Epitaxial growth of Sc-doped ZnO films on Si by sol-gel route

The epitaxial growth of doped ZnO films is of great technological importance. Present paper reports a detailed investigation of Sc-doped ZnO films grown on (1 0 0) silicon p-type substrates. The films were deposited by sol-gel technique using zinc acetate dihydrate as precursor, 2-methoxyethanol as solvent and monoethanolamine (MEA) as a stabilizer. Scandium was introduced as dopant in the solution by taking 0.5 wt%¹ of scandium nitrate hexahydrate. The effect of annealing on structural and photoluminescence properties of nano-textured Sc-doped films was investigated in the temperature range of 300-550 °C. Structural investigations were carried out using X-ray diffraction, scanning electron microscopy and atomic force microscopy. X-ray diffraction study revealed that highly c-axis oriented films with full-width half maximum of 0.21° are obtained at an annealing temperature of 400 °C. The SEM images of ZnO:Sc films have revealed that coalescence of ZnO grains occurs due to annealing. Ostwald ripening was found to be the dominant mass transport mechanism in the coalescence process. A surface roughness of 4.7 nm and packing density of 0.93 were observed for the films annealed at 400 °C. Room temperature photoluminescence (PL) measurements of ZnO:Sc films annealed at 400 °C showed ultraviolet peak at about (382 nm) with FWHM of 141 meV, which are comparable to those found in high-quality ZnO films. The films annealed below or above 400 °C exhibited green emission as well. The presence of green emission has been correlated with the structural changes due to annealing. Reflection high energy electron diffraction pattern confirmed the nearly epitaxial growth of the films.     

From Zn microspheres to hollow ZnO microspheres: A simple route to the growth of large scale metallic Zn microspheres and hollow ZnO microspheres

Large scale metallic Zn microspheres and hollow ZnO microspheres are synthesized by thermal evaporation and vapor transport by heating a ZnO/graphite mixture at 1000 °C. Firstly, metallic Zn microspheres are fabricated with diameters in the range of 1–10 μm. The Zn microspheres are then annealed at 600 °C in air, which form hollow semiconducting ZnO microspheres. EDX and XRD spectra reveal that the oxidized material is indeed ZnO. Room temperature photoluminescence spectra of the oxidized material show a sharp peak at 380 nm and a wider broad peak centered at 490 nm. This growth mechanism is discussed and further investigated for other metallic and metal oxide microstructures.     

Synthesis and field emission of patterned ZnO nanorods

A simple and self-catalytic method has been developed for synthesizing finely patterned ZnO nanorods on ITO-glass substrates under a low temperature of 500 °C. The patterned ZnO nanorod arrays, a unit area is of 400 × 100 μm², are synthesized via vapor phase transport method. The surface morphology and composition of the as-synthesized ZnO nanorods are characterized by means of scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX). The mechanism of formation of ZnO nanorods is also discussed. The measurement of field emission (FE) reveals that the as-synthesized ZnO nanorods arrays have a turn-on field of 3.3 V/μm at the current density of 0.1 μA/cm² and a low threshold field of 6.2 V/μm at the current density of 1 mA/cm². So this approach must have a potential application of fabricating micropatterned oxide thin films used in FE-based flat panel displays.     

Annealing effect on the superconductivity of In2O3–ZnO thin films

We have investigated the relation among ρ–T characteristics, superconductivity, annealing conditions and the crystallinity of polycrystalline (In₂O₃)_1−x–(ZnO)_x films. We annealed as-grown amorphous films in air by changing annealing temperature and time. It is found that the films annealed at 200 °C or 300 °C for a time over 0.5 h shows the superconductivity. Transition temperature T_c and the carrier density n are T_c < 3.3 K and n ≈ 10²⁵–10²⁶ m⁻³, respectively. Investigations for films with x = 0.01 annealed at 200 °C have revealed that the T_c, n and crystallinity depend systematically on annealing time. Further, we consider that there is a suitable annealing time for sharp resistive transition because the transition width becomes wider with longer annealing times. We studied the upper critical magnetic field H_c2(T) for the film with different annealing time. From the slope of dH_c2/dT for all films, we have obtained the resistivity ρ dependence of the coherence length ξ(0) at T = 0 K.     

