Transmission electron microscopy study of Ni–Si nanocomposite films

Nickel induced crystallization of amorphous Si (a-Si) films is investigated using transmission electron microscopy. Metal-induced crystallization was achieved on layered films deposited onto thermally oxidized Si(3 1 1) substrates by electron beam evaporation of a-Si (400 nm) over Ni (50 nm). The multi-layer stack was subjected to post-deposition annealing at 200 and 600 °C for 1 h after the deposition. Microstructural studies reveal the formation of nanosized grains separated by dendritic channels of 5 nm width and 400 nm length. Electron diffraction on selected points within these nanostructured regions shows the presence of face centered cubic NiSi₂ and diamond cubic structured Si. Z-contrast scanning transmission electron microscopy images reveal that the crystallization of Si occurs at the interface between the grains of NiSi₂ and a-Si. X-ray absorption fine structure spectroscopy analysis has been carried out to understand the nature of Ni in the Ni–Si nanocomposite film. The results of the present study indicate that the metal induced crystallization is due to the diffusion of Ni into the a-Si matrix, which then reacts to form nickel silicide at temperatures of the order of 600 °C leading to crystallization of a-Si at the silicide–silicon interface.     

Structure and oxidation resistance of plasma sprayed Ni–Si coatings on carbon steel

Ni–Si coatings consisting of mainly NiSi₂ and NiSi were deposited on a carbon steel by air plasma spraying. Isothermal oxidation tests of the carbon steel substrates with the Ni–Si coatings at 500–800 °C have been carried out. The result indicated that a protective SiO₂-based oxide scale was formed on the surface of the coatings after oxidation. On the other hand, during oxidation, phase transformation occurred among the NiSi₂, NiSi and Ni₂Si phases constructing the Ni–Si coatings. This was caused by the extraction of silicon from the silicides and the reformation of silicides at the silcide/Si-blocks interface. Above 700 °C, the outward diffusion of iron and carbon became very fast and consequently decarburization happened at the coating/substrates interface, which induced the formation of pores in the substrates near the interface. In addition, grain boundary oxidation of Cr in the steel substrate was observed above 700 °C.     

Thermal and ion-induced dissociation of NiSi and NiSi2 in contact with nickel

The interaction of nickel with NiSi and NiSi₂ was investigated using backscattering spectrometry and glancing angle X-ray diffraction. With nickel films deposited onto NiSi or NiSi₂, Ni₂Si was formed at the original compound-nickel interface by the dissociation of the compounds on annealing at temperatures of about 300 °C. The dissociation of NiSi and NiSi₂ into Ni₂Si has also been observed when the samples were irradiated with argon ions. We attribute similarities in the two processes to the presence of thermodynamic forces in ion-induced reactions and the dependence of the radiation-enhanced migration on the intrinsic diffusion properties in the system.     

Atomic layer deposition and post-deposition annealing of PbTiO3 thin films

Lead titanate thin films were deposited by atomic layer deposition on Si(100) using Ph₄Pb and Ti(O-i-Pr)₄ as metal precursors and O₃ and H₂O as oxygen sources. The influence of the Ti : Pb precursor pulsing ratio on the film growth, stoichiometry and quality was studied at two different temperatures, i.e. 250 and 300 °C. Uniform and stoichiometric films were obtained using a Ti : Pb precursor pulsing ratio of 1 : 10 at 250 °C or 1 : 28 at 300 °C. The as-deposited films were amorphous but the crystalline PbTiO₃ phase was obtained by rapid thermal annealing at 600-900 °C both in N₂ and O₂ ambient. Thin PbTiO₃ films were visually uniform and roughness values for as-deposited and annealed films were observed by atomic force microscopy.     

