well-crystallized garnet Y₃Al₅O₁₂:Er³⁺ were successfully coated on the silica particles with the thickness of 20 nm. The near infrared and upconversion luminescent spectra of the SiO₂@Y₃Al₅O₁₂:Er³⁺ powders further confirm that a Y₃Al₅O₁₂:Er³⁺ coating layer has formed on the surface of silica spherical particles.     

Modification of the electronic properties of the TiO2 (1 1 0) surface upon deposition of the ultrathin conjugated organic layers

A few nm thick 3,4,9,10-perylenetetracarboxylic acid dianhydride (PTCDA) and Cu-phthalocyanine (CuPc) overlayers were thermally deposited in situ in UHV onto TiO₂ (1 1 0) surface. Atomic composition of the surfaces under study was monitored using Auger electron spectroscopy (AES). The formation of the interfacial potential barrier and the structure of the unoccupied electronic states located 5-25 eV above the Fermi level (E_F) was monitored using a probing beam of low-energy electrons according to the total current electron spectroscopy (TCS) method. The work function values upon the overlayer deposition changed from 4.6 to 4.9 eV at the PTCDA/TiO₂ (1 1 0) interface and from 4.6 to 4.3 eV at the CuPc/TiO₂ (1 1 0) interface. Band bending in the TiO₂ substrate, molecular polarization in the organic film and changes in the work function due to the change in the surface composition were found to contribute to the formation of the interfacial potential barriers. Oxygen admixture related peaks were observed in the AES and in the TCS spectra of the CuPc overlayers. A mechanism of the transformations in the PTCDA and CuPc overlayers on the TiO₂ (1 1 0) upon elevating temperature from 25 to 400 °C was suggested.     

TiO<Subscript>2</Subscript> nanotube height effect on the efficiency of dye-sensitized solar cells

Performance of dye-sensitized solar cells (DSSCs) based on TiO₂ nanotubes (NTs) filled with TiO₂ nanoparticles (NPs) was studied as a function of NT height (h). The NT height was varied in the range of 1.5–7.0 μm, while the NT diameter was kept constant at ~80 nm. The studies showed that DSSC efficiency, current density, and fill factor linearly increased with h and ranged in 1.76–6.5%, 3.62–13.2 mA/cm², and 0.66–0.76, respectively, within the h range studied. The electrochemical impedance spectroscopy was also performed to study DSSC electron transport properties. Based on both photovoltaic and electrochemical impedance spectroscopy data, the results were explained as being due to the increased dye loading that led to higher light-harvesting efficiency.     

Photodesorption from ultra-thin metal films – a comparison of SO<Subscript>2</Subscript> and NO<Subscript>2</Subscript> on Ag/Si(100)

The photochemistry of SO₂ on thin epitaxial Ag films (5–60 nm) deposited on Si(100) has been studied using laser light with the wavelengths of 266, 355, and 532 nm. SO₂ desorbs with cross sections of 1.7×10^-19,1.7×10^-20 and 2.9×10^-21 cm², respectively. The average translation energy, 〈E_trans/2k〉, is 440 K for 266 and 355 nm light, and 270 K for 532 nm light. Cross sections for a 60 nm thick Ag film are practically identical to the ones for Ag(111) as the substrate. An increase by a factor of ∼3.5 is observed when the film thickness is reduced to 5 nm for 266 and 355 nm light. No significant change is observed for 532 nm excitation. The film thickness has no significant influence on the translational energy of the photodesorbed molecules. The data are discussed in connection with the change of absorptivity of the metal film–semiconductor system. A model is put forward which takes into account the light absorption in the Si substrate and the reduced relaxation of excited electrons in Si. Modelling indicates that electrons excited in the Si substrate with energies and parallel momenta not allowed in Ag contribute to the surface chemistry after crossing the gap in the projected band structure of Ag(111). PACS 82.45.MP; 73.63.-b; 82.50.Bc     

Photoemission study of SrTiO<Subscript>3</Subscript> surface layers instability upon metal deposition

In this work we study the Pt/SrTiO₃ (STO) interface system using X-ray photoelectron spectroscopy (XPS). The polycrystalline Pt layers with a thickness of about 2–3 nm are deposited by sputtering and thermal evaporation methods on STO(100) single crystals with two different type of terminations. We propose and show local conductivity (LC) measurements as a good method to check whether such very thin metal layers are continuous. The XPS data show that both methods of Pt deposition lead to changes of the chemical composition of the crystal surface layers, and such chemical instability should be taken into consideration when studying the physical properties of a metal–insulator interface. PACS 68.35.-p; 68.35.Dy; 73.40.Ns; 79.60.-i; 81.07.–b     