Thermal annealing effects on I–V–T characteristics of sputtered Cr/n-GaAs diodes

Sputtered Cr/n-GaAs Schottky diodes have been prepared and annealed at 200 and 400 °C. The current–voltage (I–V) characteristics of the as-deposited and annealed diodes have been measured in the temperature range of 60–320 K with steps of 20 K. The effect of thermal annealing on the temperature-dependent I–V characteristics of the diodes has been investigated experimentally. The ideality factor and barrier height (BH) values for 400 °C annealed diode approximately remain unchanged from 120 to 320 K, and those of the as-deposited sample from 160 to 320 K. The departures from ideality at low temperatures have been ascribed to the lateral fluctuations of the BH. The BH values of 0.61 and 0.74 eV for the as-deposited and 400 °C annealed diodes were obtained at room temperature, respectively. A Richardson constant value of 9.83 A cm⁻² K⁻² for 400 °C annealed Schottky diode, which is in close agreement with the known value of 8.16 A cm⁻² K⁻² for n-type GaAs. Furthermore, T₀ anomaly values of 15.52, 10.68 and 5.35 for the as-deposited and 200 and 400 °C annealed diodes were obtained from the nT versus T plots. Thus, it has been seen that the interface structure and quality improve by the thermal annealing at 400 °C.     

Ordered ultra thin ZnO films on metal substrate

Ultra thin ZnO films were prepared on metal Mo(1 1 0) substrate under ultrahigh vacuum conditions either by depositing Zn in 10⁻⁵ Pa oxygen or by oxidizing pre-deposited Zn films. The films were characterized in situ by various surface analytical techniques, including Auger electron spectroscopy, X-ray and ultraviolet photoelectron spectroscopies, low energy electron diffraction and high resolution electron energy loss spectroscopy. The results indicate that a long-range ordered and stoichiometric ZnO films are formed along its [0 0 0 1] direction. The annealing experiments show that as-prepared ZnO films are thermal stable until 800 K. This study provides constructive information to further understand the growth mechanism of ZnO films on different substrates.     

Anodization of aluminium thin films on pSi and annihilation of strong luminescence from Al2O3

Photoluminescence (PL) of Al₂O₃ films obtained by anodization of thermally evaporated and annealed thin Al films on p⁺⁺Si in 0.3 M oxalic acid has been investigated. Thermal annealing at 200–950 °C under the dry nitrogen atmosphere was used for deactivation of luminescence centres. Luminescence from as grown films was broad and located at 425 nm. This luminescence reached to highest level after annealing at 600 °C. Maximum 10 min was required for full optical activation and prolonged annealing up to 4 h did not change the luminescence intensity. Because of deep levels, absorption band edge of as grown films was shifted to the lower energy which is 3.25 eV. Annealing above 800 °C reduced the PL intensity and this observation was correlated with the blue shift of band edge as the defects annealed out. Disappearing PL intensity and blue shift of band edge absorption after annealing at 950 °C was mainly attributed to the oxygen-related defects and partly to impurities that may be originated from oxalic acid. AFM results did not show any hexagonally ordered holes but uniformly distributed nanosized Al₂O₃ clusters that were clearly seen. XRD measurements on as grown Al₂O₃ showed only [1 1 0] direction of α phase. Debye–Scherer calculation for this line indicates that cluster size is 35.7 nm. XRD and AFM pictures suggest that nanocrystalline Al₂O₃ are embedded in amorphous Al₂O₃.     

Effects of Cr dopant on the microstructure and electromigration performance of Cu interconnects

Cu and Cu(Cr) alloy films were deposited on SiO₂ substrates by magnetron sputtering. The microstructure and electromigration performance of films were investigated. A small amount of Cr refines the Cu grains and improves the surface morphology of Cu films. After annealing at 450 °C, in contrast to the Cu film with large lateral grown grains, the Cu(Cr) alloy film exhibits fine columnar grains with a 1 1 1 preferred orientation. Most of Cr in the annealed Cu(Cr) film has segregated at the film surface and the film/substrate interface. The grain boundary grooving at the film/substrate interface is completely prohibited for Cu(Cr) films. As a result, the electromigration lifetimes of annealed Cu(Cr) lines are 10–100 times longer than those of annealed Cu lines. The final resistivity of the annealed Cu(Cr) film is 2.55 μΩ cm which is close to that of the annealed Cu film. With the improved surface morphology and high electromigration resistance, the dilute Cu(Cr) alloy film can be a viable interconnect material or a seed layer in the Cu-damascene technology.     