Self-limiting low-temperature growth of crystalline AlN thin films by plasma-enhanced atomic layer deposition

We report on the self-limiting growth and characterization of aluminum nitride (AlN) thin films. AlN films were deposited by plasma-enhanced atomic layer deposition on various substrates using trimethylaluminum (TMA) and ammonia (NH₃). At 185 °C, deposition rate saturated for TMA and NH₃ doses starting from 0.05 and 40 s, respectively. Saturative surface reactions between TMA and NH₃ resulted in a constant growth rate of ~ 0.86 Å/cycle from 100 to 200 °C. Within this temperature range, film thickness increased linearly with the number of deposition cycles. At higher temperatures (≥ 225 °C) deposition rate increased with temperature. Chemical composition and bonding states of the films deposited at 185 °C were investigated by X-ray photoelectron spectroscopy. High resolution Al 2p and N 1s spectra confirmed the presence of AlN with peaks located at 73.02 and 396.07 eV, respectively. Films deposited at 185 °C were polycrystalline with a hexagonal wurtzite structure regardless of the substrate selection as determined by grazing incidence X-ray diffraction. High-resolution transmission electron microscopy images of the AlN thin films deposited on Si (100) and glass substrates revealed a microstructure consisting of nanometer sized crystallites. Films exhibited an optical band edge at ~ 5.8 eV and an optical transmittance of > 95% in the visible region of the spectrum.     

Carbon incorporation in chemical vapor deposited aluminum oxide films

We report results from an investigation into the nature and extent of carbon incorporation into aluminum oxide thin films deposited from the pyrolysis of dimethylaluminum isopropoxide via high-vacuum chemical vapor deposition. The chemical nature and distribution of carbon in films deposited in the 417-659 °C temperature range were investigated through X-ray photoelectron spectroscopy and Auger electron spectroscopy. Carbon composition increased with increasing deposition temperature, up to approximately 8 at.% at 659 °C. Carbon in films deposited at 477 °C was bonded only to oxygen or carbon, but films deposited above 538 °C also contained metal carbide-like bonding. Carbon content in films deposited on hydrogen-terminated Si (100) substrates increased toward the film-substrate interface, but no silicon-carbon bonding was observed.     

Effect of substrate temperature and bias voltage on the crystallite orientation in RF magnetron sputtered AlN thin films

The crystal orientation and residual stress of AlN thin films were investigated using X-ray diffraction and substrate curvature method. The AlN films were deposited on Si(100) by RF magnetron sputtering in a mixed plasma of argon and nitrogen under various substrate negative bias V_s (up to − 100 V) and deposition temperature T_s up to 800 °C. The results show that lower temperature and moderate bias favor the formation of (002) plane parallel to the substrate surface. On the contrary, strong biasing beyond − 75 V and deposition temperature higher than 400 °C lead to the growth of (100) plane. At the same time nanoindentation hardness and compressive stress measured by substrate curvature method showed significant enhancement with substrate bias and temperature. The biased samples develop compressive stress while unbiased samples exhibit tensile or compressive stress depending on plasma power and temperature. The relationships between deposition conditions and crystallographic orientation of the films are discussed in terms of surface energy minimization and ion bombardment effects.     

Characteristics of highly orientated BiFeO3 thin films on a LaNiO3-coated Si substrate by RF sputtering

BiFeO₃ (BFO) films were grown on LaNiO₃-coated Si substrate by a RF magnetron sputtering system at temperatures in the range of 300-700 °C. X-ray reflectivity and high-resolution diffraction measurements were employed to characterize the microstructure of these films. For a substrate temperature below 300 °C and at 700 °C only partially crystalline films and completely randomly polycrystalline films were grown, whereas highly (001)-orientated BFO film was obtained for a substrate temperature in the range of 400-600 °C. The crystalline quality of BFO thin films increase as the deposition temperature increase except for the film deposited at 700 °C. The fitted result from X-ray reflectivity curves show that the densities of the BFO films are slightly less than their bulk values. For the BFO films deposited at 300-600 °C, the higher the deposition temperature, the larger the remnant polarization and surface roughness of the films present.     

