Formation of gold nanoparticles in heat-treated reactive co-sputtered Au-SiO2 thin films

In this work, formation of gold nanoparticles in radio frequency (RF) reactive magnetron co-sputtered Au-SiO₂ thin films post annealed at different temperatures in Ar + H₂ atmosphere has been investigated. Optical, surface topography, chemical state and crystalline properties of the prepared films were analyzed by using UV-visible spectrophotometry, atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and X-ray diffractometry (XRD) techniques, respectively. Optical absorption spectrum of the Au-SiO₂ thin films annealed at 800 °C showed one surface plasmon resonance (SPR) absorption peak located at 520 nm relating to gold nanoparticles. According to XPS analysis, it was found that the gold nanoparticles had a tendency to accumulate on surface of the heat-treated films in the metallic state. AFM images showed that the nanoparticles were uniformly distributed on the film surface with grain size of about 30 nm. Using XRD analysis average crystalline size of the Au particles was estimated to about 20 nm.     

Surface chemical states of barium zirconate titanate thin films prepared by chemical solution deposition

Ba(Zr_0.05Ti_0.95)O₃ (BZT) thin films grown on Pt/Ti/SiO₂/Si(1 0 0) substrates were prepared by chemical solution deposition. The structural and surface morphology of BZT thin films has been studied by X-ray diffraction (XRD) and scanning electron microscope (SEM). The results showed that the random oriented BZT thin film grown on Pt/Ti/SiO₂/Si(1 0 0) substrate with a perovskite phase. The SEM surface image showed that the BZT thin film was crack-free. And the average grain size and thickness of the BZT film are 35 and 400 nm, respectively. Furthermore, the chemical states and chemical composition of the films were determined by X-ray photoelectron spectroscopy (XPS) near the surface. The XPS results show that Ba, Ti, and Zr exist mainly in the forms of BZT perovskite structure.     

A comparative study of structural, compositional, thermal and optical properties of non stoichiometric (Zn,Fe)S chalcogenide pellets and thin films

Non-stiochiometric ternary chalcogenides Zn_1−xFe_xS, were prepared in the bulk form by co-precipitation of ZnS and FeS by Na₂S from aqueous solution containing FeSO₄ and ZnSO₄ and sintering of pellets of the co-precipitate repeatedly at 1073K in vacuum sealed quartz ampoules. Concomitant with the bulk form; thin fims of (Zn,Fe)S were synthesized by pyrolytic spray deposition method on quartz substrates from aqueous precursor solution containing ZnCl₂, FeCl₂ and thiourea in varying concentration under optimized conditions of substrate temperature (653K) carrier gas flowrate (11 l min⁻¹) and solution flow rate (8-6 ml min⁻¹).The structure, chemical composition, optical and thermoelectrical properties of the (bulk) pellets and thin films are studied as a function of initial solution concentration.X-ray diffraction of the pellets and thin films indicated the presence of solid solutions Zn_1−xFe_xS (sphalerite), while surface morphology as determined by SEM revealed a granular structure. Electrical resistivity of pellets and thin films, measured using two probe method (for pellets) and four probe van der Pauw method (for thin films) indicated that they are semiconducting while resistivity studies could not be carried out for a few thin films due to their high resistance (>20 MΩ).The chemical composition of the resulting solids as analyzed by X-ray fluorescence and that of thin films as analyzed by energy dispersive X-ray, reflected the composition of the solutions from which precipitation (for pellets) and deposition (for thin films) was carried out, with Fe contents up to x=0.4.SEM micrograph of pellets and thin films reveal that later have smaller grain size.Thermoelectric studies revealed that both solids and thin films possess the ability of ‘n’ as well as ‘p’ type conductivity.The diffuse optical reflectance measurements of pellets and transmittance measurements for thin films; as a function of wavelength reveal the dependence of direct optical band-gap on Fe content.     

