Superconducting properties of an NbN–SiO2 disordered system obtained by ammonolysis of NbN–SiO2 sol–gel derived coatings

Studies in superconducting properties of NbN–SiO₂ films are reported. The films were obtained through nitridation of sol–gel derived Nb₂O₅–SiO₂ coatings at 1200 °C, a process leading to the formation of disordered structures with NbN metallic grains dispersed in the insulating SiO₂ matrix. Electrical resistivity was measured with the conventional four-terminal method in the temperature range from 5 to 280 K. The samples’ superconducting properties, examined with magnetically modulated microwave absorption (MMMA), depend on the NbN/SiO₂ molar ratio and the film’s thickness.     

Effect of substrate temperature on the properties of reactively sputtered TiN/NbN multilayers

TiN/NbN multilayer coatings were deposited with various substrate temperatures by DC reactive magnetron sputtering method onto Si (111) and glass substrates. The effect of substrate temperature on the structural and optical properties of TiN/NbN multilayers was investigated by X‐ray diffraction, X‐ray photoelectron spectroscopy, Field emission scanning electron microscopy and Photoluminescence measurements. The composition was analyzed by X‐ray photoelectron spectroscopy. X‐ray diffraction results showed that the layers crystallized in cubic structure for TiN and hexagonal structure for NbN. It was found that grain size increased with increase in substrate temperature. The surface morphology of the TiN/NbN thin films showed a dense and smooth surface with substrate temperature upto 200 °C but after 300 °C, the grains became larger and coarse surface was observed. The TiN/NbN multilayer coatings exhibited the characteristic peaks centered at 180, 210 and 560 cm^‐1. Red band emission peaks were observed in the wavelength range of 700‐710 nm. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structure and electrical properties of nitrided NbN–TiN sol–gel derived films

The results of investigations of electrical conductivity and the structure of NbN–TiN thin films in a different NbN/TiN molar ratio are presented in this work. Sol–gel derived xNb₂O₅?(100?x)TiO₂ coatings (where x = 100, 90, 80, 70, 60, 50, 40, 0 mol%) were nitrided at 1200 °C to obtain NbN–TiN films. The structural transformations occurring in the films as a result of ammonolysis were studied using X-ray diffraction (XRD), atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The electrical conductivity was measured with a conventional four-terminal method in the temperature range of 5–280 K. The NbN–TiN samples exhibited a negative temperature coefficient of resistivity. The positive temperature coefficient of resistivity was observed only for the x = 0 sample. The results of conductivity versus temperature may be described on the grounds of a model proposed for a weakly disordered system. The film thickness effect on the superconducting properties was studied for x = 80 and x = 100 samples. The superconducting transition was not observed in all samples, the exception was x = 80 sample, 1050 nm in thickness. It is not clear, why all x = 100 samples do not exhibit superconducting transition in resistivity measurements. It seems to be possible, that the Josephson junction formation between NbN grains could be blocked by non-superconducting phases present in these samples.     

Accurate measurement of deposition rates for growth of Bi‐based oxide thin films

Bi‐based oxide thin films are important superconducting materials because of its wide applicability, high transition temperatures, and low toxicity. To achieve high quality Bi‐based oxide thin films by molecular beam epitaxy (MBE), the composition is a key parameter. Here, Bi, Cu, Cu/Sr and Cu/Ca thin films on glass substrates prepared by MBE have been examined by using both X‐ray reflectivity and surface profiler. The thickness and surface roughness were obtained through calculation and simulation. In comparison with the film thicknesses measured by these two methods, they are in good agreement. The lines of thickness deposition rate (R) versus source temperature (T) are according with LogR=a+b/T based on Clausius‐Clapeyron equation. Moreover, the Bi_2.1Ca_ySr_1.9‐yCuO_6+δ thin films with different composition and thickness were successfully prepared by MBE by applying the thickness deposition rate lines. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Influence of temperature on the microcrystalline structure of thermally evaporated Sb2S3 thin films

