Structure evolution and stoichiometry control of Pb(Zr, Ti)O3 thick films fabricated by electrospray assisted vapour deposition

Well-crystallized and stoichiometric Pb(Zr, Ti)O₃ (PZT) films, typically ∼5 μm thick, with pure perovskite-type rhombohedral structures have been successfully prepared via an electrospray assisted vapour deposition (ESAVD) method. Control of the deposition temperature within a narrow range of 300-400 °C resulted in films with the most desirable phases. PZT films with close stoichiometric match with the expected composition ratio and uniform element distribution were obtained by adding the appropriate levels of excess Pb in the precursor solutions. The annealed films were uniform, dense, compact and adherent to the substrates. The dielectric constant, ?_r, and loss tangent, tan δ, of the fabricated PZT films measured at 10 kHz were 442 and 0.09, respectively. The ESAVD deposited PZT films showed a remanent polarization, P_r, of 15.3 μC/cm² and coercive field, E_c, of 86.7 kV/cm. These results demonstrate the clear potential of the ESAVD method as a promising technique for the fabrication of thick PZT films.     

Metallo-organic decomposition derived (Ca, Sr)ZrO3 dielectric thin films on Pt coated Si substrate

Metallo-organic decomposition derived dielectric thin films of calcium zirconate doped with various concentrations of strontium ((Ca, Sr)ZrO₃) were prepared on Pt coated silicon substrate. Mainly in this paper, we present the investigations of their structural developments and present their electric and dielectric properties as well. The structural developments show that the CaZrO₃ film has amorphous structure with carbonate existing when annealed at 600 °C, while annealed at 650 °C and above, the carbonate is decomposed and those films crystallize into perovskite phase without preferred orientation. In addition, the prepared (Ca, Sr)ZrO₃ films with their Zr-O bonds affected by strontium doping are homogenous and stable as solid solutions in any concentration of strontium and all Bragg diffraction characteristics for the films shift downward with the increase in the concentration of strontium. Moreover, the electric properties show that the (Ca, Sr)ZrO₃ films have very low leakage current density and high breakdown strength; typically, the CaZrO₃ film annealed at 650 °C has the leakage current density approximately 9.5 × 10⁻⁸ A cm⁻² in the field strength of 2.6 MV cm⁻¹. Furthermore, the dielectric properties show that their dielectric constants are higher than 12.8 with very little dispersion in the frequency range from 100 Hz to 1 MHz and are independent of applied dc bias as well. The dielectric properties, in combination with the electric properties, make the materials promising candidates for high-voltage and high-reliability capacitor applications.     

Effects of rapid thermal annealing on structural, magnetic and optical properties of Ni-doped ZnO thin films

XPS depth profiles were used to investigate the effects of rapid thermal annealing under varying conditions on the structural, magnetic and optical properties of Ni-doped ZnO thin films. Oxidization of metallic Ni from its metallic state to two-valence oxidation state occurred in the film annealed in air at 600 °C, while reduction of Ni²⁺ from its two-valence oxidation state to metallic state occurred in the film annealed in Ar at 600 and 800 °C. In addition, there appeared to be significant diffusion of Ni from the bottom to the top surface of the film during annealing in Ar at 800 °C. Both as-deposited and annealed thin films displayed obvious room temperature ferromagnetism (RTFM) which was from metallic Ni, Ni²⁺ or both with two distinct mechanisms. Furthermore, a significant improvement in saturation magnetization (M_s) in the films was observed after annealing in air (M_s = 0.036 μ_B/Ni) or Ar (M_s = 0.033 μ_B/Ni) at 600 °C compared to that in as-deposited film (M_s = 0.017 μ_B/Ni). An even higher M_s value was observed in the film annealed in Ar at 800 °C (M_s = 0.055 μ_B/Ni) compared to that at 600 °C mainly due to the diffusion of Ni. The ultraviolet emission of the Ni-doped ZnO thin film was restored during annealing in Ar at 800 °C, which was also attributed to the diffusion of Ni.     