Thin films prepared from tungstate glass matrix

Vitreous samples containing high concentrations of WO₃ (above 40% M) have been used as a target to prepare thin films. Such films were deposited using the electron beam evaporation method onto soda-lime glass substrates. These films were characterized by X-ray diffraction (XRD), perfilometry, X-ray energy dispersion spectroscopy (EDS), M-Lines and UV-vis absorption spectroscopy. In this work, experimental parameters were established to obtain stable thin films showing a chemical composition close to the glass precursor composition and with a high concentration of WO₃. These amorphous thin films of about 4 μm in thickness exhibit a deep blue coloration but they can be bleached by thermal treatment near the glass transition temperature. Such bleached films show several guided modes in the visible region and have a high refractive index. Controlled crystallization was realized and thus it was possible to obtain WO₃ microcrystals in the amorphous phase.     

BC2N薄膜的柱状生长及生长机理

应用热丝辅助等离子体化学气相沉积法(CVD)合成了表面呈柱状的BC₂N薄膜,X射线、红外及X射线电子能谱分析表明,薄膜的化学组分主要为BC₂N,B,C和N原子间互相结合成键.扫描电镜观察到,薄膜表面形貌呈排列整齐、取向一致的柱体,并且发现这种生长方式与沉积参数密切相关.最后从结合能方面讨论了柱状BC₂N的生长机理. 关键词： 2N')" href="#">BC₂N 柱状生长 CVD法     

Revisiting the physical processes of vapodeposited thin gold films on chemically modified glass by atomic force and surface plasmon microscopies

The preparation of very thin (at the scale of a few tens of nanometers) gold films by thermal evaporation and deposition on a solid substrate (glass) remains a key step for the elaboration of transparent and sensitive optical biosensors. We study the influence of the glass surface treatment and its thermal conductivity on the structure and composition of evaporated gold films. Using a combination of atomic force microscopy (AFM), high resolution surface plasmon resonance (SPR) imaging, and X-ray photoelectron spectroscopy (XPS), we demonstrate that the grafting of a layer of long chain mercaptant, using 11-mercaptoundecyltrimethoxysilane (S_ξSi), prior to gold deposition produces a drastic modification of gold inner and surface textures. A thorough investigation of AFM image topography by 2D wavelet-based segmentation method reveals the flat conical shape of the gold surface grains and their shape invariance with the glass surface chemical treatment. However, this treatment leads to a drastic decrease of the mean size and polydispersity of these grains by a factor of 2, thereby lowering the gold surface roughness. The rationale is that the combination of surface forces and thermal transfer drives the formation of homogeneous and flatter gold films.     

Morphological and optical characterization of thermally evaporated copper sulphide thin films

Thin films of Cu₂S on opaque gold layers and quartz substrates at the temperature of 393 K were deposited by a thermal evaporation technique. The surface morphology of the Cu₂S thin films at different thicknesses is investigated by AFM. It is seen that all the films are composed of highly coordinated spherical nano-sized particles well adhered to the substrate. The transmittance and reflectance spectra of Cu₂S thin films on the quartz substrate were recorded by a UV–visible spectrophotometer. The results show that the thermally evaporated Cu₂S thin films have the characteristic transmittance and reflectance suitable for optoelectronic applications. The stoichiometry and surface morphology of a grown Cu₂S thin film were confirmed by energy-dispersive X-ray spectroscopy (EDAX) and scanning electron microscopy (SEM), respectively. The dependence of the refractive index and the extinction coefficient on the photon energy for both the surface film and the opaque gold layer have been determined by ellipsometry. From the spectral behaviour of the absorption coefficient at two distinct absorption regions, a dual-band scheme of optical absorption for a Cu₂S thin film is described. The indirect and direct edges of Cu₂S are found to be about at 0.91 eV and 2.68 eV, respectively.     

Effects of annealing treatment on the formation of CO2 in ZnO thin films grown by metal-organic chemical vapor deposition

Post-growth annealing was carried out on ZnO thin films grown by metal-organic chemical vapor deposition (MOCVD). The grain size of ZnO thin film increases monotonically with annealing temperature. The ZnO thin films were preferential to c-axis oriented after annealing as confirmed by X-ray diffraction (XRD) measurements. Fourier transformation infrared transmission measurements showed that ZnO films grown at low temperature contains CO₂ molecules after post-growth annealing. A two-step reaction process has been proposed to explain the formation mechanism of CO₂, which indicates the possible chemical reaction processes during the metal-organic chemical vapor deposition of ZnO films.     