Effect of catalyst for nickel films for NiSi formation with improved interface roughness

Iodine is an effective catalyst to obtain homogeneous and smooth metal films with good interface properties. We adopted an iodine catalyst during the nickel film deposition by using atomic layer deposition (ALD) with bis(1-dimethylamino-2-methyl-2-butoxide)nickel [Ni(dmamb)₂] precursor and hydrogen reactant gas. The effect of iodine catalyst to nickel nucleation process was studied. The deposited films were silicided by rapid thermal process (RTP) which was performed by varying temperature from 400 °C to 900 °C in nitrogen ambient. The crystalline properties of nickel and nickel silicide films were examined by X-ray diffractometer (XRD) with various deposition temperatures. The interface properties and the surface morphology of nickel silicide films were studied by using Auger electron spectroscopy (AES) depth profile analyses and scanning electron microscopy (SEM). The experimental results showed that the iodine-catalyzed silicide film, which have a clean and smooth interface, exhibit lower resistivity, and lower leakage current density compared to that of non iodine-catalyzed films in implemented n⁺/p junction diode.     

Fabrication of low-resistivity and gold-colored TiN films by halide chemical vapor deposition with a low [NH3]/[TiCl4] flow ratio

This work describes the preparation of titanium nitride (TiN) films on Si (111) substrates by atmospheric pressure halide chemical vapor deposition (AP-HCVD). Various TiN films were obtained by exploiting TiCl₄ + NH₃ gas chemistry with flow ratios [NH₃]/[TiCl₄] from 0.2 to 1.4, and deposition temperatures (T_d) from 600 to 900 °C. When T_d = 800 °C gold-colored films with electrical resistivities of under 100 μΩ cm were formed at almost all of the investigated [NH₃]/[TiCl₄] flow ratios. In particular, a lowest resistivity of about 23.7 μΩ cm, which is quite close to that of bulk TiN, was achieved using an [NH₃]/[TiCl₄] flow ratio of 0.3. Atomic force microscopy indicated that the root mean square surface roughness of that film was only about 5.1 nm. Under the same [NH₃]/[TiCl₄] flow ratio as above, X-ray diffraction analyses revealed the presence of a cubic TiN phase with a preferred orientation of (200) for T_d ≤ 800 °C, while additional (111) and (220) orientations emerged when the film was deposited at 900 °C. In conclusion, a low resistivity (< 100 μΩ cm) TiN film can be formed by AP-HCVD with very low [NH₃]/[TiCl₄] flow ratios 0.3-1.4.     

Deposition and characterization of BN/Si(0 0 1) using tris(dimethylamino)borane

Boron nitride thin films could be deposited on Si(0 0 1) by chemical vapor deposition (CVD) at atmospheric pressure using a single source precursor. IR absorption spectra of films deposited between 750 and 1000°C using B[N(CH₃)₂]₃ (tris(dimethylamino)borane, TDMAB) as the boron and nitrogen source showed a peak absorption at ∼1360 cm⁻¹ characteristic of the in-plane vibrational mode seen in h-BN. It was noted that the mode at 800 cm⁻¹ is very weak. The observed growth rate varied exponentially with temperature in the range 850-900°C. Ellipsometry measurements were used to investigate the thickness and optical constant of the films. The refractive index, slightly lower than the bulk material, is close to 1.65-1.7 depending on the surface morphology of the films. The surface morphology of thin layers has been observed by atomic force microscopy with an increase of the surface roughness from 0.3 to 3.5 nm as the growth temperature increases from 800 to 950°C.     

Temperature dependent biaxial texture evolution in Ge films under oblique angle vapor deposition

The morphology and texture of Ge films grown under oblique angle vapor deposition on native oxide covered Si(001) substrates at temperatures ranging from 230 °C to 400 °C were studied using scanning electron microscopy, X-ray diffraction and X-ray pole figure techniques. A transition from polycrystalline to {001}<110> biaxial texture was observed within this temperature range. The Ge films grown at substrate temperatures < 375 °C were polycrystalline. At substrate temperatures of 375 °C and 400 °C, a mixture of polycrystalline and biaxial texture was observed. The 230 °C sample consisted of isolated nanorods, while all other films were continuous. The observed biaxial texture is proposed to be a result of the loss of the interface oxide layer, resulting in epitaxial deposition of Ge on the Si and a texture following that of the Si(001) substrates used. The rate of oxide loss was found to increase under oblique angle vapor deposition.     

