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.     

Formation of Nickel Silicide Films from Nickel Acetylacetonate and Organosilicon Compounds

Nickel films were deposited from nickel acetylacetonate vapor on silicon, gallium arsenide, and germanium wafers and SiO₂/Si structures, and their composition and properties were studied. Annealing in dimethyldichlorosilane or hexamethyldisilazane vapor exerts a considerable effect on the composition and properties of Ni/Si structures. Films deposited from the gas phase containing nickel acetylacetonate and an organosilicon compound (OSC) were examined. As found by Auger electron spectroscopy with Ar⁺ion profiling of the surface, nickel silicide films can be obtained by Ni(AcAc)₂vapor deposition followed by annealing the resulting nickel film in OSC vapor and by OSC + Ni(AcAc)₂vapor deposition.     

Fabrication of scandium stabilized zirconia thin film by electrostatic spray deposition technique for solid oxide fuel cell electrolyte

A cost-effective and promising simple deposition method, electrostatic spray deposition (ESD), was used to fabricate dense scandium stabilized zirconia (ScSZ) thin films. The effect of solvent mixtures on their surface morphology was investigated. The films deposited using a mixed ethanol-butyl carbitol solvent with high boiling point showed higher smoothness compared with those deposited using ethanol and a mixture of ethanol and ethylene glycol, respectively. Single-phase ScSZ dense films were formed within 2 h at a low deposition temperature of 450 °C. Analysis of as heat-treated films using scanning electron microscope and atomic force microscope also indicated the formation of the uniform, smooth and dense thin films even at a low densification temperature. Furthermore, the ScSZ film deposited under the optimal condition showed the maximum in electrical conductivity of approximately 0.33 S cm^− 1 at a low operating temperature of 800 °C.     

Effect of filament temperature and deposition time on the formation of tungsten silicide with silane

The effect of filament temperature and deposition time on the formation of tungsten silicide upon exposure to the SiH₄ gas in a hot wire chemical vapor deposition process was studied using the techniques of cross-sectional scanning electron microscopy and Auger electron spectroscopy. At a relatively low temperature of 1500 °C, the decomposition of WSi₂ phase and the diffusion of Si towards the silicide/W interface produce a thick W₅Si₃ layer. The diffusional nature leads to a parabolic rate law for silicide growth. An exponential decrease of silicide thickness with temperature between 1600 and 2000 °C illustrates the dominance of Si evaporation at higher temperatures (T ≥ 1600 °C) over the silicide formation.     

Sol-gel synthesis of nickel oxide thin films and their characterization

Sol-gel method has been employed for the synthesis of nanocrystalline nickel oxide (NiO). The NiO powders were sintered at 400-700 °C for 1 h in an air. Thin films of sintered powders were prepared on glass substrate using spin coating technique and changes in the structural, morphological, electrical and optical properties were studied. The structural and microstructural properties of nickel oxide films were studied by means of X-ray diffraction and field emission scanning electron microscopy. Structural analysis shows that all the films are crystallized in the cubic phase and present a random orientation. Surface morphology of the nickel oxide film consists of nanocrystalline grains with uniform coverage of the substrate surface with randomly oriented morphology. The electrical conductivity showed the semiconducting nature with room temperature electrical conductivity increased from 10^− 4 to 10^− 2 (Ω cm) ^− 1 after sintering. The electron carrier concentration (n) and mobility (μ) of NiO films annealed at 400-700 °C were estimated to be of the order of 1.30 to 3.75 × 10¹⁹ cm^− 3 and 1.98 to 4.20 × 10^− 5 cm² V^− 1 s^− 1.The decrease in the band gap energy from 3.86 to 3.47 eV was observed for NiO sintered between 400 and 700 °C. These mean that the optical quality of NiO films is improved by sintering.     

