Structure and thermal stability of (Zr0.6Al0.4)O1.8 thin film on strained SiGe layer

Zr_0.6Al_0.4O_1.8 dielectric films were deposited directly on strained SiGe substrates at room temperature by ultra-high vacuum electron-beam evaporation (UHV-EBE) and then annealed in N₂ under various temperatures. X-ray diffraction (XRD) reveals that the onset crystallization temperature of the Zr_0.6Al_0.4O_1.8 film is about 900 °C, 400 °C higher than that of pure ZrO₂. The amorphous Zr_0.6Al_0.4O_1.8 film with a physical thickness of ∼12 nm and an amorphous interfacial layer (IL) with a physical thickness of ∼3 nm have been observed by high-resolution transmission electron microscopy (HRTEM). In addition, it is demonstrated there is no undesirable amorphous phase separation during annealing at temperatures below and equal to 800 °C in the Zr_0.6Al_0.4O_1.8 film. The chemical composition of the Zr_0.6Al_0.4O_1.8 film has been studied using secondary ion mass spectroscopy (SIMS).     

A partial molar volume for La2O3 in silicate melts

The densities of several La-bearing silicate melts distributed along binary joins have been measured using the double-bob Archimedean method. The results show that the addition of La₂O₃ leads to an increase in the melt density. From these density data, the partial molar volume of La₂O₃ in silicate melts has been determined. Distinct values for partial molar volume of La₂O₃ have been obtained (i.e., 44.01 and 37.04 cm³/mol at 1273 K for the La₂O₃-Na₂O-SiO₂ and La₂O₃-CaO-MgO-Al₂O₃-SiO₂ systems, respectively) indicating a compositional dependence of the partial molar volume of La₂O₃. Nevertheless, a single value for the partial molar volume of La₂O₃ (i.e., 43.47 cm³/mol at 1273 K) suffices to describe the molar volume of melts within errors in the entire multi-component system La₂O₃-Na₂O-CaO-MgO-Al₂O₃-SiO₂ and for La₂O₃ concentrations not greater than 7 mol%. In addition, this work points out that the molar volumes behave ideally within the composition range investigated (i.e., linear variation of the molar volume along the binary joins). Distinct values for the partial molar volume of La₂O₃ obtained in this study and their differences with the molar volumes of molten La₂O₃ given in the literature raise the possibility however that this ideality is not maintained within the entire system.     

Different substrate materials effect on structure of ta-C films by Raman spectroscopy for magnetic recording sliders

Raman spectra, using visible (514 nm) and ultraviolet (244 nm) excitation, of tetrahedral amorphous carbon (ta-C) films of thickness of 5 nm have been studied as a function of different substrates materials. These materials are Fe-Co (Fe: 67 at.%, Co: 33 at.%) alloy, Fe-Ni alloy (Fe: 18 at.%, Ni: 82 at.%), Au and Al₂O₃-TiC (Al₂O₃: 64 at.%, TiC: 36 at.%), which are mainly used in magnetic recording sliders. The spectra show that the films deposited on Al₂O₃-TiC contain the highest sp³ content, with a lower sp³ content observed in films deposited to Fe-Co and Fe-Ni alloys. The lowest sp³ content was observed in films on the Au substrate. The results also indicate that the anti-wear performance of ta-C film on different substrates varies as Al₂O₃-TiC (the best) > Fe-Co and Fe-Ni alloy > Au (the worst). Also mechanisms are proposed to explain the effect of substrate material on these thin film properties.     

Growth and microstructural features of laser ablated LiCoO2 thin films

Thin films of LiCoO₂ were prepared by pulsed laser deposition technique and the properties were studied in relation to the deposition parameters. The films deposited from a sintered composite target (LiCoO₂+Li₂O) in an oxygen partial pressure of 100 mTorr and at a substrate temperature of 300 °C exhibited preferred c-axis (0 0 3) orientation perpendicular to the substrate surface. The AFM data demonstrated that the films are composed of uniform distribution of fine grains with an average grain size of 80 nm. The grain size increased with an increase in substrate temperature. The (0 0 3) orientation decreased with increase in (1 0 4) orientation for the films deposited at higher substrate temperatures (>500 °C) indicating that the films’ growth is parallel to the substrate surface. The composition of the experimental films was analyzed using X-ray photoelectron spectroscopy (XPS). The binding energy peaks of Co(2p_3/2) and Co(2p_1/2) are, respectively, observed at 779.3 and 794.4 eV, which can be attributed to the Co³⁺ bonding state of LiCoO₂. The electrochemical measurements were carried out on Li//LiCoO₂ cells with a lithium metal foil as anode and LiCoO₂ film as cathode of 1.5 cm² active area using a Teflon home-made cell hardware. The Li//LiCoO₂ cells were tested in the potential range 2.6-4.2 V. Specific capacity as high as 205 mC/cm² μm was measured for the film grown at 700 °C. The growth of LiCoO₂ films were studied in relation to the deposition parameters for their effective utilization as cathode materials in solid-state microbattery application.     

