GISAXS study of Si nanoclusters in SiO/SiO2 layers

We present a study on amorphous SiO/SiO₂ superlattice using grazing-incidence small-angle X-ray scattering (GISAXS). Such nanostructured material might be of great interest for photovoltaic conversion and optoelectronics. Amorphous SiO/SiO₂ superlattices were prepared by magnetron sputtering of thin SiO and SiO₂ films (20 layers each) on Si (1 0 0) substrate. Rotation of the Si substrate during evaporation ensures homogeneity of the films over the whole substrate. After the evaporation, the samples were annealed at 1100 °C for 1 h in vacuum. The analysis of the 2-D GISAXS pattern has shown that Si nanocrystals are formed in the remaining SiO₂ films in the annealed samples. From the 2-D GISAXS pattern, their shape, size and inter-particle distance are determined.     

GISAXS study of Si nanocrystals formation in SiO2 thin films

We present a study on amorphous SiO/SiO₂ superlattice using grazing incidence small-angle X-ray scattering (GISAXS). Amorphous SiO/SiO₂ superlattices were prepared by high vacuum evaporation of 3 nm thin films of SiO and SiO₂ (10 layers each) on Si(100) substrate. After the evaporation, samples were annealed at 1100 °C for 1 h in vacuum, yielding Si nanocrystals formation. Using a Guinier approximation, the shape and the size of the crystals were obtained.     

Effects of annealing atmosphere and substrate on the photoluminescence and Raman scattering from Si nanocrystals in a SiO2 matrix

Thin films of SiO _x have been prepared on quartz or c-Si substrates by thermal evaporation of SiO in vacuum and post-annealed at 1373 K in an argon or hydrogen atmosphere. High-resolution electron microscopy has shown the existence of silicon nanocrystals in the annealed films, and this result has been confirmed by Raman scattering. Photoluminescence has been observed from annealed films and attributed to radiative recombination in Si nanocrystals. Its intensity is appreciably higher upon annealing in Ar than in H₂. It is shown that substrates strongly affect the Raman scattering from Si nanocrystals in nc-Si–SiO₂ thin films with low filling factors.     

Nanocrystalline Si formation in the a-Si/Al system on polyimide and silicon dioxide substrates

Polysilicon (poly-Si) films fabricated on flexible substrates are of considerable interest because of their potential application in flexible displays. In this study, an 800 nm layer of amorphous silicon (a-Si), followed by a 20 nm layer of aluminum (Al), were deposited on polyimide/silicon and silicon dioxide/silicon (SiO₂/Si) substrates. Samples on polyimide were rapid thermal annealed at 900 °C for 20 s, while those on SiO₂/Si were vacuum annealed at temperatures between 200 and 600 °C for 1 h. Film properties were analyzed using Rutherford backscattering spectrometry, cross-section transmission electron microscopy, and X-ray diffraction. Silicon films containing nanocrystallites and pores were obtained, with a pore formation activation energy (E_A) of 0.59 eV. A short-range self-diffusion model is proposed for the formation of Si crystallites in cases where the solid-solubility limit for Si dissolution into Al has not been reached.     

On the optical properties of Mn/SiO and SiO thin films

The ultraviolet, visible and infrared properties of unannealed and annealed amorphous Mn/SiO cermet thin films (300 to 1000 nm thick) prepared by vacuum evaporation at 5.0×10^–4 Pa are investigated. The ultraviolet and visible results are analysed assuming optical absorption by indirect transitions. A systematic reduction of the optical energy gap and an increase in the width of the band-tail region is observed with increasing metallic content. The effects of the ratio deposition rate/residual pressure and substrate temperature on the optical properties of SiO _x (1<x<2) thin films are also investigated.     

Growth and vacuum post-annealing effect on the properties of the new absorber CuSbS2 thin films

Post-growth treatments in vacuum atmosphere were performed on CuSbS₂ films prepared by the single-source thermal evaporation method on glass substrates. The films were annealed in vacuum atmosphere for 2 h in temperature range 130-200 °C. The effect of this thermal treatment on the structural, optical and electrical properties of the films was studied. X-ray diffraction (XRD) patterns indicated that the films exhibited an amorphous structure for annealing temperature below 200 °C and a polycrystalline structure with CuSbS₂ principal phase. For the films annealed at temperatures below 200 °C one direct optical transition in range 1.8-2 eV was found. For the films annealed at 200 °C, two optical direct transitions emerged at 1.3 and 1.79 eV corresponding to the CuSbS₂ and Sb₂S₃ values respectively. The electrical measurements showed a conversion from low resistivities (3.10^− 2-9.10^− 2) Ω cm for the samples annealed at temperatures below 200 °C to relatively high resistivities (2 Ω cm) for the samples annealed at 200 °C. In all cases the samples exhibited p-Ztype conductivity.     