Anode material properties of Ga-doped ZnO thin films by pulsed DC magnetron sputtering method for organic light emitting diodes

This study examined the anode material properties of Ga-doped zinc oxide (GZO) thin films deposited by pulsed DC magnetron sputtering along with the device performance of organic light emitting diodes (OLEDs) using GZO as the anode. The structure and electrical properties of the deposited films were examined as a function of the substrate temperature. The electrical properties of the GZO film deposited at 200 °C showed the best properties, such as a low resistivity, high mobility and high work function of 5.3 × 10^− 4Ω cm, 9.9 cm²/Vs and 4.37 eV, respectively. The OLED characteristics with the GZO film deposited under the optimum conditions showed good brightness > 10,000 cd/m². These results suggest that GZO films can be used as the anode in OLEDs, and a lower deposition temperature of 200 °C is suitable for flexible devices.     

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.     

Low-temperature atomic layer deposition of ZnO thin films: Control of crystallinity and orientation

Low-temperature atomic layer deposition (ALD) processes are intensely looked for to extend the usability of the technique to applications where sensitive substrates such as polymers or biological materials need to be coated by high-quality thin films. A preferred film orientation, on the other hand, is often required to enhance the desired film properties. Here we demonstrate that smooth, crystalline ZnO thin films can be deposited from diethylzinc and water by ALD even at room temperature. The depositions were carried out on Si(100) substrates in the temperature range from 23 to 140 °C. Highly c-axis-oriented films were realized at temperatures below ~ 80 °C. The film crystallinity could be further enhanced by post-deposition annealing under O₂ or N₂ atmosphere at 400-600 °C while keeping the original film orientation intact.     

Hysteresis-free HfO2 film grown by atomic layer deposition at low temperature

Hysteresis-free hafnium oxide films were fabricated by atomic layer deposition at 90 °C without any post-deposition annealing, and their structures and properties were compared with films deposited at 150 °C and 250 °C. The refractivity, bandgap, dielectric constant and leakage current density all increase with deposition temperature, while the growth rate and breakdown field decrease. All films are amorphous with roughly the same composition. Although the thin films deposited at the above-mentioned temperatures all show negligible hysteresis, only the 90 °C-deposited films remain hysteresis-free when the film thickness increases. The 90 °C-deposited films remain hysteresis-free after annealing at 300 °C. The hysteresis in films deposited at high temperatures increases with deposition temperature. Evidences show such hysteresis originates in the HfO₂ film instead of the interface. Based on a careful structure analysis, middle-range order is suggested to influence the trap density in the films. HfO₂ films deposited at low temperature with negligible hysteresis and excellent electrical properties have great potential for the fabrication and integration of devices based on non-silicon channel materials and in applications as tunneling and blocking layers in memory devices.     

Effects of growth variables on the properties of single crystalline ZnO thin film grown by inductively coupled plasma metal organic chemical vapor deposition

Single crystalline undoped and Ga-doped n-type zinc oxide (ZnO) films were grown on sapphire (Al₂O₃) substrates by inductively coupled plasma (ICP) metal organic chemical vapor deposition. Effects of growth variables on the structural, optical, and electrical properties of ZnO films have been studied in detail. Single crystal films with flat and smooth surfaces were reproducibly obtained, with application of sample bias and O₂ ICP. The best film properties were obtained at the growth condition of 650 °C, 400 W ICP power, − 94 V bias voltage, O/Zn (VI/II) ratio of 75. Single crystalline Ga doped n-ZnO films were also obtained, with free carrier concentration of about 1.5 × 10¹⁹/cm³ at 1 at.% Ga concentration.     

High-rate synthesis of microcrystalline silicon films using high-density SiH4/H2 microwave plasma

A high electron density (> 10¹¹ cm^− 3) and low electron temperature (1-2 eV) plasma is produced by using a microwave plasma source utilizing a spoke antenna, and is applied for the high-rate synthesis of high quality microcrystalline silicon (μc-Si) films. A very fast deposition rate of ∼ 65 Å/s is achieved at a substrate temperature of 150 °C with a high Raman crystallinity and a low defect density of (1-2) × 10¹⁶ cm^− 3. Optical emission spectroscopy measurements reveal that emission intensity of SiH and intensity ratio of H_α/SiH are good monitors for film deposition rate and film crystallinity, respectively. A high flux of film deposition precursor and atomic hydrogen under a moderate substrate temperature condition is effective for the fast deposition of highly crystallized μc-Si films without creating additional defects as well as for the improvement of film homogeneity.     