Unidirectional variation of lattice constants of Al-N-codoped ZnO films by RF magnetron sputtering

Al-N-codoped ZnO films were fabricated by RF magnetron sputtering in the ambient of N₂ and O₂ on silicon (1 0 0) and homo-buffer layer, subsequently, annealed in O₂ at low pressure. X-ray diffraction (XRD) spectra show that as-grown and 600 °C annealed films grown by codoping method are prolonged along crystal c-axis. However, they are not prolonged in (0 0 1) plane vertical to c-axis. The films annealed at 800 °C are not prolonged in any directions. Codoping makes ZnO films unidirectional variation. X-ray photoelectron spectroscopy (XPS) shows that Al content hardly varies and N escapes with increasing annealing temperature from 600 °C to 800 °C.     

Post-sintering annealing effect on the diffuse phase transition in (Pb1−xBax)(Yb0.5Ta0.5)O3 ceramics

The effect of post sintering annealing on the dielectric response of (Pb_1−xBa_x)(Yb_0.5Ta_0.5)O₃ ceramics in the diffuse phase transition range (x=0.2) has been investigated. The samples are prepared by conventional solid-state reaction method. The samples are sintered at 1300 °C for 2 h and annealed at different temperatures (800, 900 and 1000 °C) for 8 h and at 800 °C for different time durations (8, 12 and 24 h). A significant change in the dielectric response has been observed in all the samples. The dielectric constant increases remarkably and the dielectric loss tangent decreases. The dielectric peaks of the annealed samples are observed to be more diffused with noticeable frequency dispersion compared to the as sintered sample.     

The influence of substrate temperature and annealing on the properties of pulsed laser-deposited YIG films on fused quartz substrate

Yttrium iron garnet (YIG) thin films were deposited on fused quartz substrate at different substrate temperatures (T_s) varying from room temperature (RT) to 850 °C using pulsed laser deposition (PLD) technique. All the films in the as-deposited state were X-ray amorphous and non-magnetic at RT. The film deposited at RT after annealing at temperatures T_a?700 °C showed both X-ray peaks and the magnetic order. The films deposited at higher T_s (500–850 °C) and then annealed at 700 °C resulted in better-quality films with higher 4πM_s value. The highest value of magnetization was for the sample deposited at 850 °C and annealed at 700 °C, which is 68% of the bulk 4πM_s value.     

Microstructure development and properties of the AlCuFe quasicrystalline coating on near-α titanium alloy

A protective quasicrystalline AlFeCu coating was deposited on TIMETAL 834 substrate by nonreactive magnetron sputtering in order to improve resistance of the alloy to oxidation. Microstructure characterisation of the substrate and the coating was performed by analytical scanning- and transmission electron microscopy as well as X-ray diffractometry. Depending on annealing temperature and time, the deposited coating (2.7 μm thick) has a different microstructure. The coating in Specimen 1 (annealed 600 °C/4 h in vacuum) consisted of two zones: outer, composed of Al₅Fe₂ and Al₂Cu₃ phases and inner, in which only quasicrystalline ψ phase was present. The coating in Specimen 2 (annealed 600 °C/4 h + 700 °C/2 h in vacuum) was fully quasicrystalline and consisted of icosahedral ψ phase.Both coatings exhibit higher microhardness than the substrate material. It was established that the applied surface treatment essentially improves oxidation resistance of the alloy tested at 750 °C during 250 h in static air. Sample weight gain was 60% lower than in the case of uncoated sample. Oxide scale spallation occurred for uncoated alloy while the coated one did not show any spallation. It was found that the very brittle scale formed during oxidation on the uncoated alloy was consisting of TiO₂, while that on the coated one consisted mainly of α-Al₂O₃.     

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.     

Crystallization of hydrogenated amorphous silicon carbon films with laser and thermal annealing

The crystallization of silicon rich hydrogenated amorphous silicon carbon films prepared by Plasma Enhanced Chemical Vapor Deposition technique has been induced by excimer laser annealing as well as thermal annealing. The excimer laser energy density (E_d) and the annealing temperature were varied from 123 to 242 mJ/cm² and from 250 to 1200 °C respectively. The effects of the two crystallization processes on the structural properties and bonding configurations of the films have been studied. The main results are that for the laser annealed samples, cubic SiC crystallites are formed for E_d ≥ 188 mJ/cm², while for the thermal annealed samples, micro-crystallites SiC and polycrystalline hexagonal SiC are observed for the annealing temperature of 800 and 1200 °C respectively. The crystallinity degree has been found to improve with the increase in the laser energy density as well as with the increase in the annealing temperature.     