Selective Synthesis of Mesoporous and Nanorod CeVO<Subscript>4</Subscript> without Template

A simple and efficient method has been established for the selective synthesis of mesoporous and nanorod CeVO₄ with different precursors by sonochemical method. CeVO₄ nanorod can be simply synthesized by ultrasound irradiation of Ce(NO₃)₃ and NH₄VO₃ in aqueous solution without any surfactant or template. While mesoporous CeVO₄ with high specific surface area can be prepared with Ce(NO₃)₃, V₂O₅ and NaOH in the same way. Mesoporous CeVO₄ has a specific surface area of 122 m² g⁻¹ and an average pore size of 5.2 nm; CeVO₄ nanorods have a diameter of about 5 nm, and a length of 100–150 nm. The ultrasound irradiation and ammonia in the reactive solution are two key factors in the formation of such rod-like products. X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), thermogravimetric (TG) and differential thermal analyses (DTA), UV/vis absorption spectroscopy and Brunauer–Emmett–Teller (BET) were applied for characterization of the as-prepared products.     

Physical property characterization of bulk MgB<Subscript>2</Subscript> superconductor

We report synthesis, structure/micro-structure, resistivity under magnetic field [ρ(T)H], Raman spectra, thermoelectric power S(T), thermal conductivity κ(T), and magnetization of ambient pressure argon annealed polycrystalline bulk samples of MgB₂, processed under identical conditions. The compound crystallizes in hexagonal structure with space group P6/mmm. Transmission electron microscopy (TEM) reveals electron micrographs showing various types of defect features along with the presence of 3–4 nm thick amorphous layers forming the grain boundaries of otherwise crystalline MgB₂. Raman spectra of the compound at room temperature exhibited characteristic phonon peak at 600 cm^-1. Superconductivity is observed at 37.2 K by magnetic susceptibility χ(T), resistivity ρ(T), thermoelectric power S(T), and thermal conductivity κ(T) measurements. The power law fitting of ρ(T) give rise to Debye temperature (Θ_D) at 1400 K which is found consistent with the theoretical fitting of S(T), exhibiting Θ _D of 1410 K and carrier density of 3.81 × 10²⁸/m³. Thermal conductivity κ(T) shows a jump at 38 K, i.e., at T_c, which was missing in some earlier reports. Critical current density (J_c) of up to 10⁵ A/cm² in 1–2 T (Tesla) fields at temperatures (T) of up to 10 K is seen from magnetization measurements. The irreversibility field, defined as the field related to merging of M(H) loops is found to be 78, 68 and 42 kOe at 4, 10 and 20 K respectively. The superconducting performance parameters viz. irreversibility field (H_irr) and critical current density J_c(H) of the studied MgB₂ are improved profoundly with addition of nano-SiC and nano-diamond. The physical property parameters measured for polycrystalline MgB₂ are compared with earlier reports and a consolidated insight of various physical properties is presented.     

Anti-stokes luminescence of Zn<Subscript>0.6</Subscript>Cd<Subscript>0.4</Subscript>S solid solutions with adsorbed organic dye molecules and few-atom silver clusters

For microcrystals of Zn_0.6Cd_0.4S with adsorbed molecules of a number of organic dyes, we have observed sensitized anti-Stokes luminescence excited by radiation with wavelengths in the range 610–750 nm and flux density 10¹⁴–10¹⁵ photons/cm²·sec. The positions of the bands in the excitation spectra for such luminescence match those of the absorption spectra for the adsorbed dye molecules, which is evidence in favor of a cooperative mechanism for its appearance. We have shown that enhancement of the anti-Stokes luminescence is possible when silver atoms and few-atom clusters appear on the Zn_0.6Cd_0.4S surface in addition to the dye molecules. We hypothesize that its excitation in the latter case occurs as a result of two-photon optical transitions. These transitions occur sequentially, with transfer of an electron or the electronic excitation energy from the dye molecules to silver atoms and few-atom clusters adsorbed on the surface of Zn_0.6Cd_0.4S, creating deep localized states in the bandgap with photoionization energies 1.80–2.00 eV. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 5, pp. 617–621, September–October, 2007.     