Characterisation of ALCVD Al2O3-ZrO2 nanolaminates, link between electrical and structural properties

Al₂O₃ and ZrO₂ mixtures for gate dielectrics have been investigated as replacements for silicon dioxide aiming to reduce the gate leakage current and reliability in future CMOS devices. Al₂O₃ and ZrO₂ films were deposited by atomic layer chemical vapor deposition (ALCVD) on HF dipped silicon wafers. The growth behavior has been characterized structurally and electrically. ALCVD growth of ZrO₂ on a hydrogen terminated silicon surface yields films with deteriorated electrical properties due to the uncontrolled formation of interfacial oxide while decent interfaces are obtained in the case of Al₂O₃. Another concern with respect to reliability aspects is the relatively low crystallization temperature of amorphous high-k materials deposited by ALCVD. In order to maintain the amorphous structure at high temperatures needed for dopant activation in the source drain regions of CMOS devices, binary Al/Zr compounds and laminated stacks of thin Al₂O₃ and ZrO₂ films were deposited. X-ray diffraction and transmission electron microscope analysis show that the crystallization temperature can be increased dramatically by using a mixed oxide approach. Electrical characterization shows orders of leakage current reduction at 1.1-1.7 nm of equivalent oxide thickness. The permittivity of the deposited films is determined by combining quantum mechanically corrected capacitance voltage measurements with structural analysis by transmission electron microscope, X-ray reflectivity, Rutherford backscattering, X-ray photoelectron spectroscopy, and inductively coupled plasma optical emission spectroscopy. The k-values are discussed with respect to formation of interfacial oxide and possible silicate formation.     

Surface smoothing of sputter deposited amorphous CNx films by silicon addition

Amorphous carbon nitride (CN_x) films with silicon addition up to 16 at.% are sputter deposited on Si(1 0 0) substrate, and the surface morphology is studied with scaling method based on atomic force microscopy. The surface roughness σ, the roughness exponent α, and the lateral correlation length ξ decrease with silicon content of the films, reaching 0.33 nm, 0.80 and 50 nm, respectively, for the film with [Si] = 16 at.%. The addition of silicon in the films leads to additional Si-N, Si-C-N and CN bonds revealed by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. The films undergo a structural transition from columnar to smooth morphology in cross-section with silicon addition demonstrated by field emission scanning electron microscopy. Nano-sized clusters sparsely dispersed in amorphous matrix of the film with [Si] = 16 at.% are observed by high-resolution transmission microscopy. According to the surface growth mechanism in which surface diffusion and geometrical shadowing drive structural and morphological evolution of the sputter deposited films, surface smoothing of the amorphous CN_x films by silicon addition is explained by the formation of Si-N and Si-C-N bonds that impede surface diffusion of the adsorbed species during film growth, which leads to the reduced size of the columnar structures.     

Electrical properties of Bi3.15Nd0.85Ti2.8-xZr0.2MnxO12 thin films with different Mn content synthesized by chemical solution deposition (CSD)

Bi_3.15Nd_0.85Ti_2.8-xZr_0.2Mn_xO₁₂ (BNTZM) thin films with various Mn content (x = 0, 0.005, 0.01, 0.03, and 0.05) have been prepared on Pt/Ti/SiO₂/Si (100) substrates by a chemical solution deposition (CSD) technique. The crystal structures of BNTZM thin film have been analyzed by X-ray diffraction (XRD). The dependence of Mn contents on the ferroelectric, dielectric properties, and leakage current of these BNTZM films have been thoroughly investigated. The XRD analysis demonstrated that all the BNTZM thin films were of typical bismuth-layer-structured ferroelectrics (BLSF) polycrystalline structure and exhibited a highly preferred (117) orientation. Among these BNTZM films, the BNTZM thin film with Mn content equal to 0.01 exhibits the maximum remnant polarization (2P_r) of 48μC/cm² and a low coercive field (2E_c) of 177 kV/cm. In addition, the BNTZM thin film with x = 0.01 (Mn) showed a fatigue-free behavior up to 1 × 10¹⁰ read/write cycles.     

