Energetic electronic processes and negative resistance in amorphous TaTa2O5Au and AlAl2O3Au diodes

Voltage-controlled negative resistance (VCNR) can be established in metal-insulator-metal structures by applying a potential to the diode, which is usually in vacuum. Light emission due to electroluminescence (E.L.), and electron emission into vacuum, accompany the formation of conductivity; these energetic electronic phenomena are closely related to the “forming” of VCNR and to the resultant current-voltage characteristics. For Al₂O₃ diodes with impure oxides, VCNR forms at constant voltage, independent of oxide thickness; for clean oxides, forming depends on field and on the metal counterelectrode. The intensity and energy distribution of light emitted from TaTa₂O₅Au diodes have been measured, and are compared to E.L. from AlAl₂O₃Au diodes. The voltage threshold for the appearance of E.L. in TaTa₂O₅Au diodes is 1.2 V, for AlAl₂O₃Au it is 1.4 V. The respective voltages for maximum current, V_m, are 1.9 V and 2.8 V. In Al₂O₃, the E.L. spectrum covers the visible range with peaks at 1.8 eV, 2.3 eV, and 4.0 eV. For Ta₂O₅, the E.L. intensity is constant over most of the visible, but has a maximum between 1.6 eV and 1.8 eV which is also the energy of E.L. of TaTa₂O₅Au diodes before the establishment of VCNR. For both Al₂O₃ and Ta₂O₅ diodes, electron emission into vacuum is anomalous since emission is detectable at diode voltages of ∼2 V. Electron emission in the two insulators, though qualitatively similar, shows differences that depend on differences in trapping levels and band gaps of the insulators.     

Properties of atomic-vapor and atomic-layer deposited Sr, Ti, and Nb doped Ta2O5 Metal-Insulator-Metal capacitors

Atomic Vapor Deposition and Atomic Layer Deposition techniques were applied for the depositions of Ta₂O₅, Ti-Ta-O, Sr-Ta-O and Nb-Ta-O oxide films for Metal-Insulator-Metal (MIM) capacitors used in back-end of line for Radio Frequency applications. Structural and electrical properties were studied. Films, deposited on the TiN bottom electrodes, in the temperature range of 225-400 °C, were amorphous, whereas the post deposition annealing at 600 °C resulted in the crystallization of Nb-Ta-O films. Electrical properties of MIM structures, investigated after sputtering Au top electrodes, revealed that the main characteristics were different for each oxide. On one hand, Ti-Ta-O based MIM capacitors possessed the highest dielectric constant (50), but the leakages currents were also the highest (~ 10^− 5 A/cm² at − 2 V). On the other hand, Sr-Ta-O showed the lowest leakage current densities (~ 10^− 9 A/cm² at − 2 V) as well as the smallest capacitance-voltage nonlinearity coefficients (40 ppm/V²), but the dielectric constant was the smallest (20). The highest nonlinearity coefficients (290 ppm/V²) were observed for Nb-Ta-O based MIM capacitors, although relatively high dielectric constant (40) and low leakage currents (~ 10^− 7 A/cm² at − 2 V) were measured. Temperature dependent leakage-voltage measurements revealed that only Sr-Ta-O showed no dependence of leakage current as a function of the measurement temperature.     

Lightweight geopolymer made of highly porous siliceous materials with various Na2O/Al2O3 and SiO2/Al2O3 ratios

The syntheses of lightweight geopolymeric materials from highly porous siliceous materials viz. diatomaceous earth (DE) and rice husk ash (RHA) with high starting SiO₂/Al₂O₃ ratios of 13.0-33.5 and Na₂O/Al₂O₃ ratios of 0.66-3.0 were studied. The effects of fineness and calcination temperature of DE, concentrations of NaOH and KOH, DE to RHA ratio; curing temperature and time on the mechanical properties and microstructures of the geopolymer pastes were investigated. The results indicated that the optimum calcination temperature of DE was 800 °C. Increasing fineness of DE and starting Na₂O/Al₂O₃ ratio resulted in an increase in compressive strength of geopolymer paste. Geopolymer pastes activated with NaOH gave higher compressive strengths than those with KOH. The optimum curing temperature and time were 75 °C and 5 days. The lightweight geopolymer material with mean bulk density of 0.88 g/cm³ and compressive strength of 15 kg/cm² was obtained. Incorporation of 40% RHA to increase starting SiO₂/Al₂O₃ and Na₂O/Al₂O₃ ratios to 22.5 and 1.7 and enhanced the compressive strength of geopolymer paste to 24 kg/cm² with only a marginal increase of bulk density to 1.01 g/cm³. However, the geopolymer materials with high Na₂O/Al₂O₃ (>1.5) were not stable in water submersion.     