Post-annealing influence on properties of N-In codoped ZnO thin films prepared by ion beam enhanced deposition method

N-In codoped ZnO thin films were prepared by ion beam enhanced deposition method (IBED) and were annealed in nitrogen and oxygen ambient after deposition. The influence of post-annealing on structure, electrical and optical properties of thin films were investigated. As-deposited and all post-annealed samples showed preferential orientation along (0 0 2) plane. Electrical property studies indicated that the as-deposited ZnO film showed p-type with a sheet resistance of 67.5 kΩ. For ZnO films annealed in nitrogen with the annealing temperature increasing from 400 to 800 °C, the conduction type of the ZnO film changed from p-type to n-type. However, for samples annealed in oxygen the resistance increased sharply even at a low annealing temperature of 400 °C and the conduction type did not change. Room temperature PL spectra of samples annealed in N₂ and in O₂ showed UV peak located at 381 and 356 nm, respectively.     

Grain size refinement and magnetostriction of ferromagnetic shape memory Fe–Pd–Rh alloys

This paper reports the forging of bulk ferromagnetic shape memory (FSM) Fe–30Pd–2Rh (at%) alloys to a 40% reduction in thickness, followed by thermal annealing at 950–1100 °C for various times and quenching in ice brine to induce recrystallization (i.e. grain size refinement). Investigation with the Vickers microhardness test reveals that the process of recrystallization results in increased ductility of the fine grains. TEM and magnetostriction investigations reveal two kinds of twins contained in the strain-forged sample annealed at 950 °C for 3 h, i.e. deformation and transformation twins, and these twins also improved a higher magnetostriction as well as ductility in the alloys that may be useful in magneto-mechanical applications (such as microactuator or spring).     

Si-nanostructures formation in amorphous silicon nitride SiNx:H deposited by remote PECVD

The formation of silicon nanoclusters embedded in amorphous silicon nitride (SiN_x:H) can be of great interest for optoelectronic devices such as solar cells. Here amorphous SiN_x:H layers have been deposited by remote microwave-assisted chemical vapor deposition at 300 °C substrate temperature and with different ammonia [NH₃]/silane [SiH₄] gas flow ratios (R=0.5−5). Post-thermal annealing was carried out at 700 °C during 30 min to form the silicon nanoclusters. The composition of the layers was determined by Rutherford back scattering (RBS) and elastic recoil detection analysis (ERDA). Fourier transform infrared spectroscopy (FTIR) showed that the densities of SiH (2160 cm⁻¹) and NH (3330 cm⁻¹) molecules are reduced after thermal annealing for SiN:H films deposited at flow gas ratio R>1.5. Breaking the SiH bonding provide Si atoms in excess in the bulk of the layer, which can nucleate and form Si nanostructures. The analysis of the photoluminescence (PL) spectra for different stoichiometric layers showed a strong dependence of the peak characteristics (position, intensity, etc.) on the gas flow ratio. On the other hand, transmission electron microscopy (TEM) analysis proves the presence of silicon nanoclusters embedded in the films deposited at a gas flow ratio of R=2 and annealed at 700 °C (30 min).     

Influence of annealing temperature on structural and optical properties of ZnO: In thin films prepared by ultrasonic spray technique

Transparent conducting indium doped zinc oxide was deposited on glass substrate by ultrasonic spray method. The In doped ZnO samples with indium concentration of 3 wt.% were deposited at 300, 350 and 400 °C with 2 min of deposition time. The effects of substrate temperature and annealing temperature on the structural, electrical and optical properties were examined. The DRX analyses indicated that In doped ZnO films have polycrystalline nature and hexagonal wurtzite structure with (0 0 2) preferential orientation and the maximum average crystallite size of ZnO: In before and annealed at 500 °C were 45.78 and 55.47 nm at a substrate temperature of 350 °C. The crystallinity of the thin films increased by increasing the substrate temperature up 350 °C, the crystallinity improved after annealing temperature at 500 °C. The film annealed at 500 °C and deposited at 350 °C show lower absorption within the visible wavelength region. The band gap energy increased from E_g = 3.25 to 3.36 eV for without annealing and annealed films at 500 °C, respectively, indicating that the increase in the transition tail width. This is due to the increase in the electrical conductivity of the films after annealing temperature.     