Effect of deposition temperature and thermal annealing on the dry etch rate of a-C: H films for the dry etch hard process of semiconductor devices

The effect of deposition and thermal annealing temperatures on the dry etch rate of a-C:H films was investigated to increase our fundamental understanding of the relationship between thermal annealing and dry etch rate and to obtain a low dry etch rate hard mask. The hydrocarbon contents and hydrogen concentration were decreased with increasing deposition and annealing temperatures. The I(D)/I(G) intensity ratio and extinction coefficient of the a-C:H films were increased with increasing deposition and annealing temperatures because of the increase of sp² bonds in the a-C:H films. There was no relationship between the density of the unpaired electrons and the deposition temperature, or between the density of the unpaired electrons and the annealing temperature. However, the thermally annealed a-C:H films had fewer unpaired electrons compared with the as-deposited ones. Transmission electron microscopy analysis showed the absence of any crystallographic change after thermal annealing. The density of the as-deposited films was increased with increasing deposition temperature. The density of the 600 °C annealed a-C:H films deposited under 450 °C was decreased but at 550 °C was increased, and the density of all 800 °C annealed films was increased. The dry etch rate of the as-deposited a-C:H films was negatively correlated with the deposition temperature. The dry etch rate of the 600 °C annealed a-C:H films deposited at 350 °C and 450 °C was faster than that of the as-deposited film and that of the 800 °C annealed a-C:H films deposited at 350 °C and 450 °C was 17% faster than that of the as-deposited film. However, the dry etch rate of the 550 °C deposited a-C:H film was decreased after annealing at 600 °C and 800 °C. The dry etch rate of the as-deposited films was decreased with increasing density but that of the annealed a-C:H films was not. These results indicated that the dry etch rate of a-C:H films for dry etch hard masks can be further decreased by thermal annealing of the high density, as-deposited a-C:H films. Furthermore, not only the density itself but also the variation of density with thermal annealing need to be elucidated in order to understand the dry etch properties of annealed a-C:H films.     

Optimization in fabricating bismuth telluride thin films by ion beam sputtering deposition

N-type bismuth telluride (Bi₂Te₃) thermoelectric thin films were deposited on BK7 glass substrates by ion beam sputtering method. Various substrate temperatures were tried to obtain optimal thermoelectric performance. The influence of deposition temperature on microstructure, surface morphology and thermoelectric properties was investigated. X-ray diffraction shows that the films are rhombohedral with c-axis as the preferred crystal orientation when the deposition temperature is above 250 °C. All the films with single Bi₂Te₃ phase are obtained by comparing X-ray diffraction and Raman spectroscopy. Scanning electron microscopy result reveals that the average grain size of the film is larger than 500 nm when the deposition temperature is above 300 °C. Thermoelectric properties including Seebeck coefficient and electrical conductivities were measured at room temperature, respectively. It is found that Seebeck coefficients increase from − 28 μV k^− 1 to − 146 μV k^− 1 and the electrical conductivities increase from 1.87 × 10³ S cm^− 1 to 3.94 × 10³ S cm^− 1 when the deposition temperature rose to 250 °C and 300 °C, respectively. An optimal power factor of 6.45 × 10^− 3 Wm^− 1 K^− 2 is gained when the deposition temperature is 300 °C. The thermoelectric properties of bismuth telluride thin films have been found to be strongly enhanced by increasing the deposition temperature.     