Effect of the annealing process on the microstructure of La2Zr2O7 thin layers epitaxially grown on LaAlO3 by metalorganic decomposition

La₂Zr₂O₇ (LZO) films have been grown by metalorganic decomposition (MOD) to be used as buffer layers for coated conductors. A characteristic feature of LZO thin films deposited by MOD is the formation of nanovoids in an almost single crystal structure of LZO pyrochlore phase. Annealing parameters (heating ramp, temperature, pressure, etc.) were varied to establish their influence on the microstructure of the LZO layers. X-ray diffraction (XRD) and transmission electron microscopy (TEM) were used for sample characterization. The epitaxial pyrochlore phase was obtained for annealing temperatures higher than 850 °C whatever the other annealing conditions. However, the film microstructure, in particular, nanovoids shape and size, is strongly dependent on heating ramp and pressure during annealing. When using low heating ramp, percolation of voids creates diffusion channels for oxygen which are detrimental for the substrate protection during coated conductor fabrication. From this point of view high heating rates are more adapted to the growth of LZO layers.     

Fluorinated nanoporous SiO2 films with ultra-low dielectric constant

Fluorinated nanoporous silica (denoted as SiO₂:F) thin films with low dielectric constant were prepared by a sol-gel method and spin coating technique. The leakage current densities of the SiO₂:F thin films were 10⁻⁸ and 3 × 10⁻⁶ A/cm² respectively for the as-deposited films and for those subjected to annealing at a temperature of 450 °C. These currents are more than one order of magnitude lower than those of the common SiO₂ films. Photoluminescent results showed strong blue-light emission and a small blue shift in the SiO₂:F films that were related to the increment of the porosity. The dielectric properties were also characterized and the k value of the annealed SiO₂:F film was found to be about 1.67. The hole size in the films is small and the size distribution is uniform for the annealed SiO₂:F samples due to the effects of fluorination. The underlying mechanism for fluorination is discussed in this paper.     

An easy sol–gel route for deposition of oriented Ln2Ti2O7 (Ln=La,Nd) films on SrTiO3 substrates

The effect of the orientation of SrTiO₃ (STO) substrates, (1 0 0) or (1 1 0), on the growth of La₂Ti₂O₇ (LTO) and Nd₂Ti₂O₇ (NTO) thin films was investigated. The films were deposited via a sol–gel process coupled to the spin-coating technique. Depending on the substrate orientation, a similar effect was observed on the structural properties for both the LTO and NTO thin films. For (1 1 0)-oriented STO substrate, the films are preferentially (0 0 1) oriented while for (1 0 0)-oriented STO substrates, the orientation is mainly (0 1 2). Those matching appear to be in good agreement with the compatibility between the film/substrate crystal lattices, in relation with the existence of perovskite slabs in Ln₂Ti₂O₇ (Ln=rare earth) compounds. In these latter, a slight disorientation of the (0 1 2) planes with respect to the surface of the substrate was measured. This tilting is even more marked in the case of NTO. The surface morphology was studied by atomic force microscopy.     

Preparation of single-crystalline ZnO films on ZnO-buffered a-plane sapphire by chemical bath deposition

High-quality zinc oxide (ZnO) films were successfully grown on ZnO-buffered a-plane sapphire (Al₂O₃ (1 1 2¯ 0)) substrates by controlling temperature for lateral growth using chemical bath deposition (CBD) at a low temperature of 60 °C. X-ray diffraction analysis and transmission electron microscopy micrographs showed that the ZnO films had a single-crystalline wurtzite structure with c-axis orientation. Rocking curves (ω-scans) of the (0 0 0 2) reflections showed a narrow peak with full width at half maximum value of 0.50° for the ZnO film. A reciprocal space map indicated that the lattice parameters of the ZnO film (a=0.3250 nm and c=0.5207 nm) were very close to those of the wurtzite-type ZnO. The ZnO film on the ZnO-buffered Al₂O₃ (1 1 2¯ 0) substrate exhibited n-type conduction, with a carrier concentration of 1.9×10¹⁹ cm⁻³ and high carrier mobility of 22.6 cm² V⁻¹ s⁻¹.     