Electronic properties of the surface of perylene tetracarboxylic acid dianhydride film upon deposition of the ultrathin conjugated layers of Pyronine B

Ultrathin conjugated layers of Pyronine B were thermally deposited in UHV on the surface of perylene tetracarboxylic acid dianhydride (PTCDA) film. The structure of unoccupied electron states located 5-20 eV above the Fermi level (E_F) and the surface potential were monitored during the Pyronine B overlayer deposition, using an incident beam of low-energy electrons according to the total current electron spectroscopy (TCS) method. Electronic work function of the PTCDA surface changed from 4.9 ± 0.1 eV, during the Pyronine B deposition due to the change of the contents of the surface layer, until it reached a stable value 4.6 ± 0.1 eV at the Pyronine B film thickness 8-10 nm. The interface dipole corresponds to electron transfer from the Pyronine B overlayer to the PTCDA surface and the polarization in the Pyronine B overlayer was found confined within approximately 1 nm near the interfaces. The edges of major bands of density of unoccupied electronic states (DOUS) of PTCDA substrate and of the Pyronine B overlayer were unaffected by the process of the interface formation. The major TCS spectral features of the Pyronine B film corresponding to the DOUS band edges were identified and the assignment of the π^*, σ^*(C-C) and σ^*(CC) character was suggested.     

Electrical and optical characterization of pulsed plasma of N<Subscript>2</Subscript>–H<Subscript>2</Subscript>

This paper considers the electrical and optical characterization of glow discharge pulsed plasma in N₂/H₂ gas mixtures at a pressures range between 0.5 and 4.0 Torr and discharge current between 0.2 and 0.6 A. Electron temperature and ion density measurements were performed employing a double Langmuir probe. They were found to increase rapidly as the H₂ percentage in the mixture was increased up to 20%. This increase slows down as the H₂ percentage in the gas mixture was increased above 20% at the same pressure. Emission spectroscopy was employed to observe emission from the pulsed plasma of a steady-state electric discharge. The discharge mainly emits within the range 280–500 nm. The emission consists of N₂ (C-X) 316, 336, 358 nm narrow peaks and a broad band with a maximum at λ_max = 427 nm. Also lines of N₂, N₂ ⁺ and NH excited states were observed. All lines and bands have their maximum intensity at the discharge current of 0.417 A. The intensities of the main bands and spectral lines are determined as functions of the total pressure and discharge current. Agreement with other theoretical and experimental groups was established.     

Temperature dependence of the lowest frequency <Emphasis Type="BoldItalic">E</Emphasis><Subscript><Emphasis Type="Bold">g</Emphasis></Subscript> Raman mode in laser-synthesized anatase TiO<Subscript>2</Subscript> nanopowder

Nanosized titanium dioxide (TiO₂) powder was prepared by a laser-induced pyrolysis. Specific surface area of the as-grown powder measured by BET method was 109 m²/g. The grain size (14.5 nm) estimated from these data coincides well with the crystallite size (12.3 nm) determined by XRD measurements. The average grain size (∼35 nm) obtained from the subsequent SEM measurements refers to considerable agglomeration of nanoparticles. Raman spectroscopy has been used to investigate the structural properties of TiO₂ nanopowder and its anatase structure is confirmed. The blueshift and broadening of the lowest frequency E_g Raman mode at temperature range ∼25–550 K have been analyzed using a phonon-confinement model. Dominant influence of the strong anharmonic effect at higher temperatures was demonstrated. PACS 81.07.Wx; 78.30.-j; 63.22.+m     

FMR and TEM Studies of Co and Ni Nanoparticles Implanted in the SiO<Subscript>2</Subscript> Matrix

Fused silica plates have been implanted with 40 keV Co⁺ or Ni⁺ ions to high doses in the range of (0.25–1.0) × 10¹⁷ ions/cm², and magnetic properties of the implanted samples have been studied with ferromagnetic resonance (FMR) technique supplemented by transmission electron microscopy, electron diffraction and energy dispersive X-ray spectroscopy. The high-dose implantation with 3d-ions results in the formation of cobalt and nickel metal nanoparticles in the irradiated subsurface layer of the SiO₂ matrix. Co and Ni nanocrystals with hexagonal close packing and face-centered cubic structures have a spherical shape and the sizes of 4–5 nm (for cobalt) and 6–14 nm (for nickel) in diameter. Room-temperature FMR signals from ensembles of Co and Ni nanoparticles implanted in the SiO₂ matrix exhibit an out-of-plane uniaxial magnetic anisotropy that is typical for thin magnetic films. The dose and temperature dependences of FMR spectra have been analyzed using the Kittel formalism, and the effective magnetization and g-factor values have been obtained for Co- and Ni-implanted samples. Nonsymmetric FMR line shapes have been fitted by a sum of two symmetrical curves. The dependences of the magnetic parameters of each curve on the implantation dose and temperature are presented.     