Ellipsometric characterization of SiOx films with embedded Si nanoparticles

In this work we present results on the ellipsometric study of SiO_x films in the spectral range of 280-820 nm. The films were deposited by vacuum thermal evaporation of SiO onto Si substrates heated at 150 °C. To stimulate the formation of silicon clusters in the oxide matrix the films were annealed at temperatures 700, 1000 and 1100 °C in argon for 5, 15 and 30 min. By applying the Bruggeman effective-medium approximation theory and using multiple-layer optical models, from the ellipsometric data analysis the thickness, complex refractive index and composition of the films, as well as the size of the embedded Si nanocrystallites have been determined. Atomic-force microscopy imaging showed a very smooth surface, the roughness value of which correlated well with the top-layer thickness, determined from the ellipsometric data analysis.     

Synthesis of mono and bi-layer of Si nanocrystals embedded in a dielectric matrix by e-beam evaporation of SiO/SiO2 thin films

Si nanocrystals (ncs) were synthesized by e-beam evaporation of SiO/SiO₂ multilayer structures and subsequent annealing at high temperatures. We focused our attention on the possibility to manipulate the ncs dimension by changing the SiO layer thickness. Time of flight secondary ion mass spectrometry and X-ray photoelectron spectroscopy analyses of the annealed samples indicated that the thermal treatment induces a phase separation in the SiO layer. The formation of Si nanocrystals was confirmed by high-resolution transmission electron microscopy, although in the thinnest layers (below 2 nm) the Si clusters are probably amorphous. Preliminary results indicate that a similar approach is suitable also for synthesizing Ge nanocrystals.     

Ferroelectricity of ultrathin ferroelectric Langmuir-Blodgett polymer films on conductive LaNiO3 electrodes

LaNiO₃ (LNO) films with a surface roughness rms of 0.384 nm and a sheet resistance of about 200 Ω were prepared on SrTiO₃ and Si/SiO₂ substrates respectively by rf magnetron sputtering technique. The surface of LNO on Si/SiO₂ substrate is smoother than that on SrTiO₃ substrate. A nominal 2-monolayer (ML) poly(vinylidenefluoride-trifluoroethylene) film with a thickness of about 3 nm was deposited on LNO coated Si/SiO₂ substrate by Langmuir-Blodgett (LB) technology. Piezoresponse force microscopy (PFM) measurements show that the LB films demonstrate an obvious feature of polarization switching and good voltage durability. The results suggest that the ultrathin polymer films may be utilized to explore ferroelectric tunnel junctions.     

Influence of substrate doping on the surface chemistry and morphology of Copper Phthalocyanine ultra thin films on Si (111) substrates

16 nm thick Copper Phthalocyanine (CuPc) films were deposited at room temperature in Ultra High Vacuum onto “n” and “p” type doped Si(111) substrates covered with a native SiO₂ overlayer. Atomic Force Microscopy indicates that the two substrates are both atomically flat (0.15 nm root mean square roughness). Angle dependent X-ray photoemission spectroscopy shows that the thickness of the native SiO₂ over-layer is 0.8 nm (both for the “n” and “p” type Si substrate). Despite the identity of the substrate roughness, of the SiO₂ thickness, and of the CuPc film growth conditions, the organic films (made out of crystallites in the α-phase, as checked with X-ray Diffraction) grown on the “p” and “n” type substrate show clearly different morphological features (determined with Atomic Force Microscopy and Scanning Electron Microscopy measurements). While the CuPc film on “p” Si(111) shows a compact network of densely packed crystallites with sizes (along the substrate plane) ranging from 50 to 100 nm, the CuPc film on “n” Si(111) shows a slightly more open network of larger crystallites (with 75-150 nm size range). Accordingly, the CuPc film roughness is 0.67 nm and 1.15 nm for the “p” and “n” type substrate respectively. Due to the increased surface to volume effects (lower crystallite size) affecting the CuPc film on “p” Si(111), this film exhibits stronger interaction with oxygen and water vapor of the ambient air, as determined by photoemission spectroscopy experiments performed on samples as grown “in situ” and after prolonged (1 year) exposure to air.     