On the thermal stability of Co2Z hexagonal ferrites for low-temperature ceramic cofiring technologies

Co₂Z hexaferrite Ba₃Co₂Fe₂₄O₄₁ was prepared by a mixed oxalate co-precipitation route and the standard ceramic technology. XRD studies show that at T<1300 °C different ferrite phases coexist with the M-type hexaferrite as majority phase between 1000 and 1100 °C and the Y-type ferrite at 1230 °C. The Z-type material has its stability interval between 1300 and 1350 °C. Both synthesis routes result in almost single-phase Z-type ferrites after calcination at 1330 °C, intermediate grinding and sintering at 1330 °C. The permeability of Co₂Z-type ferrite of about μ=20 is stable up to several 100 MHz, with maximum losses μ′′ around 700 MHz. Addition of 3 wt% Bi₂O₃ as sintering aid shifts the temperature of maximum shrinkage down to 950 °C and enables sintering of Z-type ferrite powders at 950 °C. However, the permeability is reduced to μ=3. It is shown here for the first time that Co₂Z ferrite is not stable under these conditions; partial thermal decomposition into other hexagonal ferrites is found by XRD studies. This is accompanied by a significant decrease of permeability. This shows that Co₂Z hexagonal ferrite is not suitable for the fabrication of multilayer inductors for high-frequency applications via the low-temperature ceramic cofiring technology since the material is not compatible with the typical process cofiring temperature of 950 °C.     

Influence of temperature annealing on optical properties of SrTiO3/BaTiO3 multilayered films on indium tin oxide

We have prepared SrTiO₃/BaTiO₃ thin films with multilayered structures deposited on indium tin oxide (ITO) coated glass by a sol-gel deposition and heating at 300-650 °C. The optical properties were obtained by UV-vis spectroscopy. The films show a high transmittance (approximately 85%) in the visible region. The optical band gap of the films is tunable in the 3.64-4.19 eV range by varying the annealing temperature. An abrupt decrease towards the bulk band gap value is observed at annealing temperatures above 600 °C. The multilayered film annealed at 650 ° C exhibited the maximum refractive index of 2.09-1.91 in the 450-750 nm wavelength range. The XRD and AFM results indicate that the films annealed above 600 ° C are substantially more crystalline than the films prepared at lower temperatures which were used to change their optical band gap and complex refractive index to an extent that depended on the annealing temperature.     

Structural characterizations of Co2MnSi/MgO/Co2MnSi magnetic tunnel junctions by transmission electron microscopy

We have investigated the structure of Co₂MnSi/MgO/Co₂MnSi magnetic tunneling junctions with different tunnel magnetoresistance values depending on the in situ annealing temperatures just after the deposition of the upper Co₂MnSi electrodes. The nano-beam diffraction patterns indicated that the degree of order of the upper Co₂MnSi electrode annealed at 550 °C was higher than that of an electrode annealed at 400 °C. Moreover, the degree of the L2₁ order of the upper Co₂MnSi electrode annealed at 550 °C was even lower than that of the lower Co₂MnSi electrode annealed at an almost equal temperature of 600 °C. Atomic-scale observation using a high-angle annular dark-field (HAADF) method distinctly showed the existence of the L2₁-ordered regions in the B2-ordered matrix in the upper Co₂MnSi electrode annealed at 400 °C.     

