Effect of nanostructured AlN coatings on the oxidation-resistant properties of optical diamond films

Diamond film is an ultra-durable optical material with high thermal conductivity and good transmission in near-infrared and far-IR (8-14 μm) wavebands. CVD diamond is subjected to oxidation at temperature higher than 780 °C bared in air for 3 min, while it can be protected from oxidation for extended exposure in air at temperature up to 900 °C by a coating of aluminum nitride. Highly oriented AlN coatings were prepared for infrared windows on diamond films by reactive sputtering method and the average surface roughness (R_a) of the coatings was about 10 nm. The deposited films were characterized by X-ray diffraction (XRD) and atom force microscope (AFM). XRD confirmed the preferential orientation nature and AFM showed nanostructures. Optical properties of diamond films coated AlN thin film was investigated using infrared spectrum (IR) compared with that for as-grown diamond films.     

The effect of geometry and post-annealing on surface acoustic wave characteristics of AlN thin films prepared by magnetron sputtering

This paper describes experimental relationship between surface acoustic wave (SAW) properties of two-port SAW resonators based on polycrystalline aluminum nitride (AlN) thin films grown on Si substrates by using a pulsed reactive magnetron sputtering system and their geometry's parameters. Moreover, the influence of post-deposition heat treatment on SAW properties of AlN thin films was investigated at different annealing temperature (600 °C and 900 °C). The measurement results show the number of the inter-digital transducers (IDT) finger pairs (N), the number of reflectors grating pairs (R) and the IDT center-to-center distance (L) related to insertion loss of SAW resonators. The best result of insertion loss was 15.6 dB for SAW resonators with R = 160 pair, N = 5 pair and L = 750 μm. At the same geometry parameters, the SAW velocity and insertion loss were improved slightly after annealing at 600 °C and were worse for the films annealed at 900 °C by changes in the surface morphology and stress on the film.     

Microstructure and optical properties of nanocrystalline ZnO and ZnO:(Li or Al) thin films

Zinc oxide thin films (ZnO, ZnO:Li, ZnO:Al) were deposited on glass substrates by a sol-gel technique. Zinc acetate, lithium acetate, and aluminum chloride were used as metal ion sources in the precursor solutions. XRD analysis revealed that Li doped and undoped ZnO films formed single phase zincite structure in contrast to Al:ZnO films which did not fully crystallize at the annealing temperature of 550 °C. Crystallized films had a grain size under 50 nm and showed c-axis grain orientation. All films had a very smooth surface with RMS surface roughness values between 0.23 and 0.35 nm. Surface roughness and optical band tail values increased by Al doping. Compared to undoped ZnO films, Li doping slightly increased the optical band gap of the films.     

Electrical characteristics of insulating aluminum nitride MIS nanostructures

Capacitance-voltage measurements of high quality PECVD and MBE grown aluminum nitride (AlN) thin films have been performed. The prepared films have shown polycrystalline (0 0 2)-preferential orientation, and were deposited on p-type Si (1 0 0) substrates with Pt forming the metal gate in a metal-insulator-semiconductor (MIS) configuration. The structure, crystallinity, texture and insulating properties have been found to depend on film thickness and were substantially influenced by the increase of the thickness. C-V measurements of the epitaxial and PECVD films were carried out and their insulating characteristics with increasing thickness (200-1000 nm) were investigated. The epitaxial films exhibited no hysteresis in capacitance behaviour, owing to better crystalline quality over the PECVD grown ones. Capacitance curves versus bias voltage have also been acquired at different temperatures; 10 K, 30 K and 50 K for deposited polycrystalline AlN films of (0 0 2) orientation. We have found that the defects trapped in the Pt/AlN/Si structure played a key role in dominating the overall behaviour of the C-V measurement curves. The trapped charges at the interface between the AlN insulating film and Si substrate caused the capacitance characteristics to shift to negative voltages, and the estimated charge density was of the order of 10¹⁰ and 10⁸ cm⁻² eV⁻¹ for the PECVD and epitaxial samples respectively. The I-V measurements referred to space-charge conduction mechanism, and the deduced leakage current was found to be of the order of 10⁻⁹ A at 200 nm film thickness.     