Optical and structural properties of Eu-diffused and doped ZnO nanowires

Single crystal ZnO nanowires diffused with europium (Eu) from a solid source at 900 °C for 1 h or doped with Eu during growth have been characterized. The ZnO nanowires were grown by chemical vapor deposition on Si substrates employing Au as a catalyst. The diameter of the resulting nanowires was 200 nm with a length of 1 μm. Photoluminescence spectra excited by a He–Cd laser at room temperature showed the green luminescence at 515 nm in Eu-diffused nanowires. A small red shift of near-band-edge emission of ZnO nanowires was observed in the diffused wires, but sharp emission from Eu³ ions was not present. Transmission electron microscopy shows crystalline Eu₂O₃ formation on the diffused nanowire surface, which forms a coaxial heterostructure system. When Eu was incorporated during the nanowire growth, the sharp ⁵D_O–⁷F₂ transition of the Eu³⁺ ion at around 615 nm was observed.     

Electrical characterisation of phosphorus-doped ZnO thin films grown by pulsed laser deposition

Phosphorus-doped ZnO films were grown by pulsed laser deposition using a ZnO:P₂O₅-doped target as the phosphorus source with the aim of producing p-type ZnO material. ZnO:P layers (with phosphorus concentrations of between 0.01 to 1 wt%) were grown on a pure ZnO buffer layer. The electrical properties of the films were characterised from temperature dependent Hall-effect measurements. The samples typically showed weak n-type conduction in the dark, with a resistivity of 70 Ω cm, a Hall mobility of μ_n0.5 cm² V ⁻¹ s⁻¹ and a carrier concentration of n3×10¹⁷ cm⁻³ at room temperature. After exposure to an incandescent light source, the samples underwent a change in conduction from n- to p-type, with an increase in mobility and decrease in concentration for temperatures below 300 K.     

Effect of the synthesis route on the structural properties and shape of the indium oxide (In2O3) nano-particles

Nano-crystalline indium oxide (In₂O₃) particles have been synthesized by sol–gel and hydro-thermal techniques. A simple hydro-alcoholic solution consisting indium nitrate hydrate and citric acid (in sol–gel method) and 1, 4-butandiol (in hydro-thermal method) have been utilized. The structural properties of indium oxide nano-powders annealed at 450 °C (for both methods) have been characterized by the X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and specific surface area (SSA) analysis. Structural analysis of the samples shows cubic phase in sol–gel and cubic-hexagonal phase mixture in hydro-thermally prepared particles. The nano-particles prepared by sol–gel method have nearly spherical shape, whereas hydro-thermally-made ones display wire- and needle-like shape in addition to the spherical shape. The obtained In₂O₃ nano-particles surface areas were 23.2 and 55.3 in sol–gel and hydro-thermal methods, respectively. The optical direct band gap of In₂O₃ nano-particles were determined to be 4.32 and 4.24 eV for sol–gel and hydro-thermal methods, respectively. These values exhibit 0.5 eV blue shift from that the bulk In₂O₃ (3.75 eV), which is related to the particle size reduction and approaching the quantum confinement limit of nano-particles.     

Influence of annealing temperature on the properties of ZnO thin films deposited by thermal evaporation

ZnO thin films were deposited by thermal evaporation of a ZnO powder. The as-deposited films are dark brown, rich zinc and present a low transmittance. Then, these films were annealed in air atmosphere at different temperatures between 100 and 400 °C. Their microstructure and composition were studied using XRD and RBS measurements respectively. By increasing the temperature, it was found that film oxidation starts at 250 °C. XRD peaks related to ZnO appear and peaks related to Zn decrease. At 300 °C, zinc was totally oxidised and the films became totally transparent. The electrical conductivity measurement that were carried out in function of the annealing temperature showed the transition from highly conductive Zn thin film to a lower conductive ZnO thin film. The optical gap (E_g) was deduced from the UV-vis transmittance, and its variation was linked to the formation of ZnO.     