Electronic properties of the polycrystalline tin dioxide interface with conjugated organic layers

The results on the electronic structure of the unoccupied electronic states of the polycrystalline SnO₂ in the energy range from 5 eV to 25 eV above the Fermi level are presented. The modification of the electronic structure and of the surface potential upon deposition of the ultrathin films of copper phthalocyanine (CuPc) and of perylene tetracarboxylic acid dianhydride (PTCDA) film onto the SnO₂ surface were studied using the very low energy electron diffraction (VLEED) method and the total current spectroscopy (TCS) measurement scheme. A substantial attenuation of the TCS signal coming from the SnO₂ surface was observed upon formation of a 1.5–2 nm thick organic deposit layer while no new spectral features from the deposit were distinguishable. It was observed that the electronic structure typical for the organic films was formed within the organic deposit thickness range from 2 nm to 7 nm. The interfacial charge transfer was characterized by the formation of the polarization layer up to 5 nm thick in the organic films. The PTCDA deposition on SnO₂ was accompanied by the negative charge transfer onto the organic layer and to the 0.65 eV increase the surface work function. At the CuPc/SnO₂ interface, the negative charge was transferred to the SnO₂ surface and the overall surface work function decreased by 0.15 eV.     

Synthesis of nanocrystalline SnO<Subscript>2</Subscript> in supercritical water

Nanocrystalline SnO₂ was synthesized in supercritical water at 385–415°C and 30 MPa (38–106 s residence time) in a tubular flow reactor from an aqueous solution of 0.1–0.4 M SnCl₄. The conversion rate was between 53 and 81%, but increased to 97.8% when 0.1 M NaOH was added. Nanoparticles were analyzed by a series of independent analytical techniques, including TEM, Raman, XRD, SEM, EDX and FT-IR. The initial size of the particles was about 3.7 nm. After calcination at 450°C for 2 h, the particle size increased to 4 nm. The particles were of low crystallinity, as indicated by the weak Raman and XRD signals. All particles were composed of Sn and O, as verified by the EDX spectra. The crystals were tetragonal, as confirmed by the weak XRD spectrum. After calcination at 600°C for 10 h, the particle size increased to 9 nm, while high crystallinity was confirmed by Raman and XRD analyses. All the crystals had the same structure, as indicated by TEM electron diffraction patterns. Using this one-step supercritical water process, nanoparticles of SnO₂ can be conveniently produced continuously in a flow reactor in less than 2 min.     

Spectral and kinetic characteristics of CdI<Subscript>2</Subscript> and CdI<Subscript>2</Subscript>:Pb scintillators

We have studied the effect of lead dopant on the optical absorption, photoluminescence, and x-ray luminescence spectra, and the scintillation characteristics of CdI₂ at room temperature. The crystals for the study were grown by the Stockbarger-Bridgman method. Activation of CdI₂ from the melt by the compound PbI₂ leads to the appearance in the absorption spectra in the near-edge region of an activator band at 395–405 nm, which is interpreted as an A band connected with electronic transitions from the ¹S₀ state to the ³P₁ levels in the Pb²⁺ ion. For x-ray excitation, CdI₂:Pb²⁺ crystals with optimal dopant concentration (∼1.0 mol%) are characterized by a light yield with maximum in the 570–580 nm region that is an order of magnitude higher than for CdI₂ crystals in the 490–500 nm band. For α excitation, the radioluminescence kinetics for cadmium iodide is characterized by a very short (∼0.3 nsec) rise time and fast decay of luminescence, with τ₁ ≈ 4 nsec and τ₂ = 10–76 nsec. Depending on the conditions under which the crystals were obtained, the fast component fraction is 95%–99%. The crystal is characterized by a similar scintillation pulse in the case of excitation by x-ray pulses. The radioluminescence pulse shape for CdI₂:Pb in the decay stage is predominantly exponential, with luminescence decay time constants τ₁ ≈ 10 nsec and τ₂ = 200–250 nsec. This system is characterized by low afterglow, at the level for the Bi₄G₃O₁₂ scintillator. We have demonstrated the feasibility of using CdI₂:Pb as a scintillator for detecting α particles. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 6, pp. 825–830, November–December, 2008.     

Structural characteristics of ultra-low k SiO<Subscript>2</Subscript> thin films prepared using a molecular template

Nanoporous SiO₂ thin films with ultra-low dielectric constants were synthesized using a molecular template method. Uniform films with pore size between 10 and 20 nm were obtained as observed by N₂ adsorption/desorption isotherms and transmission electron microscopy. Fourier transform infrared spectroscopy (FTIR) and differential thermal analysis were carried out to investigate the effect of n-hexane washing on structural properties before and after the surface modification process. The results showed that –OH bonds were substituted with –CH₃ bonds in the films as a result of modification of trimethylchlorosilane (TMCS)/n-hexane solution. Four kinds of model were used to analyze the relationship between porosity and dielectric constant of the films, where the dielectric constant was determined from capacitance-voltage measurements. The investigation indicated that the corresponding relationship was in accord with that estimated by the Rayleigh model.