Low-macroscopic field emission from silicon-incorporated diamond-like carbon film synthesized by dc PECVD

Silicon-incorporated diamond-like carbon (Si-DLC) films were deposited via dc plasma-enhanced chemical vapor deposition (PECVD), on glass and alumina substrates at a substrate temperature 300 °C. The precursor gas used was acetylene and for Si incorporation, tetraethyl orthosilicate dissolved in methanol was used. Si atomic percentage in the films was varied from 0% to 19.3% as measured from energy-dispersive X-ray analysis (EDX). The binding energies of C 1s, Si 2s and Si 2p were determined from X-ray photoelectron spectroscopic studies. We have observed low-macroscopic field electron emission from Si-DLC thin films deposited on glass substrates. The emission properties have been studied for a fixed anode-sample separation of 80 μm for different Si atomic percentages in the films. The turn-on field was also found to vary from 16.19 to 3.61 V/μm for a fixed anode-sample separation of 80 μm with a variation of silicon atomic percentage in the films 0% to 19.3%. The turn-on field and approximate work function are calculated and we have tried to explain the emission mechanism there from. It was found that the turn-on field and effective emission barrier were reduced by Si incorporation than undoped DLC.     

Influence of substrate crystallography on the room temperature synthesis of AlN thin films by reactive sputtering

A pulsed DC reactive ion beam sputtering system has been used to synthesize aluminium nitride (AlN) thin films at room temperature by reactive sputtering. After systematic study of the processing variables, high-quality polycrystalline films with preferred c-axis orientation have been grown successfully on silicon and Au/Si substrates with an Al target under a N₂/(N₂ + Ar) gas flow ratio of 55%, 2 mTorr processing pressure and keeping the temperature of the substrate holder at room temperature. The crystalline quality of the AlN layer as well as the influence of the substrate crystallography on the AlN orientation has been characterized by high-resolution X-ray diffraction (HR-XRD). Best ω-FWHM (Full Width at Half Maximum) values of the (0 0 0 2) reflection rocking curve in the 1 μm thick AlN layers are 1.3°. Atomic Force Microscopy (AFM) measurements have been used to study the surface morphology of the AlN layer and Transmission Electron Microscopy (TEM) measurements to investigate the AlN/substrate interaction. AlN grew off-axis from the Si substrate but on-axis to the surface normal. When the AlN thin film is deposited on top of an Au layer, it grows along the [0 0 0 1] direction but showing a two-domain structure with two in-plane orientations rotated 30° between them.     

Corrosion resistant surface for vanadium nitride and hafnium nitride layers as function of grain size

In this research it was studied vanadium nitride (VN) and hafnium nitride (HfN) film, which were deposited onto silicon (Si (100)) and AISI 4140 steel substrates via r.f. magnetron sputtering technique in Ar/N₂ atmosphere with purity at 99.99% for both V and Hf metallic targets. Both films were approximately 1.2±0.1 µm thick. The crystallography structures that were evaluated via X-ray diffraction analysis (XRD) showed preferential orientations in the Bragg planes VN (200) and HfN (111). The chemical compositions for both films were characterized by EDX. Atomic Force Microscopy (AFM) was used to study the morphology; the results reveal grain sizes of 78±2 nm for VN and 58±2 nm for HfN and roughness values of 4.2±0.1 nm for VN and 1.5±0.1 nm for HfN films. The electrochemical performance in VN and HfN films deposited onto steel 4140 were studied by Tafel polarization curves and impedance spectroscopy methods (EIS) under contact with sodium chloride at 3.5 wt% solution, therefore, it was found that the corrosion rate decreased about 95% in VN and 99% for HfN films in relation to uncoated 4140 steel, thus demonstrating, the protecting effect of VN and HfN films under a corrosive environment as function of morphological characteristics (grain size).     

Structural and optical properties of RF magnetron sputtered aluminum nitride films without external substrate heating

We report structural and optical properties of aluminum nitride (AlN) thin films prepared by RF magnetron sputtering. A ceramic AlN target was used to sputter deposit AlN films without external substrate heating in Ar-N₂ (1:1) ambient. The X-ray diffraction and high resolution transmission electron microscopy results revealed that the films were preferentially oriented along c-axis. Cross-sectional imaging revealed columnar growth perpendicular to the substrate. The secondary ion mass spectroscopy analysis confirmed that aluminum and nitrogen distribution was uniform within the thickness of the film. The optical band gap of 5.3 eV was evaluated by UV-vis spectroscopy. Photo-luminescence broad band was observed in the range of 420-600 nm with two maxima, centered at 433 nm and 466 nm wavelengths related to the energy states originated during the film growth. A structural property correlation has been carried out to explore the possible application of such important well oriented nano-structured two-dimensional semiconducting objects.     