Effect of N2O/SiH4 flow ratios on properties of amorphous silicon oxide thin films deposited by inductively-coupled plasma chemical vapor deposition with application to silicon surface passivation

Silicon oxide (SiO_x) thin films have been deposited at a substrate temperature of 300 °C by inductively-coupled plasma chemical vapor deposition (ICP-CVD) using N₂O/SiH₄ plasma. The effect of N₂O/SiH₄ flow ratios on SiO_x film properties and silicon surface passivation were investigated. Initially, the deposition rate increased up to the N₂O/SiH₄ flow ratio of 2/1, and then decreased with the further increase in N₂O/SiH₄ flow ratio. Silicon oxide films with refractive indices of 1.47-2.64 and high optical band-gap values (>3.3 eV) were obtained by varying the nitrous oxide to silane gas ratios. The measured density of the interface states for films was found to have minimum value of 4.3 × 10¹¹ eV⁻¹ cm⁻². The simultaneous highest τ_eff and lowest density of interface states indicated that the formation of hydrogen bonds at the SiO_x/c-Si interface played an important role in surface passivation of p-type silicon.     

Characteristics of PbTiO3 thin films on Pt/Ti/SiO2/Si by continuous cooling process

In order to introduce a new deposition process for ferroelectric thin film, the deposition temperature was continuously cooled down from 580°C to 400°C during the deposition which we call continuous cooling process (CCP). X-ray diffraction patterns showed that the PbTiO₃ thin films deposited by the CCP and at 480°C had polycrystallinity, but at substrate temperatures of 400°C and 580°C had poor crystallinity. Scanning electron microscopy of the CCP-deposited film surface showed larger granular-like micrograins than that of the film deposited at 480°C and smaller than that of the film at 580°C. While there was no other phase formation at the PbTiO₃-Pt interface in the CCP-deposited film, resulting in a sharp interface, there was severe interface reaction at the PbTiO₃-Pt and the Pt-Si in the film deposited at 580°C, resulting in an abrupt interface. Atomic force microscopy under ambient conditions showed smoother surface of the film by the CCP than that of the films at 580°C. Furthermore, the film by the CCP had higher packing density than that of the film at 480°C. Besides enhancement of the structural properties, the CCP deposition appeared to have improved the electrical properties such as dielectric constant, dissipation factor, leak current density and polarization. In the case of the film by the CCP, polarization-electrical field measurement showed the saturation polarization of 27 Ccm^–2, remanent of 14 Ccm^–2 and coercive of 150 kV. These results indicate that the CCP in metalorganic chemical vapour deposition has a possibility for fabrication of PbTiO₃ ferroelectric thin films.     

Effect of microwave power and C2 emission intensity on structural and surface properties of nanocrystalline diamond films

Nanocrystalline diamond (NCD) films are synthesized using microwave plasma enhanced chemical vapour deposition technique at 2 × 10⁴ Pa and 600 °C with microwave power of 600-1600 W. Deposition is carried out on n-type (100) silicon wafer with Ar/H₂/CH₄ gas mixtures. The film properties are analyzed using micro Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), scanning electron microscopy and atomic force microscopy. Raman spectra show two predominant peaks centered around 1335 cm⁻¹ and 1560 cm^− 1 and two humps around 1160 cm^− 1 and 1450 cm^− 1, respectively. FTIR spectra show C:H stretching modes around 3000 cm^− 1. XRD patterns show a peak at 44° (2θ). In situ diagnostic of plasma is carried out using Optical Emission Spectroscopy. It has been observed that C₂ dimer plays an important role in the nucleation of diamond crystals during NCD film deposition and the emission intensity of C₂ can be adjusted by varying the microwave power. It has also been observed that the structural properties like growth rate, surface morphology and grain size of the growing film are dependent on the C₂ intensity during deposition.     