Thin films of antimony trisulfide (Sb₂S₃) were prepared by thermal evaporation under vacuum (p=5×10^–5 torr) on glass substrates maintained at various temperatures between 293 K and 523 K. Their microstructural properties have obtained by transmission electron microscopy (TEM). The electron diffraction analysis showed the occurrence of amorphous to polycrystalline transition in the films deposited at higher temperature of substrates (523 K). The polycrystalline thin films were found to have an orthorhombic structure. The interplanar distances and unit‐cell parameters were determined by high‐resolution transmission electron microscopy (HRTEM) and compared with the standard values for Sb₂S₃. The surface morphology of Sb₂S₃ thin films was investigated by scanning electron microscopy (SEM). The optical transmission spectra at normal incidence of Sb₂S₃ thin films have been measured in the spectral range of 400–1400 nm. The analysis of the absorption spectra revealed indirect energy gaps, characterizing of amorphous films, while the polycrystalline films exhibited direct energy gap. From the photon energy dependence of absorption coefficient, the optical band gap energy, E_g, were calculated for each thin films. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Some aspects of property tailoring of sol-gel derived thin SiO2 films

The sol-gel process in the dip-coating variant opens an interesting way for the production of thin metal oxide or transition metal oxide films with useful properties. This paper present result on the desposition and the characterization of thin SiO₂ films. The influence different process parameters, such as the composition and the aging behaviour of the coating solution, the withdrawal speed and the thermal treatment on important properties such as refractive index, film thickness, crystallinity and topography was tested. Viscosity and transmission measurements, Fourier transformation infrared reflection spectroscopy (FTIRS), transmission electron microscopy (TEM) and reflection high energy electron diffraction (RHEED) were used.     

Possible Ultrasonic Evidence for the Existence of Vortex-Antivortex Pairs

The attenuation of surface acoustic waves in the 700 MHz frequency range passing through 1000 Å NbN films has been measured on several NbN films. The films have a columnar structure where the columns are about 200 Å in diameter separated by 20 Å voids. In the superconducting state the attenuation does not follow the usual BCS curve. It appears to be composed of the sum of a BCS curve plus another curve which has a maximum below the superconducting transition temperature. The attenuation data may also be analyzed to yield an effective energy gap which is quenched at about one fifth of the BCS zero temperature energy gap. Tentatively, the Kosterlitz-Thouless vortex-antivortex model is used to determine the temperature dependence of an effective order parameter that yields reduced attenuation data which agree qualitatively with the experimental results.     

Structure and electrical conduction of Sb2O3 thin films

Antimony trioxide (Sb₂O₃) thin films have been deposited onto glass substrates using thermal evaporation technique at room temperature. The structural feature and surface morphology were characterized by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Sandwich‐type structures were deposited with films thickness d = 0.55 μm using evaporated electrodes of silver. Current‐voltage (J‐U) characteristics have been measured at various fixed temperatures in the range 293‐473 K. In all cases, at low electric field (E <10⁴ V/cm), ohmic behavior is observed. However, at high electric field (E >10⁴ V/cm), non‐ohmic behavior is observed. An analysis of the experimental data indicates that in the range of high‐applied electric field, the dominant conduction mechanism is space charge limited currents (SCLC). Using the relevant SCLC theory, the carrier concentration, total trap concentration and the ratio of free charge to trapped charge have been calculated and correlated with changes in the structures of antimony trioxide thin films. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Electron Energy-Loss Spectroscopy Study of the Change in the Free-Electron Density in Thin Superconducting NbN Films under Ion-Beam Irradiation

The change in the free-electron density in ultrathin (5 nm) superconducting NbN films in the initial state and after irradiation by O⁺ ions to doses of (0.1–0.9) × 10¹⁷ cm^–2 has been studied by electron energy-loss spectroscopy (EELS). The analysis has been performed on cross section samples prepared by the focused ion beam method, using plasmon oscillations with energies up to 50 eV. The radiation-induced replacement of nitrogen atoms with oxygen atoms in niobium nitride is found to change the electrical properties of the material, which leads to a decrease in the free-electron density with an increase in the irradiation dose.     

XAFS investigations of nitrided NbN–SiO2 sol–gel derived films

This work presents the results of the structural analysis of xNbN–(100-x)SiO₂ (x = 100, 80, 60 mol%) thin films by X-ray absorption spectroscopy (XAS). To prepare the films, thermal nitridation of sol–gel derived coatings have been performed. The resulting films have a granular structure with NbN grains distributed in the SiO₂ matrix. The size of the grains depends on the NbN/SiO₂ molar ratio. A detailed X-ray absorption fine structure (XAFS) data analysis shows that in all the samples both nitrogen and oxygen atoms are present as nearest neighbours of Nb. The intra-granular phase is an ordered NbN phase, whereas the shells around the grains are formed mainly by an oxide phase and, possibly, by other niobium nitride phases (probably with low nitrogen content). Two possible origins of the inter-granular oxide phase were considered: incomplete nitridation of Nb₂O₅ and addition of SiO₂. Both of them are connected with the sample preparation method. The obtained XAS results allowed us to correlate the thickness and stoichiometry of the films under study with the electronic structure of the Nb ions and with the local geometric structure in their environment.     