Sensitisation of erbium emission by silicon nanocrystals-doped SnO2

SnO₂ thin films undoped and doped with antimony (Sb), erbium (Er) and Si nanocrystals (Si-nc) have been grown on silicon (Si) substrate using sol-gel method. Room-temperature photoluminescence (PL) measurement of undoped SnO₂, under excitation at 280 nm, shows only one broad emission at 395 nm, which is related to oxygen vacancies. The PL of Er³⁺ ions was found to be enhanced after doping SnO₂ with Sb and Si-nc. The excitation process of Er is studied and discussed. The calculation of cross-section suggests a sensitisation of Er PL by Si-nc.     

Effect of doping on structural,optical and electrical properties of nanostructure ZnO films deposited onto a-Si:H/Si heterojunction

We investigated the structural; optical and electrical properties of ZnO thin films as the n-type semiconductor for silicon a-Si:H/Si heterojunction photodiodes. The ZnO film forms the front contact of the super-strata solar cell and has to exhibit good electrical (high conductivity) and optical (high transmittance) properties. In this paper we focused our attention on the influence of doping on device performance. The results show that the X-ray diffraction (XRD) spectra revealed a preferred orientation of the crystallites along c-axis. SEM images show that all films display a granular, polycrystalline morphology and the ZnO:Al exhibits a better grain uniformity. The transmittance of the doped films was found to be higher when compared to undoped ZnO. A low resistivity of the order of 2.8 × 10⁻⁴ Ω cm is obtained for ZnO:Al using 0.4 M concentration of zinc acetate. The photoluminescence (PL) spectra exhibit a blue band with two peaks centered at 442 nm (2.80 eV) and 490 nm (2.53 eV). It is noted that after doping the ZnO films a shift of the band by 22 nm (0.15 eV) is recorded and a high luminescence occurs when using Al as a dopant. Dark I–V curves of ZnO/a-Si:H/Si structure showed large difference, which means there is a kind of barrier to current flow between ZnO and a-Si:H layer. Doping films was applied and the turn-on voltages are around 0.6 V. Under reverse bias, the current of the ZnO/a-Si:H/Si heterojunction is larger than that of ZnO:Al/a-Si:H/Si. The improvement with ZnO:Al is attributed to a higher number of generated carriers in the nanostructure (due to the higher transmittance and a higher luminescence) that increases the probability of collisions.     

Self filling of Ni nanoparticles in amorphous AlN nanotubes and its field emission property

Unique aluminum nitride amorphous nanotubes filled with Ni nanoparticles have been successfully synthesized through the reaction of NH₃ over Ni-Al thin film at 1000 °C, which is similar to the extended vapor-liquid-solid technique. The X-ray diffraction and high-resolution transmission electron microscopic results are in good agreement with the amorphous nature of AlN nanotubes and crystallinity of Ni nanoparticles. The AlN nanotubes were having average diameter 35 nm and length ∼4 μm, whereas the Ni nanoparticles were having 5 nm in diameter. The unique structure showed excellent field emission property and high electrical conductivity ∼0.43 kmho/m at room temperature. The mechanism of good field emission property has been explained in detail.     

Field electron emission from HfNxOy thin films deposited by direct current sputtering

HfN_xO_y thin films were deposited on Si substrates by direct current sputtering at room temperature. The samples were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD). SEM indicates that the film is composed of nanoparticles. AFM indicates that there are no sharp protrusions on the surface of the film. XRD pattern shows that the films are amorphous. The field electron emission properties of the film were also characterized. The turn-on electric field is about 14 V/μm at the current density of 10 μA/cm², and at the electric field of 24 V/μm, the current density is up to 1 mA/cm². The field electron emission mechanism of the HfN_xO_y thin film is also discussed.     