Comparative study of annealing and gold dopant effect on DC sputtered vanadium oxide films for bolometer applications

Vanadium oxide (VO_x) thin film has been widely used for IR detectors and it is one of the promising materials for THz detectors due to its high temperature coefficient of resistance (TCR) values. VO_x films with proper TCR values have also high resistance and it restricts bolometer performance especially for uncooled bolometers. To overcome this problem, deposition at elevated temperatures or annealing approach has been accepted and used but gold co-deposition approach has been proposed recently. In this study, vanadium oxide films were fabricated on high resistivity silicon substrates by reactive direct current magnetron sputtering in different O₂/Ar atmosphere at room temperature. We investigated influence of oxygen partial pressure during deposition process and fabricated VO_x thin films with sufficient TCR values for bolometer applications. In order to decrease resistivity of the deposited films, post annealing and gold doping approaches were performed separately. Effect of both post annealing process and gold doping process on structural and electrical properties of VO_x thin films deposited at room temperature were investigated and detailed comparison between these methods were presented. We obtained the best possible approach to obtain optimum conditions for the highly reproducible VO_x thin films which have the best resistivity and suitable TCR value for bolometer applications.     

Influence of assisted ion energy on surface roughness and mechanical properties of boron carbon nitride films synthesized by DIBSD

The BCN thin films were produced by dual ion beam sputtering deposition (DIBSD). The influence of assisted ion energy on surface roughness and mechanical properties of BCN films were investigated. The surface roughness was determined by atomic force microscopy (AFM) and the mechanical properties of BCN firms were evaluated by nano-indentation in N₂ gas. The composition, structure and chemical bonding of the BCN thin films were analyzed by using energy dispersive spectroscopy (EDS), transmission electron microscopy (TEM), laser Raman spectroscopy and Fourier transform infrared spectroscopy (FTIR). These films appeared as amorphous structure. As a result, the BCN films with the smoothest surface (R_a = 0.35 nm and R_p-v = 4.4 nm) and the highest nano-hardness of 30.1 GPa and elastic modulus of 232.6 GPa were obtained at 200 eV and 12 mA with N₂:Ar = 1:1, and the chemical composition of this BCN film was 81 at.% B, 14 at.% C and 5 at.% N. Moreover, several bonding states such as B-N, B-C and C-N were observed in BCN thin films.     

A significant enhancement in thermoelectric power factor of In2Te3 thin films by Se doping and Te composition tuning

Thermoelectric power factor of a material significantly relies on its electrical conductivity, thermal conductivity, and Seebeck coefficient. Herein, an attempt has been made to enhance the thermoelectric power factor of In₂Te₃ thin films by tuning their Te composition and via Se doping. The optimum Se-doping concentration and Te composition enhanced the power factor of pristine In₂Te₃ films by 14 and 7.4 times, respectively. The modified chemical composition, structural characteristics, and surface morphological features of In₂Te₃ films are observed to be pivotal in improving their thermoelectric power factor. Overall, this study offers a facile approach to control the thermoelectric power factor of In₂Te₃ thin films which is significant for their futuristic applications.     

Fabrication and characterization of indium sulfide thin films deposited on SAMs modified substrates surfaces by chemical bath deposition

In an effort to explore the optoelectronic properties of nanostructured indium sulfide (In₂S₃) thin films for a wide range of applications, the In₂S₃ thin films were successfully deposited on the APTS layers (-NH₂-terminated) modified ITO glass substrates using the chemical bath deposition technique. The surface morphology, structure and composition of the resultant In₂S₃ thin films were characterized by FESEM, XRD, and XPS, respectively. Also, the correlations between the optical properties, photocurrent response and the thickness of thin films were established. According to the different deposition mechanisms on the varying SAMs terminational groups, the positive and negative micropatterned In₂S₃ thin films were successfully fabricated on modified Si substrates surface combining with the ultraviolet lithography process. This offers an attractive opportunity to fabricate patterned In₂S₃ thin films for controlling the spatial positioning of functional materials in microsystems.     