Lead zirconate titanate thin film capacitors on electroless nickel coated copper foils for embedded passive applications

Lead zirconate titanate (PZT, 52/48) thin film capacitors were prepared on electroless Ni coated Cu foil by chemical solution deposition for printed wiring board embedded capacitor applications. Phase development, dielectric properties, and leakage characteristics of capacitors were investigated, in particular as a function of the process temperature. Dielectric properties of the capacitors were dependent on the crystallization temperature, and capacitance densities of more than 350 nF/cm² and loss tangent of less than 0.03 were measured for capacitors crystallized below 600 °C. Lowest leakage current densities (around 2 × 10^− 7 A/cm² at 10 V direct current (DC)) and highest breakdown fields could be obtained for capacitors crystallized at 650 °C.Capacitors with different thickness and a two-layer capacitor model were used in analyzing the interface layer between PZT and the underlying electroless Ni. From the capacitance and leakage measurements, it is suggested that the interface reaction layer has low permittivity (K around 30) and high defect concentration, which has an important effect on the electrical properties of capacitors. This interface is from the reaction of the electroless nickel layer with the adjacent PZT, and may specifically be moderated by the nickel phosphide (Ni-P) phase, transformed from amorphous Ni during the annealing step.The results have significant implications for embedded capacitors in printed wiring boards. They demonstrate that the process can be tuned to produce either voltage independent capacitors with low leakage and high breakdown fields (above 30 V DC), or the more usual hysteretic, switching, ferroelectric capacitors with higher capacitance densities.     

Growth of RuO2 thin films by liquid injection atomic layer deposition

We have grown RuO₂ films by pulsed liquid injection atomic layer deposition using (Ru(thd)₂(cod)) dissolved in pyridine. The deposition process took place at 290 °C and consisted of four steps. The films exhibited smooth surface. Analysis of the films using secondary ion mass spectroscopy (SIMS) revealed low content of carbon in the films. Resistivity of the RuO₂ film at room temperature was about 160 µΩ cm.     

Effect of deposition temperature on the properties of CeO2 films grown by atomic layer deposition

Cerium oxide dielectric thin films have been grown on n-type silicon by atomic layer deposition using a monomeric homoleptic Ce^IV alkoxide precursor with water vapour. Herein we report the dielectric properties of CeO₂ films deposited from tetrakis(1-methoxy-2-methyl-2-propanolate)cerium. The resulting films exhibit permittivities in the range 25-42 at 1 MHz with a strong dependency on the deposition temperature. The microstructural origin of this behaviour has been investigated. The as-deposited films were found to be crystalline and they exhibited the cubic fluorite structure for deposition temperatures in the range 150 °C to 350 °C. Variations in the crystallite sizes are governed by the deposition temperature and have been estimated using a Debye-Scherrer analysis of the X-ray diffraction patterns. The changing crystallite size correlates with changes seen in the triply-degenerate F_2g first-order Raman line half-width at 465 cm^− 1. It is concluded that the frequency dependency of the film dielectric properties is strongly influenced by the crystallite size which in turn is governed by the growth temperature.     

The effect of annealing on Al-doped ZnO films deposited by RF magnetron sputtering method for transparent electrodes

In this study, transparent conducting Al-doped zinc oxide (AZO) films with a thickness of 150 nm were prepared on Corning glass substrates by the RF magnetron sputtering with using a ZnO:Al (Al₂O₃: 2 wt.%) target at room temperature. This study investigated the effects of the post-annealing temperature and the annealing ambient on the structural, electrical and optical properties of the AZO films. The films were annealed at temperatures ranging from 300 to 500 °C in steps of 100 °C by using rapid thermal annealing equipment in oxygen. The thicknesses of the films were observed by field emission scanning electron microscopy (FE-SEM); their grain size was calculated from the X-ray diffraction (XRD) spectra using the Scherrer equation. XRD measurements showed the AZO films to be crystallized with strong (002) orientation as substrate temperature increases over 300 °C. Their electrical properties were investigated by using the Hall measurement and their transmittance was measured by UV-vis spectrometry. The AZO film annealed at the 500 °C in oxygen showed an electrical resistivity of 2.24 × 10^− 3 Ω cm and a very high transmittance of 93.5% which were decreased about one order and increased about 9.4%, respectively, compared with as-deposited AZO film.