Epitaxial growth of tin oxide film on TiO2(1 1 0) using molecular beam epitaxy

Growth of tin oxide thin films using molecular beam epitaxy in a pyrolyzed nitrogen dioxide atmosphere on a titanium dioxide (1 1 0) substrate was investigated using X-ray photoelectron spectroscopy (XPS), electron diffraction, and atomic force microscopy (AFM). Properties of deposited films were studied for their dependence on substrate temperature and oxidation gas pressure. Analyses using XPS data revealed that tin atoms were fully oxidized to Sn⁴⁺ and SnO₂ films were grown epitaxially in deposition conditions of substrate temperatures of 627 K or higher and NO₂ pressure greater than 3×10⁻³ Pa. At a substrate temperature of 773 K, a smooth surface with atomic steps was visible in the SnO₂ films, but above or below this temperature, fine grains with crystal facets or porous structures appeared. At pressures of 8×10⁻⁴ to 3×10⁻⁴ Pa, the randomly oriented SnO phase was dominantly grown. Further decreasing the pressure, the Sn metal phase, which was epitaxially crystallized at less than 500 K, was also grown.     

Structure and growth morphology of Gd2O3-doped CeO2 thin films

Gd₂O₃-doped CeO₂ (Gd_0.1Ce_0.9O_1.95, GDC) thin films were synthesized on (1 0 0) Si single crystal substrates by a reactive radio frequency magnetron sputtering technique. Structures and surface morphologies were characterized by X-ray diffraction (XRD), Atomic Force Microscopy (AFM) and one-dimensional power spectral density (1DPSD) analysis. The XRD patterns indicated that, in the temperature range of 200–700 °C, f.c.c. structured GDC thin films were formed with growth orientations varying with temperature—random growth at 200 °C, (2 2 0) textures at 300–600 °C and (1 1 1) texture at 700 °C. GDC film synthesized at 200 °C had the smoothest surface with roughness of R_rms=0.973 nm. Its 1DPSD plot was characterized with a constant part at the low frequencies and a part at the high frequencies that could be fitted by the f^−2.4 power law decay. Such surface feature and scaling behavior were probably caused by the high deposition rate and random growth in the GDC film at this temperature. At higher temperatures (300–700 °C), however, an intermediate frequency slope (−γ₂≈−2) appeared in the 1DPSD plots between the low frequency constant part and the high frequency part fitted by f⁻⁴ power law decay, which indicated a roughing mechanism dominated by crystallographic orientation growth that caused much rougher surfaces in GDC films (R_rms>4 nm).     

Growth of polar axis oriented tetragonal Pb(Zr,Ti)O3 films on CaF2 substrates with transparent (La0.07Sr0.93)SnO3

Epitaxial (La_0.07Sr_0.93)SnO₃ [LSSO] films were deposited on CaF₂ substrates by pulse laser deposition. The (1 0 0)_c orientation of LSSO films was observed only on (1 1 0)CaF₂, whereas (1 1 0)_c orientation was found on (1 1 1)CaF₂ and (1 0 0)CaF₂. (0 0 1) polar axis oriented tetragonal Pb(Zr_0.35Ti_0.65)O₃ films were grown on the fabricated (1 0 0)_cLSSO∥(1 1 0)CaF₂ by pulsed metal organic chemical vapor deposition. The (0 0 1)Pb(Zr_0.35Ti_0.65)O₃∥(1 0 0)cLSSO∥(1 1 0)CaF₂ stack structure exhibited about 70% transparency with an adsorption edge of approximately 330 nm.     

Electrical, structural and optical properties of SnO2 thin films prepared by spray pyrolysis

This study investigated the effect of the substrate temperature on the structural, optical, morphological, and electrical properties of undoped SnO₂ films prepared by a spray deposition method. The films were deposited at various substrate temperatures ranging from 300-500 °C in steps of 50 °C and characterized by different optical and structural techniques. X-ray diffraction studies showed that the crystallite size and preferential growth directions of the films were dependent on the substrate temperature. These studies also indicated that the films were amorphous at 300 °C and polycrystalline at the other substrate temperatures used. Infrared and visible spectroscopic studies revealed that a strong vibration band, characteristic of the SnO₂ stretching mode, was present around 630 cm⁻¹ and that the optical transmittance in the visible region varied over the range 75-95% with substrate temperature, respectively. The films deposited at 400 °C exhibited the highest electrical conductivity property.     

Optical properties of and concentration quenching in Bi2O3-B2O3-Ga2O3 glasses

Er₂O₃-doped Bi₂O₃-B₂O₃-Ga₂O₃ glasses were prepared by the conventional melt-quenching method, and the Er³⁺:⁴I_13/2 → ⁴I_15/2 fluorescence properties are studied for different Er³⁺ concentrations. when the Er₂O₃ concentration increases from 0.03 to 3.0 mol%, the measured lifetime of Er³⁺:⁴I_13/2 level decrease from 2.24 to 0.9 m s, and from 0.25 to 0.20 m s for the Er³⁺:⁴I_11/2 level. The fast energy migration among Er³⁺ ions cause the reduction of lifetime of the ⁴I_13/2 level, whereas the change in the ⁴I_11/2 level is mainly due to a cooperative upconversion process (⁴I_11/2, ⁴I_11/2) → (⁴F_7/2, ⁴I_15/2). Based on the dipole-dipole interaction theory, the interaction parameter, C_Er,Er, for the migration rate of Er³⁺:⁴I_13/2 ↔ ⁴I_13/2 was calculated to be 32 × 10⁻⁴⁰ cm⁶ s⁻¹.     