Growth, structural and optical properties of CdxZn1−xS thin films deposited using spray pyrolysis technique

Cd_xZn_(1−x)S (x = 0, 0.2, 0.4, 0.6, 0.8, and 1) thin films were deposited by the chemical spray pyrolysis technique using a less used combination of chemicals. Depositions were done at 573 K on cleaned glass substrates. The composition, surface morphology and structural properties of deposited films were studied using EDAX, SEM and X-ray diffraction technique. XRD studies reveal that all the films are crystalline with hexagonal (wurtzite) structure and inclusion of Cd into the structure of ZnS improved the crystallinity of the films. The value of lattice constant ‘a’ and ‘c’ have been observed to vary with composition from 0.382 to 0.415 nm and 0.625 to 0.675 nm, respectively. The band gap of the thin films varied from 3.32 to 2.41 eV as composition varied from x = 0.0–1.0. It was observed that presence of small amount of cadmium results in marked changes in the optical band gap of ZnS.     

Electron beam evaporated LaF3 thin films prepared by different temperatures and deposition rates

LaF₃ thin films were prepared by electron beam evaporation with different temperatures and deposition rates. Microstructure properties including crystalline structure and surface roughness were investigated by X-ray diffraction (XRD) and optical profilograph. X-ray photoelectron spectroscopy (XPS) was employed to study the chemical composition of the films. Optical properties (transmittance and refractive index) and laser induce damage threshold (LIDT) at 355 nm of the films were also characterized. The effects of deposition rate and substrate temperature on microstructure, optical properties and LIDT of LaF₃ thin films were discussed, respectively.     

(Zr,V)N复合膜的结构、力学性能及摩擦性能研究

通过非平衡磁控溅射的方法制备了不同V含量的(Zr,V)N复合薄膜, 采用EDS, XRD, XPS, 纳米压痕仪和摩擦磨损仪等对薄膜的化学成分、微结构、力学性能及摩擦性能进行了研究. 结果表明, V的加入虽未改变ZrN的fcc晶体结构, 但使薄膜的择优取向由ZrN的(200)面转变为(Zr,V)N的(111)面. 随着V含量增加, (Zr,V)N复合膜的硬度略有升高后缓慢降低, 并在含25.8 at.%V后迅速降低. 与此同时, 薄膜的常温摩擦系数亦有小幅降低. 高温摩擦研究表明, (Zr,V)N薄膜在300 ℃时出现V₂O₃, V₂O₅ 在500 ℃后形成, 其含量也随温度的提高而增加. 薄膜的摩擦系数因V₂O₅ 的形成而得到显著降低. 关键词： (Zr,V)N 薄膜 微结构 力学性能 摩擦性能     

A study of structural, compositional and optical properties of spray-deposited non-stoichiometric (Zn,Fe)S thin films

Non-stoichiometric ternary chalcogenides (Zn,Fe)S were prepared in the film form by pyrolytic spray deposition technique, using air/nitrogen as the carrier gas. The precursor solution comprised of ZnCl₂, FeCl₂ and thiourea. The depositions were carried out under optimum conditions of experimental parameters viz. carrier gas (air/nitrogen) flow rate, concentration of precursor constituents, nozzle substrate distance and temperature of quartz substrate. The deposited thin films were later sintered in argon at 1073 K for 120 min.The structural, compositional and optical properties of the sintered thin films were studied. X-ray diffraction studies of the thin films indicated the presence of (Zn,Fe)S solid solution with prominent cubic sphalerite phase while surface morphology as determined by scanning electron microscopy (SEM) revealed a granular structure.The chemical composition of the resulting thin films as analyzed by energy dispersive X-ray analysis (EDAX) reflected the composition of the precursor solutions from which the depositions were carried out with Fe at% values ranging from 0.4 up to 33.SEM micrographs of thin films reveal that the grain sizes of the thin films prepared using air as carrier gas and N₂ as carrier gas are in the vicinity of 300 and 150 nm, respectively.The diffuse transmittance measurements for thin films, as a function of wavelength reveal the dependence of direct optical band gap on Fe content and type of phase.     