Enhanced photoluminescence response of Er-Si nanoparticle codoped Al2O3 films by controlled synthesis in the nanoscale and thermal processing

Nanostructured Er³⁺-Si nanoparticles (NPs) codoped Al₂O₃ films were synthesized by a one step laser based deposition process which allows to form the Si NPs in situ at room temperature, and to control their size and separation with the Er ions in the nanoscale. Two different thermal annealing treatments are studied in order to optimize the photoluminescence (PL) emission: rapid thermal annealing (RTA) at 900 °C during 2 min, and conventional furnace step annealing at different temperatures up to 750 °C for 1 h. After RTA process the films show an important enhancement on the photoluminescence lifetime values which is related to a reduction of the non-radiative decay channels. Nevertheless, the Si NPs to Er ions energy transfer is strongly reduced. In contrast after conventional furnace annealing up to 700 °C, although there is only a moderate increase of the photoluminescence lifetime values, the excitation of Er ions through Si NPs is still active and as a consequence a large enhancement of the photoluminescence intensity with respect to the Er-only doped film is achieved. These different behaviours are most likely related to structural and chemical changes in the Er environment upon the different annealing processes.     

Influence of deposition temperature on structure and morphology of nanostructured SnO2 films synthesized by pulsed laser deposition

Nanostructured tin oxide thin films were deposited on the Si (100) substrate using the pulsed laser deposition technique at different substrate temperatures (300, 450 and 600 °C) in an oxygen atmosphere. The structure and morphology of the as-deposited films indicate that the film crystallinity and surface topography are influenced by the deposition temperature by changing from an almost amorphous to crystalline microstructure and smoother topography at a higher substrate temperature. The photoluminescence measurement of the SnO₂ films shows three stable emission peaks centered at respective wavelengths of 591, 554 and 560 nm with increasing deposition temperature, contributed by the oxygen vacancies.     

Growth and characterization of Bi2Se3 thin films by pulsed laser deposition using alloy target

Bi₂Se₃ thin films were deposited on the (100) oriented Si substrates by pulsed laser deposition technique at different substrate temperatures (room temperature −400 °C). The effects of the substrate temperature on the structural and electrical properties of the Bi₂Se₃ films were studied. The film prepared at room temperature showed a very poor polycrystalline structure with the mainly orthorhombic phase. The crystallinity of the films was improved by heating the substrate during the deposition and the crystal phase of the film changed to the rhombohedral phase as the substrate temperature was higher than 200 °C. The stoichiometry of the films and the chemical state of Bi and Se elements in the films were studied by fitting the Se 3d and the Bi 4d5/2 peaks of the X-ray photoelectron spectra. The hexagonal structure was seen clearly for the film prepared at the substrate temperature of 400 °C. The surface roughness of the film increased as the substrate temperature was increased. The electrical resistivity of the film decreased from 1 × 10⁻³ to 3 × 10⁻⁴ Ω cm as the substrate temperature was increased from room temperature to 400 °C.     

Ultralow surface recombination in p-Si passivated by catalytic-chemical vapor deposited alumina films

The passivation effects of AlOx films were investigated for p-type crystalline Si (c-Si) solar cells. The AlOx films were deposited on 10 Ωcm c-Si substrates by catalytic chemical vapor deposition (Cat-CVD) using tri-methyl aluminum (TMA) and O₂ at a film temperature of 230 °C. The surface recombination velocity (S₀) at the AlOx/Si interface was measured to be below 0.5 cm/s for AlOx films deposited with O₂/TMA gas flow-rate ratios of 15-35. This ultra low S₀ was achieved primarily by band bending due to the negative interface fixed-charge density (N_f) of an order of 10¹² charges/cm². The decrease in interface trapping density D_it in the negative fixed charge region assists in decreasing S₀.     