Dimensional evolution of silicon nanowires synthesized by Au–Si island-catalyzed chemical vapor deposition

This study explores the nucleation and morphological evolution of silicon nanowires (Si-NWs) on Si (0 0 1) and (1 1 1) substrates synthesized using nanoscale Au–Si island-catalyzed rapid thermal chemical vapor deposition. The Au–Si islands are formed by Au thin film (1.2–3.0 nm) deposition at room temperature followed by annealing at 700 °C, which are employed as a liquid-droplet catalysis during the growth of the Si-NWs. The Si-NWs are grown by exposing the substrates with Au–Si islands to a mixture of gasses SiH₄ and H₂. The growth temperatures and the pressures are 500–600 °C and 0.1–1.0 Torr, respectively. We found a critical thickness of the Au film for Si-NWs nucleation at a given growth condition. Also, we observed that the dimensional evolution of the NWs significantly depends on the growth pressure and temperature. The resulting NWs are 30–100 nm in diameter and 0.4–12.0 μm in length. For Si (0 0 1) substrates 80% of the NWs are aligned along the 1 1 1 direction which are 30° and 60° with respect to the substrate surface while for Si (1 1 1) most of the NWs are aligned vertically along the 1 1 1 direction. In particular, we observed that there appears to be two types of NWs; one with a straight and another with a tapered shape. The morphological and dimensional evolution of the Si-NWs is significantly related to atomic diffusion kinetics and energetics in the vapor–liquid–solid processes.     

The order with respect to oxygen and the activation energy for the burning of an anthracitic char in O2 in a fluidised bed, as measured using a rapid analyser for CO and CO2

Measurements of the oxidation of a coal char in a fluidised bed have the advantages that the rates of heat and mass transfer to and from a reacting particle are large and characterised well. However, problems have arisen from a combination of the slow, but typical, response–time (4 s) of the analysers for CO and CO₂ and the slow mixing of gases when filling a fairly large fluidised bed. The resulting time constant for the sampling system was 8 s and comparable to the time for combustion at 900 °C or above. The purpose of this work was to measure the kinetics of oxidation of a char in a smaller fluidised bed (with a shorter mixing time) using an analyser for CO and CO₂ with a response time as low as 0.1 s. The result is that the oxidation of an anthracitic char is now found to be first order in O₂ between 700 and 900 °C; at 900 °C the order previously measured was almost zero. The activation energy is now measured here to be 145 ± 25 kJ/mol, in agreement with some early work.     

Effect of surface roughness of TiO2 films on short-circuit current density of photoelectrochemical cell of ITO/TiO2/PVC-LiClO4/graphite

This paper reports the effect of surface topography of titanium dioxide films on short-circuit current density of photoelectrochemical solar cell of ITO/TiO₂/PVC-LiCLO₄/graphite. The films were deposited onto ITO-covered glass substrate by screen-printing technique. The films were tempered at 300 °C, 350 °C, 400 °C, 450 °C and 500 °C for 30 min to burn out the organic parts and to achieve the films with porous structure. The surface roughness of the films were studied using scanning electron microscope (SEM). Current–voltage relationship of the devices were characterized in dark at room temperature and under illumination of 100 mW cm⁻² light from tungsten halogen lamp at 50 °C. The device utilising the TiO₂ film annealed at 400 °C produces the highest short-circuit current density and open-circuit voltage as it posses the smoothest surface topography with the electrolyte. The short-circuit current density and open-circuit voltage of the devices increase with the decreasing grain size of the TiO₂ films. The short-circuit current density and open-circuit voltage are 0.6 μA/cm² and 109 mV respectively.     

Transparent conductive ZnO:Ga films prepared by DC reactive magnetron sputtering at low temperature

Ga-doped ZnO (ZnO:Ga) transparent conductive films were deposited on glass substrates by DC reactive magnetron sputtering. The structural, electrical, and optical properties of ZnO:Ga films were investigated in a wide temperature range from room temperature up to 400 °C. The crystallinity and surface morphology of the films are strongly dependent on the growth temperatures, which in turn exert an influence on the electrical and optical properties of the ZnO:Ga films. The film deposited at 350 °C exhibited the relatively well crystallinity and the lowest resistivity of 3.4 × 10⁻⁴ Ω cm. More importantly, the low-resistance and high-transmittance ZnO:Ga films were also obtained at a low temperature of 150 °C by changing the sputtering powers, having acceptable properties for application as transparent conductive electrodes in LCDs and solar cells.