采用溶液沉积及快速退火制备LiMn2O4薄膜的研究

采用溶液沉积及快速退火制备了不同厚度的LiMn2O4薄膜,用X射线衍射及扫描电子显微镜检测分析薄膜的物相及形貌;采用恒电流充放电及交流阻抗技术研究了LiMn2O4薄膜的电化学性质.结果表明,制备的LiMn2O4薄膜均匀,晶粒大小相近,晶粒尺寸在20～50 nm之间.经热处理后LiMn2O4薄膜断面清晰,薄膜与基片之间扩散很轻微.随着薄膜厚度的增加,薄膜的粗糙度减小,平整度变好.不同厚度的LiMn2O4薄膜的比容量介于42～47 μAh/(cm2·μm)之间,经50次循环后,薄膜的容量损失率从0.18 μm的0.64;上升到1.04 μm的9.0;,循环性能随着薄膜厚度的增加而变差.电化学阻抗测试表明不同厚度的LiMn2O4薄膜锂离子扩散系数差别不大,数量级为10-11cm2/s.     

Optical properties and synthesis of CuInSe2 thin films by selenization of Cu/In layers

In this paper, we report the effect of annealing temperature on the properties of copper indium diselenide (CuInSe₂) thin films. The CuInSe₂ thin films were fabricated at 500 °C for 2 h by annealing Cu‐In layers (as precursors) selenized in a glass tube with pure selenium powder. The structural and morphological properties of the CuInSe₂ thin films were characterized respectively by means of x‐ray diffraction (XRD) and field‐emission scanning electron microscope (FE‐SEM). The type of CuInSe₂ thin film has been identified as direct allowed and the band gap value was determined. The study of UV/Visible/NIR absorption shows that the band gap value of CuInSe₂ thin film is about 1.07 eV, which is within an optimal range for harvesting solar radiation energy. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and characterization of manganese sulphide thin films deposited by spray pyrolysis

Manganese sulphide (MnS) thin films have been deposited onto glass substrate by a low cost spray‐pyrolysis technique at 220 °C. The as‐deposited MnS thin films have been characterized using scanning electron microscopy (SEM), energy dispersive X‐ray (EDX) spectroscopy, atomic force microscopy (AFM), X‐ray diffraction, UV visible spectroscopy and photo electrochemical (PEC) measurement. The SEM and AFM images showed that the MnS thin films were well covered onto the substrate surface. The as‐deposited raw thin film was found to be amorphous in nature and perfectly crystalline phase after annealing the sample. Optical band gap of the MnS thin films was found to vary from 3.1 to 3.21 eV and the band gap decreases with the increase in film thickness. Optical constants such as refractive index, extinction coefficient have been evaluated using reflectance and absorbance data. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

TEM investigation of precipitates in VCz GaAs crystals

Bulk GaAs crystals were grown from various Ga‐rich melts by the vapour‐pressure controlled Czochralski method in order to reduce As precipitates. The correlation of the melt composition with both, structural perfection and solid composition was examined by various methods of transmission electron microscopy (TEM). From transmission electron diffraction and diffraction contrast imaging a direct correlation between melt composition and sample properties is missing. High‐resolution TEM imaging hints to inhomogeneities only for the sample grown from a melt with a mole fraction of y = 0.492. Strain analysis of a selected defect reveals a strained crystal lattice in the surrounding of the defect. For the same sample, high angle annular dark‐field imaging and energy dispersive X‐ray spectroscopy verify the formation of precipitates. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Correlation between the method of preparation and the properties of the sol–gel HfO2 thin films

This work describes the preparation of HfO₂ thin films by the sol–gel method, starting with different precursors such as hafnium ethoxide, hafnium 2,4-pentadionate and hafnium chloride. From the solution prepared as mentioned above, thin films on silicon wafer substrates have been realized by ‘dip-coating’ with a pulling out speed of 5 cm min^?1. The films densification was achieved by thermal treatment for 10 min at 100 °C and 30 min at 450 °C or 600 °C, with a heating rate of 1 °C min^?1. The structural and optical properties of the films are determined employing spectroellipsometric (SE) measurements in the visible range (0.4–0.7 μm), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM). The main objective of this paper was to establish a correlation between the method of preparation (precursor, annealing temperature) and the properties of the obtained films. The samples prepared from pentadionate and ethoxide precursors are homogenous and uniform in thickness. The samples prepared starting from chloride precursor are thicker and proved to be less uniform in thickness. Higher non-uniformity develops in multi-deposition films or in crystallized films. A nano-porosity is present in the quasi-amorphous films as well in the crystallized one. For the samples deposited on silicon wafer, the thermal treatment induced the formation of a SiO₂ layer at the coating–substrate interface.     