Highly conductive and transparent laser ablated nanostructured Al: ZnO thin films

Al doped ZnO thin films are prepared by pulsed laser deposition on quartz substrate at substrate temperature 873 K under a background oxygen pressure of 0.02 mbar. The films are systematically analyzed using X-ray diffraction, atomic force microscopy, micro-Raman spectroscopy, UV-vis spectroscopy, photoluminescence spectroscopy, z-scan and temperature-dependent electrical resistivity measurements in the temperature range 70-300 K. XRD patterns show that all the films are well crystallized with hexagonal wurtzite structure with preferred orientation along (0 0 2) plane. Particle size calculations based on XRD analysis show that all the films are nanocrystalline in nature with the size of the quantum dots ranging from 8 to 17 nm. The presence of high frequency E₂ mode and longitudinal optical A₁ (LO) modes in the Raman spectra suggest a hexagonal wurtzite structure for the films. AFM analysis reveals the agglomerated growth mode in the doped films and it reduces the nucleation barrier of ZnO by Al doping. The 1% Al doped ZnO film presents high transmittance of ∼75% in the visible and near infrared region and low dc electrical resistivity of 5.94 × 10⁻⁶ Ω m. PL spectra show emissions corresponding to the near band edge (NBE) ultra violet emission and deep level emission in the visible region. Nonlinear optical measurements using the z-scan technique shows optical limiting behavior for the 5% Al doped ZnO film.     

Structural, electrical and piezoelectric properties of LiNbO3 thin films for surface acoustic wave resonators applications

In this work, 0.30 μm thick LiNbO₃ layers have been deposited by sputtering on nanocrystalline diamond/Si and platinised Si substrates. The films were then analyzed in terms of their structural and optical properties. Crystalline orientations along the (0 1 2), (1 0 4) and (1 1 0) axes have been detected after thermal treatment at 500 °C in air. The films were near-stoichiometric and did not reveal strong losses or diffusion in lithium during deposition or after thermal annealing. Pronounced decrease of the roughness on top of the LiNbO₃ layer and at the interface between LiNbO₃ and diamond was also observed after annealing, compared to the bare nanocrystalline diamond on Si substrate. Furthermore, ellipsometry analysis showed a better density and a reduced thickness of the surface layer after post-deposition annealing. The dielectric constant and losses have been measured to 50 and less than 3.5%, respectively, for metal/insulator/metal structures with 0.30 μm thick LiNbO₃ layer. The piezoelectric coefficient d₃₃ was found to be 7.1 pm/V. Finally, we succeeded in switching local domain under various positive and negative voltages.     

A comparative study on structural and optical properties of ZnO and Al-doped ZnO thin films obtained by ultrasonic spray method using different solvents

Transparent conducting ZnO and Al doped ZnO thin films were deposited on glass substrate by ultrasonic spray method. The thin films with concentration of 0.1 M were deposited at 350 °C with 2 min of deposition time. The effects of ethanol and methanol solution before and after doping on the structural, optical and electrical properties were examined. The DRX analyses indicated that ZnO films have nanocrystalline nature and hexagonal wurtzite structure with (1 0 0) and (0 0 2) preferential orientation corresponding to ZnO films resulting from methanol and ethanol solution, respectively. The crystallinity of the thin films improved with methanol solution after doping to (0 0 2) oriented. All films exhibit an average optical transparency about 90%, in the visible range. The band gaps values of ZnO thin films are increased after doping from 3.10 to 3.26 eV and 3.27 to 3.30 eV upon Al doping obtained by ethanol and methanol solution, respectively. The electrical conductivity increase from 7.5 to 15.2 (Ω cm)⁻¹ of undoped to Al doped ZnO thin films prepared by using ethanol solution. However, for the methanol solution; the electrical conductivity of the film is stabilized after doping.     

Effects of Si doping on the structural and electrical properties of Ge2Sb2Te5 films for phase change random access memory

The effects of Si doping on the structural and electrical properties of Ge₂Sb₂Te₅ film are studied in detail. Electrical properties and thermal stability can be improved by doping small amount of Si in the Ge₂Sb₂Te₅ film. The addition of Si in the Ge₂Sb₂Te₅ film results in the increase of both crystallization temperature and phase-transition temperature from face-centered cubic (fcc) phase to hexagonal (hex) phase, however, decreases the melting point slightly. The crystallization activation energy reaches a maximum at 4.1 at.% and then decreases with increasing dopant concentration. The electrical conduction activation energy increases with the dopant concentration, which may be attributed to the increase of strong covalent bonds in the film. The resistivity of Ge₂Sb₂Te₅ film shows a significant increase with Si doping. When doping 11.8 at.% of Si in the film, the resistivity after 460 °C annealing increases from 1 to 11 mΩ cm compared to the undoped Ge₂Sb₂Te₅ film. Current-voltage (I-V) characteristics show Si doping may increase the dynamic resistance, which is helpful to writing current reduction of phase-change random access memory.     