Femtosecond laser deposited zinc oxide film and its optical properties

Zinc oxide (ZnO) thin films have been grown on Si (100) substrates using a femto-second pulsed laser deposition (fsPLD) technique. The effects of substrate temperature and laser energy on the structural, surface morphological and optical properties of the films are discussed. The X-ray diffraction results show that the films are highly c-axis oriented when grown at 80 °C and (103)-oriented at 500 °C. In the laser energy range of 1.0 mJ-2.0 mJ, the c-axis orientation increases and the mean grain size decreases for the films deposited at 80 °C. The field emission scanning electron microscopy indicates that the films have a typical hexagonal structure. The optical transmissivity results show that the transmittance increases with the increasing substrate temperature. In addition, the photoluminescence spectra excited with 325 nm light at room temperature are studied. The structural properties of ZnO films grown using nanosecond (KrF) laser are also discussed.     

Interconnect and contact for nanoelectronics: Metallic TaSi2 nanowires

TaSi₂ nanowires have been synthesized on Si substrate by annealing FeSi₂ thin film and NiSi₂ films at 950 °C in an ambient containing Ta vapor whose length would be grown up to 13 μm. The metallic TaSi₂ nanowires exhibit excellent electrical properties with remarkable high failure current density of 3 × 10⁸ A cm^− 2. In addition, the growth mechanism is addressed in detail, The TaSi₂ nanowires are formed in three steps: segregation of Si atoms from the FeSi₂ thin film and NiSi₂ films underlayer to form Si base, growth of TaSi₂ nanodots on Si base, and elongation of TaSi₂ nanowire along the growth direction. This simple approach promises future applications in nanoelectronics and nano-optoelectronics.     

Deposition and characterisation of MoSi2 films

Deposition of MoSi₂ films on silicon and tantalum substrates applying pulsed laser deposition technique has been performed. Crystalline, hexagonal symmetry, MoSi₂ films were prepared directly from stoichiometric MoSi₂ tetragonal target on room temperature and heated substrates (500 °C). Textured MoSi₂ films having privileged (110) and (115) orientations and average crystallite size of about 105 nm were grown on Si(111) substrates with a good degree of axial texture (rocking curve full width half maximum of 1.5°). MoSi₂ films grown on Ta(211) substrates, instead, turned out to be polycrystalline, with an average crystallite size of about 100 nm and 50 nm on substrates kept at room temperature and at 500 °C, respectively. Vickers hardness for 1.2 μm thick MoSi₂ films on Si(111) substrates resulted to be 15 GPa both at room temperature and 500 °C, while for 0.4 μm thick MoSi₂ films on Ta(211) substrates — 26 GPa at room temperature and 30 GPa at 500 °C.     

Growth and characterization of epitaxial anatase TiO2(001) on SrTiO3-buffered Si(001) using atomic layer deposition

Epitaxial anatase titanium dioxide (TiO₂) films have been grown by atomic layer deposition (ALD) on Si(001) substrates using a strontium titanate (STO) buffer layer grown by molecular beam epitaxy (MBE) to serve as a surface template. The growth of TiO₂ was achieved using titanium isopropoxide and water as the co-reactants at a substrate temperature of 225-250 °C. To preserve the quality of the MBE-grown STO, the samples were transferred in-situ from the MBE chamber to the ALD chamber. After ALD growth, the samples were annealed in-situ at 600 °C in vacuum (10^− 7 Pa) for 1-2 h. Reflection high-energy electron diffraction was performed during the MBE growth of STO on Si(001), as well as after deposition of TiO₂ by ALD. The ALD films were shown to be highly ordered with the substrate. At least four unit cells of STO must be present to create a stable template on the Si(001) substrate for epitaxial anatase TiO₂ growth. X-ray diffraction revealed that the TiO₂ films were anatase with only the (004) reflection present at 2θ = 38.2°, indicating that the c-axis is slightly reduced from that of anatase powder (2θ = 37.9°). Anatase TiO₂ films up to 100 nm thick have been grown that remain highly ordered in the (001) direction on STO-buffered Si(001) substrates.