Synthesis of ZnO films in different solvents and their photocatalytic activities

ZnO thin films have been successfully synthesized via the chemical bath deposition (CBD) method without using any catalysts or templates. The effects of solvents (such as water, ethanol and n‐propanol) on structure and morphology of ZnO thin films have been studied. XRD analysis showed that all ZnO thin films with wurtzite crystal structure were obtained via various solvents. SEM images showed that ZnO thin films prepared in different solvents have different sizes and morphologies. TEM images showed that crystalline ZnO samples prepared in different solvents have different growth habits. Photoluminescence and photocatalysis properties have been investigated at room temperature. ZnO thin films prepared in water showed superior photocatalytic activity in the degradation of rhodamine B (RhB) compared to other samples.     

Electron microscopy studies of epitaxial MgB2 superconducting thin films grown by in situ reactive evaporation

The morphology and chemistry of epitaxial MgB₂ thin films grown using reactive Mg evaporation on different substrates have been characterized by transmission electron microscopy methods. For polycrystalline alumina and sapphire substrates with different surface planes, an MgO transition layer was found at the interface region. No such layer was present for films grown on MgO and 4-H SiC substrates, and none of the MgB₂ films had any detectable oxygen incorporation nor MgO inclusions. High-resolution electron microscopy revealed that the growth orientation of the MgB₂ thin films was closely related to the substrate orientation and the nature of the intermediary layer. Electrical measurements showed that very low resistivities (several μΩ cm at 300 K) and high superconducting transition temperatures (38 to 40 K) could be achieved. The correlation of electrical properties with film microstructure is briefly discussed.     

Effect of Mn concentration and growth temperature on nanostructures and magnetic properties of Ge1−xMnx grown on Si

The nanostructures and magnetic properties of Ge_1−xMn_x thin films grown on Si substrates by molecular beam epitaxy, with different nominal Mn concentrations (1−4%) and different growth temperatures, have been systematically investigated by transmission electron microscopy and superconducting quantum interference device. It was discovered that when Ge_1−xMn_x thin films were grown at 70 °C, with increase in Mn concentration, Mn-rich tadpole shaped clusters started to nucleate at 1% Mn and become dominate in the entire film at 4% Mn. While for the thin films grown at 150 °C, tadpoles was firstly seen in the film with 1% Mn and subsequently Mn-rich secondary precipitates became dominant. The magnetic properties show specific features, which are mainly related to the nature and amount of Mn-rich clusters/precipitates within these thin films.     

Preparation of indium tin oxide thin films without external heating for application in solar cells

Indium tin oxide (ITO) films were grown without external heating in an ambient of pure argon by RF-magnetron sputtering method. The influence of argon ambient pressure on the electro-optical properties of as-deposited ITO films was investigated. The morphology, structural and optical properties of ITO films were examined and characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM) and UV–VIS transmission spectroscopy. The deposited ITO films with a thickness of 300 nm show a high transparency between 80% and 90% in the visible spectrum and 14–120 Ω/□ sheet resistance under different conditions. The ITO films deposited in the optimum argon ambient pressure were used as transparent electrical contacts for thin film Cu(In,Ga)Se₂ (CIGS) solar cells. CIGS solar cells with efficiencies of the order of 7.0% were produced without antireflective films. The results have demonstrated that the developed ITO deposition technology has potential applications in thin film solar cells.     

Crystallization of silicon thin films by current‐induced joule heating using a tungsten overcoat

A modified crystallization process using current‐induced joule heating under vacuum is presented. A thin layer of high temperature resistant tungsten was sputtered on the amorphous silicon as the conducting and annealing medium. The thin film thickness was measured by α‐stepper. The high current density provided effective means in crystallizing the amorphous silicon layer. The crystalline morphology was studied by scanning electron microscopy (SEM) after Secco‐etch, transmission electron microscopy (TEM), and x‐ray diffraction (XRD), under different annealing conditions. The grain size was controlled in the range of 0.1‐0.5 μm and could be increased with annealing time. No tungsten silicide was found. Some defects were formed due to electron‐migration effect near the electrodes. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)