Microstructural,dielectric and magnetic behavior of spin-deposited nanocrystalline nickel–zinc ferrite thin films for microwave applications

Nanocrystalline nickel ferrite and zinc doped nickel ferrite thin films with general composition Ni_1−xZn_xFe₂O₄; x=0.0, 0.2 and 0.5 were fabricated by the spin-deposition technique. Citrate precursor method was adopted to prepare coating solution used for film deposition. This method resulted in single phase, transparent, homogeneous and crack-free nanocrystalline ferrite thin films at annealing temperature as low as 400 °C. The substrates used for film deposition were ITO-coated 7059 glass, fused quartz and Si (1 0 0). The thickness of films was found to be in the range ∼1000–5500 Å. The surface microstructure and morphology investigated by atomic force microscopy (AFM) confirmed the grain size of nickel–zinc ferrite films to be in nanometer range indicating nanocrystalline nature of the films. Dielectric properties such as the real (∈′) and imaginary parts (∈″) of complex permittivity were measured in the X-band microwave frequency region (8–12 GHz) by employing extended cavity perturbation technique. The M–H hysteresis measurements on the films annealed at 650 °C revealed narrow hysteresis curves with H_c and M_s varying for different compositions.     

Structural and mechanical characteristics of (1 0 3) AlN thin films prepared by radio frequency magnetron sputtering

The (1 0 3)-oriented aluminum nitride (AlN) thin film is an attractive piezoelectric material for the applications in surface acoustic wave and film bulk acoustic wave resonator devices. In this work, we repot structural and mechanical characteristics of (1 0 3) AlN thin films deposited onto (1 0 0) Si substrates with radio frequency magnetron sputtering at different sputtering powers at 150, 250, and 350 W. Comparisons were made on their crystalline structures with X-ray diffraction, surface morphologies with atomic force microscopy, mechanical properties with nanoindentation, and tribological responses with nanoscratch. Results indicate that for the sputtering power of 350 W, a high-quality (1 0 3) AlN thin film, whose hardness is 18.91 ± 1.03 GPa and Young's modulus is 242.26 ± 8.92 GPa, was obtained with the most compact surface condition.     

Synthesis and characterization of Ni-doped ZnO: A transparent magnetic semiconductor

We report synthesis of a transparent magnetic semiconductor by incorporating Ni in zinc oxide (ZnO) matrix. ZnO and nickel-doped zinc oxide (ZnO:Ni) thin films (∼60 nm) are prepared by fast atom beam (FAB) sputtering. Both undoped and doped films show the presence of ZnO phase only. The Ni concentration (in at%) as determined by energy dispersive X-ray (EDX) technique is ∼12±2%. Magnetisation measurement using a SQUID magnetometer shows that the Ni-doped films are ferromagnetic, having coercivity (H_c) values 192, 310 and 100 Oe and saturation magnetization (M_s) values of 6.22, 5.32 and 4.73 emu/g at 5, 15 and 300 K, respectively. The Ni-doped film is transparent (>80%) across visible wavelength range. Resistivity of the ZnO:Ni film is ∼2.5×10⁻³ Ω cm, which is almost two orders of magnitude lower than the resistivity (∼4.5×10⁻¹ Ω cm) of its undoped counterpart. Impurity d-band splitting is considered to be the cause of increase in conductivity. Interaction between free charges generated by doping and localized d spins of Ni is discussed as the reason for ferromagnetism in the ZnO:Ni film.     

Effect of indium doping in CdO thin films prepared by spray pyrolysis technique

Preparation of transparent and conducting indium doped CdO thin films by spray pyrolysis on glass substrate is reported for various concentration of indium (2-8 wt%) in the spray solution. The electrical, optical and structural properties of indium doped CdO films were investigated using different techniques such as Hall measurement, optical transmission, X-ray diffraction and scanning electron microscope. X-ray analysis shows that the undoped CdO films are preferentially orientated along (2 0 0) crystallographic direction. Increase of indium doping concentration increases the films packing density and reorient the crystallites along (1 1 1) plane. A minimum resistivity of 4.843×10⁻⁴ Ω cm and carrier concentration of 3.73×10²⁰ cm⁻³ with high transmittance in the range 300-1100 nm were achieved for 6 wt% indium doping. The band gap value increases with doping concentration and reaches a maximum of 2.72 eV for 6 wt% indium doping from 2.36 eV of that of undoped film. The minimum resistivity achieved in the present study is found to be the lowest among the reported values for In-doped CdO films prepared by spray pyrolysis method.