Electrical properties of Al2O3 film deposited at low temperatures

Amorphous Al₂O₃ films were deposited on p-Si by rf magnetron sputtering to investigate their potential as a gate dielectric in organic thin film transistors (OTFTs). The deposition was performed at room temperature, 200 and 300 °C using Al₂O₃ and Al targets. Achieved Al₂O₃ films have higher capacitance values than thermally grown SiO₂ as characterized by capacitance-voltage measurements. It is also found from current-voltage and roughness measurements that the leakage current and the surface roughness can be least when the films are deposited at room temperature. The capacitance of the film obtained from the Al₂O₃ target appears higher than that of the Al₂O₃ film from the Al target while the results of electrical breakdown are opposite. These room temperature processes are promising for applications to the gate dielectrics of organic TFTs.     

Properties of CVD alumina-titania composite films grown at different CO2/H2 inputs

Amorphous alumina-titania (Al₂O₃-TiO₂) films were prepared on silicon substrates by low-pressure chemical vapor deposition (CVD) using a mixture of aluminum tri-sec-butoxide (ATSB) and titanium tetrachloride (TiCl₄) at different CO₂/H₂ inputs (the ATSB/TiCl₄/CO₂/H₂ system). The films had increased Al contents at higher temperatures and CO₂/H₂ inputs. The `splotchy' deposits were observed. The higher compressive internal stress at higher temperature was attributed to the films with a thinner thickness. Higher compressive internal stress and more Al-O bonding resulted in higher specific critical load. Films deposited at low temperature of 350 °C have a defected structure and a higher dielectric property, due to the non-stoichiometric nature at the Ti-rich composition. Resistivity decreased from 10¹¹ to 10⁸-10⁹ Ω cm after annealing. Breakdown voltages increased slightly with substrate temperature and were in the range of 2.3-6.4 MV/cm. Refractive indices were in the range of 1.71-2.28. Greater than 60% transmittance was observed at visible range for all films.     

Spectroscopic properties of Er-doped Na2O-Sb2O3-B2O3-SiO2 glasses

Spectroscopic properties of Er³⁺-doped Na₂O-Sb₂O₃-B₂O₃-SiO₂ glasses have been investigated for developing 1.5-μm broadband fiber amplifiers. An intense 1.5-μm near infrared emission with a broad full width at half maximum (FWHM) of 88 nm has been obtained for Er³⁺-doped 5Na₂O-20Sb₂O₃-35B₂O₃-40SiO₂ glass upon excitation with a 980 nm laser diode. The obtained emission cross-section of the ⁴I_13/2 → ⁴I_15/2 transition and the lifetime of the ⁴I_13/2 level of Er³⁺ ions are 6.8 × 10⁻²¹ cm² and 0.36 ms, respectively. It is noted that the product of the emission cross-section and the FWHM of the glass, σ_e × FWHM, is as great as 598.4 × 10⁻²¹ cm² nm, which is comparable or higher than that of Er³⁺-doped bismuth-based and tellurite-based glasses. These special optical properties encourage in identifying them as important materials for potential applications in high performance optics and optical communication networks.     

Thermal and some physical properties of glasses in the La2O3−CaO−B2O3 ternary system

Glasses in the La₂O₃−CaO−B₂O₃ ternary system were studied. The glass forming range as determined by the appearance of the annealed cast was found to match previously published findings. Clear glasses were formed in the composition range of 5.7−19.1 mol% La₂O₃ with constant B₂O₃ content of 71.4 mol%, and in glasses of constant La₂O₃:CaO ratio of 1:4 with B₂O₃ content in the range of 71.4-55.0 mol%. The non-linear optical crystalline phase La₂Ca₂B₁₀O₁₉ was crystallized from the clear glasses after heat treatments, as determined by powder XRD. Two types of the LaBO₃ crystalline phases were detected in the partially and the fully crystallized glass compositions outside the glass forming range. Data are reported for the glass transition temperature (T_g), dilatometric softening point (T_d), linear coefficient of expansion (α), onset crystallization temperature (T_x), exothermal peak temperature (T_P), density (ρ) and index of refraction (n_D) in the clear glasses.