Structural characterization of thin amorphous Si films

We present a study of structural changes occurring in thin amorphous silicon (a-Si). The a-Si films were deposited on single-crystalline Si substrates held at room temperature or 200 °C by magnetron sputtering of a Si target in pure Ar atmosphere, and therefore the films were hydrogen-free. All samples were annealed in vacuum and subsequently studied by EPR and GISAXS. A strong decrease in the dangling bonds content at lower annealing temperatures, and then an increase of it at around 550 °C, suggested significant structural changes. In parallel the samples were studied by GISAXS which confirmed changes at the nanometric scale attributed to voids in the material. A nice correlation of the results of the two techniques shows advantages of this approach in the analysis of structural changes in a-Si material.     

Investigation of structural properties of ITO thin films deposited on different substrates

The influence of the substrate nature on the structure and morphology of ITO thin films grown by thermal evaporation in vacuum is investigated. The as-prepared metal films with Sn/In molar ratio of 0.1 were subsequently annealed for 2 h at 723 K in air (to obtain tin doped indium oxide), then annealed in vacuum at 523 K, followed by UV irradiation (to reduce the electrical resistivity). Irrespective of substrate nature, XRD data evidence a (222) preferential orientation in films. Substrate nature, annealing in vacuum and UV irradiation influence the structure, morphology, optical, electrical and surface wetting properties of the films' surface.     

Damping properties of epoxy-based composite embedded with sol–gel-derived Pb(Zr<Subscript>0.53</Subscript>Ti<Subscript>0.47</Subscript>)O<Subscript>3</Subscript> thin film annealed at different temperatures

Pb(Zr_0.53Ti_0.47)O₃ (PZT) thin films were prepared on Pt/Ti/SiO₂/Si substrate by sol–gel method. The effect of annealing temperature on microstructure, ferroelectric and dielectric properties of PZT films was investigated. When the films were annealed at 550–850 °C, the single-phase PZT films were obtained. PZT films annealed at 650–750 °C had better dielectric and ferroelectric properties. The sandwich composites with epoxy resin/PZT film with substrate/epoxy resin were prepared. The annealing temperature of PZT films influenced their damping properties, and the epoxy-based composites embedded with PZT film annealed at 700 °C had the largest damping loss factor of 0.923.     

Growth of Cu2ZnSnS4 thin films on Si (100) substrates by multisource evaporation

Cu₂ZnSnS₄ films were grown on Si (100) by vacuum evaporation using elemental Cu, Sn, S and binary ZnS as sources. X-ray diffraction patterns of films grown at different substrate temperatures indicated that polycrystalline growth was suppressed and the orientational growths were relatively induced in a film grown at higher temperatures. Tetragonal structure of Cu₂ZnSnS₄ films was confirmed by studying RHEED patterns. The existence of c-axis ([001] direction) growth, two kinds of a-axis (〈100〉 direction) growth and four kinds of {112} twins which can be classified as two symmetrical pairs is proposed. Broad emissions at around 1.45 eV and 1.31 eV were observed in the photoluminescence spectrum measured at 13 K.     

Role of oxygen in enhancing N-type conductivity of CuInS2 thin films

Post-growth treatments in air atmosphere were performed on CuInS₂ films prepared by the single-source thermal evaporation method. Their effect on the structural, optical and electrical properties of the films was studied by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), optical reflection and transmission and resistance measurements. The films were annealed from 100 to 350 °C in air. The stability of the observed N-type conductivity after annealing depends strongly on the annealing temperature. Indeed it is shown that for annealing temperatures above 200 °C the N-type conductivity is stable. The resistance of the N-CuInS₂ thin films correlates well with the corresponding annealing temperature. The samples after annealing have direct bandgap energies of 1.45-1.50 eV.     