Influence of deposition temperature on the structural and morphological properties of Be3N2 thin films grown by reactive laser ablation

Be₃N₂ thin films have been grown on Si(1 1 1) substrates using the pulsed laser deposition method at different substrate temperatures: room temperature (RT), 200 °C, 400 °C, 600 °C and 700 °C. Additionally, two samples were deposited at RT and were annealed after deposition in situ at 600 °C and 700 °C. In order to obtain the stoichiometry of the samples, they have been characterized in situ by X-ray photoelectron (XPS) and reflection electron energy loss spectroscopy (REELS). The influence of the substrate temperature on the morphological and structural properties of the films was investigated using scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD). The results show that all prepared films presented the Be₃N₂ stoichiometry. Formation of whiskers with diameters of 100-200 nm appears at the surface of the films prepared with a substrate temperature of 600 °C or 700 °C. However, the samples grown at RT and annealed at 600 °C or 700 °C do not show whiskers on the surface. The average root mean square (RMS) roughness and the average grain size of the samples grown with respect the substrate temperature is presented. The films grown with a substrate temperature between the room temperature to 400 °C, and the sample annealed in situ at 600 °C were amorphous; while the αBe₃N₂ phase was presented on the samples with a substrate temperature of 600 °C, 700 °C and that deposited with the substrate at RT and annealed in situ at 700 °C.     

Spray pyrolysis deposition of YSZ and YSZ-Pt composite films

In the present paper procedures are described for spray pyrolysis deposition of YSZ films (0.1-30 μm in thickness) with 8 or 15 mole % of YO_1.5 on different substrates. Aqueous or ethylene glycol solutions of Y-Zr-citrates were used as starting material and O₂ as carrier gas. The crystal structure and the morphology of the films were studied.The optimal deposition and post-deposition annealing conditions were defined, taking into account the desired film thickness and characteristics. Substrate temperatures of 250 °C during the deposition followed by heating for 10 min to 400 °C after every spraying and to 590 °C after every three sprayings with final annealing at 590 °C for 2 h in static air atmosphere were found to be suitable for the production of dense, uniform and cracks-free films.     

Influence of substrate temperature on structures and dielectric properties of pyrochlore Bi1.5Zn1.0Nb1.5O7 thin films prepared by pulsed laser deposition

The influence of substrate temperature on structural and dielectric properties of cubic pyrochlore Bi_1.5Zn_1.0Nb_1.5O₇ (BZN) thin films prepared by pulsed laser deposition process has been investigated. BZN thin films were deposited on Pt/Ti/SiO₂/Si(1 0 0) substrate and in situ annealed at 700 °C. The results indicate that the substrate temperature has a significant effect on the structural and dielectric properties of BZN thin films. The films exhibit a cubic pyrochlore structure in the substrate temperature range from 550 °C to 700 °C and at the annealing temperature of 700 °C. With further increase of substrate temperature to 750 °C, the phases of Bi₂O₃, BiNbO₄ and Bi₅Nb₃O₁₅ can be detected in the XRD pattern due to the Zn loss. The dielectric constant and loss tangent of the films deposited at 650 °C are 192 and 6 × 10⁻⁴ at 10 kHz, respectively. The tunability is 10% at a dc bias field of 0.9 MV/cm.     

Surface morphology and luminescence characterization of β-FeSi2 thin films prepared by pulsed laser deposition

β-FeSi₂ thin films were prepared on Si (1 1 1) substrates by pulsed laser deposition (PLD) with a sintering FeSi₂ target and an electrolytic Fe target. The thin films without micron-size droplets were prepared using the electrolytic Fe target; however, the surface without droplets was remarkably rougher using the Fe target than using the FeSi₂ target. After deposition at 600 °C and then annealing at 900 °C for 20 h, XRD indicated that the thin film prepared using the Fe target had a poly-axis-orientation, but that prepared using the FeSi₂ target had a one-axis-orientation. The PL spectra of the thin films prepared using the FeSi₂ and Fe targets at a growth temperature of 600 °C and subsequently annealed at 900 °C for 20 h had A-, B- and C-bands. Moreover, it was found that the main peak at 0.808 eV (A-band) in the PL spectrum of the thin films prepared using the FeSi₂ target was the intrinsic luminescence of β-FeSi₂ from the dependence of PL peak energy on temperature and excitation power density.     