Martensitic transformation in as-grown and annealed near-stoichiometric epitaxial Ni2MnGa thin films

Magnetic shape memory nanostructures have a great potential in the field of the nanoactuators. The relationship between dimensionality, microstructure and magnetism characterizes the materials performance. Here, we study the martensitic transformation in supported and free-standing epitaxial Ni₄₇Mn₂₄Ga₂₉ films grown by sputtering on (0?0?1) MgO using a stoichiometric Ni₂MnGa target. The films have a Curie temperature of ~390 K and a martensitic transition temperature of ~120 K. Similar transition temperatures have been observed in films with thicknesses of 1, 3 and 4 μm. Thicker films (with longer deposition time) present a wider martensitic transformation range that can be associated with small gradients in their chemical concentration due to the high vapour pressure of Mn and Ga. The magnetic anisotropy of the films shows a strong change below the martensitic transformation temperature. No features associated with variant reorientation induced by magnetic field have been observed. Annealed films in the presence of a Ni₂MnGa bulk reference change their chemical composition to Ni₄₉Mn₂₆Ga₂₅. The change in the chemical composition increases the martensitic transformation temperature, being closer to the stoichiometric compound, and reduces the transformation hysteresis. In addition, sharper transformations are obtained, which indicate that chemical inhomogeneities and defects are removed. Our results indicate that the properties of Ni–Mn–Ga thin films grown by sputtering can be optimized (fixing the chemical concentration and removing crystalline defects) by the annealing process, which is promising for the development of micromagnetic shape memory devices.     

Studies on growth and characterization of ternary CdS1−xSex alloy thin films deposited by chemical bath deposition technique

Ternary alloyed CdS_1−xSe_x thin films of variable composition ‘x’ were grown by the simple and economical chemical bath deposition technique. The as-grown thin films were characterized for structural, compositional, surface morphological, optical and electrical studies. The X-ray diffraction (XRD) patterns of the sample indicated that all the samples were polycrystalline in nature with hexagonal structure. Scanning electron microscopy (SEM) micrographs showed uniform morphology with spherical shaped grains distributed over entire glass substrate. EDAX studies confirmed that the CdS_1−xSe_x films were having approximately same stoichiometry initially as well as finally. Room temperature optical measurements showed that band gap engineering could be realized in CdS_1−xSe_x thin films via modulation in composition ‘x’. Electrical resistivity of CdS_1−xSe_x thin films for various compositions was found to be low. The broad and fine tunable band gap properties of ternary CdS_1−xSe_x thin films have potential applications in opto-electronic devices.     

Optical characterization of tin containing novel chalcogen rich glassy semiconductors

Amorphous thin film materials with different compositions of Se_80?xTe₂₀Sn_x (0 ≤ x ≤ 10) system have been deposited on glass substrates by a well known thermal evaporation technique. Structural characterization of different compositions of aforementioned system has been done by Raman spectroscopy. The optical properties of thin films have been studied in the wavelength range 200–1100 nm by the utilization of the optical absorbance spectra of deposited thin films. To calculate the optical band gap from the optical absorption spectra, we have used Tauc model that follows the mechanism of allowed ‘non-direct electronic transition’. Subsequently, we have determined the energy band gap, metallization criterion and refractive index of thin films of aforesaid system. The variation in optical properties with composition has been interpreted in terms of density of defect states.     

Thin film solid oxide fuel cells

We have investigated the deposition of 91% ZrO₂ − 9% Y₂O₃ thin films by a variety of sputtering techniques for the application as electrolytes in thin film solid oxide fuel cells. The deposition by RF sputtering was accomplished by using an oxide target of the desired composition. The deposition rate in these initial tests was limited to 0.5 μm/hr and the morphology of the film was substantially modified by deposition rate and substrate temperature. Using DC magnetron sputtering we deposited metallic films from a metallic target with the desired chemical composition. We introduced oxygen into the sputtering chamber to reactively deposit the desired 91% ZrO₂ − 9% Y₂O₃ thin films; however, we encountered problems with target oxidation and growth rate reproducibility. We subsequently demonstrated that controlled oxidation of the metallic films could result in adhering, non porous yttria stabilized zirconia films. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996