Composition of alumina films grown on Si at low temperature with catalytic CVD

The X-ray photoelectron spectroscopy (XPS) measurements have been used to reveal the compositions of alumina (Al₂O₃) films formed on Si wafers using tri-methyl aluminium (TMA) and molecular oxygen (O₂) with catalytic chemical vapour deposition (Cat-CVD). The atomic ratio (O/Al) for Al₂O₃ samples formed at substrate temperature of 200-400 °C has been obtained to be 1.4 which is close to stoichiometry. The increase of growth rate at substrate temperatures below 200 °C and above 400 °C can be attributed to formation of aluminum oxides with non-stoichiometry and metallic aluminum incorporated in the films resulting from deficient oxygen. Angle resolved XPS measurements have revealed that the alumina/Si interface with no SiO₂ film has been obtained at substrate temperatures below 200 °C.     

Epitaxial growth and relaxation of γ-Al2O3 on silicon

0.5-10 nm-thick single crystal γ-Al₂O₃ films was epitaxially grown, at high temperature, on Si(001) and Si(111) substrates using electron-beam evaporation techniques. Reflection High Energy Electron Diffraction studies showed that the Al₂O₃ films grow pseudomorphically on Si (100) up to thickness of 2 nm. For higher thicknesses, a cubic to hexagonal surface phase transition occurs. Epitaxial growth and relaxation were also observed for Si(111). The film surfaces are smooth and the oxide-Si interfaces are atomically abrupt without interfacial layers.     

Improved dielectric properties of chemical solution derived Pb0.5Sr0.5TiO3 thin films by a layer-by-layer annealing method

Pb_0.5Sr_0.5TiO₃ thin films were prepared on Pt/TiO₂/SiO₂/Si and LaNiO₃ (LNO)/Si substrates by using chemical solution deposition technique, and a layer-by-layer annealing method was used in an attempt to improve the dielectric properties of the thin films. The structure, dielectric, and ferroelectric properties of the thin films were investigated. Improved dielectric properties of the thin films were clearly confirmed: the dielectric constant and dielectric loss for the films on Pt/TiO₂/SiO₂/Si substrates annealed at 650 °C were 1064 and 0.027, respectively, at 1 kHz, with a dielectric tunability of more than 50%; similarly, the films prepared on LNO/Si substrates, showed a high dielectric constant of 1280 and a low dielectric loss of 0.023, at 1 kHz. P-E hysteresis loop measurements indicated that the remanent polarization and coercive field for the films on Pt/TiO₂/SiO₂/Si substrates annealed at 650 °C were 15.7 μC/cm² and 51 kV/cm, respectively.     

Nanoporous TiO2 thin film based conductometric H2 sensor

Nanoporous titanium dioxide (TiO₂) based conductometric sensors have been fabricated and their sensitivity to hydrogen (H₂) gas has been investigated. A filtered cathodic vacuum arc (FCVA) system was used to deposit ultra-smooth Ti thin films on a transducer having patterned inter-digital gold electrodes (IDTs). Nanoporous TiO₂ films were obtained by anodization of the titanium (Ti) thin films using a neutral 0.5% (wt) NH₄F in ethylene glycol solution at 5 V for 1 h. After anodization, the films were annealed at 600 °C for 8 h to convert the remaining Ti into TiO₂. The scanning electron microscopy (SEM) images revealed that the average diameters of the nanopores are in the range of 20 to 25 nm. The sensor was exposed to different concentrations of H₂ in synthetic air at operating temperatures between 100 °C and 300 °C. The sensor responded with a highest sensitivity of 1.24 to 1% of H₂ gas at 225 °C.     

The effect of sputtering gas pressure on structure and photocatalytic properties of nanostructured titanium oxide self-cleaning thin film

Titanium oxide thin films were deposited by DC reactive magnetron sputtering on ZnO (80 nm thickness)/soda-lime glass and SiO₂ substrates at different gas pressures. The post annealing on the deposited films was performed at 400 °C in air atmosphere. The results of X-ray diffraction (XRD) showed that the films had anatase phase after annealing at 400 °C. The structure and morphology of deposited layers were evaluated by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The surface grain size and roughness of TiO₂ thin films after annealing were around 10-15 nm and 2-8 nm, respectively. The optical transmittance of the films was measured using ultraviolet-visible light (UV-vis) spectrophotometer and photocatalytic activities of the samples were evaluated by the degradation of Methylene Blue (MB) dye. Using ZnO thin film as buffer layer, the photocatalytic properties of TiO₂ films were improved.