Modulation of the photoluminescence of Si quantum dots by means of CO2 laser pre-annealing

Si quantum dots (QDs) embedded in SiO₂ can be normally prepared by thermal annealing of SiO_x (x < 2) thin film at 1100 °C in an inert gas atmosphere. In this work, the SiO_x thin film was firstly subjected to a rapid irradiation of CO₂ laser in a dot by dot scanning mode, a process termed as pre-annealing, and then thermally annealed at 1100 °C for 1 h as usual. The photoluminescence (PL) intensity of Si QD was found to be enhanced after such pre-annealing treatment. This PL enhancement is not due to the additional thermal budget offered by laser for phase separation, but attributed to the production of extra nucleation sites for Si dots within SiO_x by laser irradiation, which facilitates the formation of extra Si QDs during the subsequent thermal annealing.     

Dielectric properties of continuous composition spreaded MgO-Ta2O5 thin films

The dielectric properties of MgO-Ta₂O₅ continuous composition spread (CCS) thin films were investigated. The MgO-Ta₂O₅ CCS thin films were deposited on Pt/Ti/SiO₂/Si substrates by off-Axis RF magnetron sputtering system, and then the films were annealed at 350 °C with rapid thermal annealing system in vacuum. The dielectric constant and loss of MgO-Ta₂O₅ CCS thin films were plotted via 1500 micron-step measuring. The specific point of Ta₂O₅-MgO CCS thin film (post annealed at 350 °C) showing superior dielectric properties of high dielectric constant (k ∼ 28) and low dielectric loss (tan δ < 0⋅004) at 1 MHz were found in the area of 3-5 mm apart from Ta₂O₅ side on the substrate. The cation's composition of thin film was Mg:Ta = 0.4:2 at%.     

Self-implantation of Cz-Si: Clustering and annealing of defects

Observations of vacancy clusters formed in Czochralski (Cz) Si after high energy ion implantation are reported. Vacancy clusters were created by 2 MeV Si ion implantation of 1 × 10¹⁵ ions/cm² and after annealing between 600 and 650 °C. Doppler broadening measurements using a slow positron beam have been performed on the self-implanted Si samples, both as-implanted and after annealing between 200 and 700 °C for time intervals ranging from 15 to 120 min. No change in the S parameter was noted after the thermal treatment up to 500 °C. However, the divacancies (V₂) created as a consequence of the implantation were found to start agglomerating at 600 °C, forming vacancy clusters in two distinct layers below the surface; the first layer is up to 0.5 μm and the second layer is up to 2 μm. The S-W plots of the data suggest that clusters of the size of hexavacancies (V₆) could be formed in both layers after annealing for up to an hour at 600 °C or half an hour at 650 °C. After annealing for longer times, it is expected that vacancies are a mixture of V₆ and V₂, with V₆ most probably dominating in the first layer. Further annealing for longer times or higher temperatures breaks up the vacancy clusters or anneals them away.     

Effect of substrate temperature and annealing temperature on the structural, electrical and microstructural properties of thin Pt films by rf magnetron sputtering

Influence of both substrate temperature, T_s, and annealing temperature, T_a, on the structural, electrical and microstructural properties of sputtered deposited Pt thin films have been investigated. X-ray diffraction results show that as deposited Pt films (T_s = 300, 400 °C) are preferentially oriented along (1 1 1) direction. A little growth both along (2 0 0) and (3 1 1) directions are also noticed in the as deposited Pt films. After annealing in air (T_a = 500-700 °C), films become strongly oriented along (1 1 1) plane. With annealing temperature, average crystallite size, D, of the Pt films increases and micro-strain, e, and lattice constant, a₀, decreases. Residual strain observed in the as deposited Pt films is found to be compressive in nature while that in the annealed films is tensile. This change in the strain from compressive to tensile upon annealing is explained in the light of mismatch between the thermal expansion coefficients of the film material and substrate. Room temperature resistivity of Pt films is dependant on both the T_s and T_a of the films. Observed decrease in the film resistivity with T_a is discussed in terms of annihilation of film defects and grain-boundary. Scanning electron microscopic study reveals that as the annealing temperature increases film densification improves. But at an annealing temperature of ∼600 °C, pinholes appear on the film surface and the size of pinhole increases with further increase in the annealing temperature. From X-ray photoelectron spectroscopic analysis, existence of a thin layer of chemisorbed atomic oxygen is detected on the surfaces of the as deposited Pt films. Upon annealing, coverage of this surface oxygen increases.