Gravitational waves detector mirrors: Spectroscopic ellipsometry study of Ta2O5 films on SiO2 substrates

A stack of Ta₂O₅/SiO₂ layers is presently used as coating layer of mirrors in interferometric detectors for gravitational waves. The sensitivity of these detectors is limited in the 50-300 Hz frequency range by the mirror thermal noise, and it was suggested that mechanical losses in the Ta₂O₅ are the dominant source of noise. We focus here on Spectroscopic Ellipsometry (SE) results (in the 0.75 ÷ 5 eV spectral range) obtained on high quality Ta₂O₅ films deposited on SiO₂ substrates by Double Ion Beam Sputtering at the Laboratoire des Matériaux Avancés (Lyon, France). The films are extremely flat as indicated by the 0.2 nm RMS roughness determined by Atomic Force Microscopy (AFM) on (20 × 20) μm² areas. The comparison of the optical properties determined by SE with literature data, corroborated by X-ray Photoelectron Spectroscopy (XPS) data, suggests that the films present a non-ideal bulk stoichiometry and/or some degree of nanoporosity. The possible influence of an interface layer is also discussed.     

Pyroelectric Ta-modified LiNbO3 thin films and devices for thermal infrared detection

High-performance pyroelectric infrared (IR) detectors have been fabricated using tantalate-doped lithium niobate LiNb_1 − xTa_xO₃ (abbreviated as LNT, with x = 0-1.0) thin films deposited on Pt(111)/Ti/SiO₂/Si(100) substrates by diol-based sol-gel processing, in which, tantalate (Ta) is adopted as dopant in lithium niobate. The randomly oriented LNT thin film exhibits a relatively small dielectric constant and a large pyroelectric coefficient. The pyroelectric characteristics of detectors with various tantalate contents, as a function of modulation frequency, were investigated. It was found that LiNb_0.8Ta_0.2O₃ had the largest voltage responsivity of 7020 (V/W) at 70 Hz, and a specific detectivity (D^?) of 7.76 × 10⁷ cm Hz^1/2/W at 200 Hz. These results indicate that the LNT thin film with x = 0.20 is most suitable for application as high-performance pyroelectric thin-film detectors.     

Diffusion bonding of Al2O3-TiC composite ceramic and W18Cr4V high speed steel in vacuum

Al₂O₃-TiC composite ceramic and W18Cr4V high speed steel were joined by diffusion bonding with a Ti-Cu-Ti multi-interlayer in a vacuum of 10⁻⁴-10⁻⁵ Pa. The interfacial microstructures of the Al₂O₃-TiC/W18Cr4V joint were investigated with optical microscope and scanning electron microscopy. The elemental concentration near the diffusion interface was evaluated by electron probe microanalysis. The results indicate that an obvious transition zone was formed between Al₂O₃-TiC and W18Cr4V during the vacuum diffusion bonding. The elements in the transition zone are mainly Ti and Cu with a small amount of Fe. Element Ti concentrates near the two interfaces of the Al₂O₃-TiC/transition zone/W18Cr4V. The microhardness of the transition zone is lower than that of Al₂O₃-TiC and higher than that of W18Cr4V. The formation process of the transition zone consists of five stages: (i) Formation of Cu-Ti liquid phase; (ii) Full melt of Cu; (iii) Full melt of Ti; (iv) Formation of reaction layer; (v) Formation of Cu-Ti solid solution and increment of reaction layer.     

Distribution of pyrochlore phase in Pb(Mg1/3Nb2/3)O3-PbTiO3 films and suppression with a Pb(Zr0.52Ti0.48)O3 interfacial layer

Thin films of the relaxor ferroelectric Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (PMN-PT) on Pt/Ti/SiO₂/Si (Pt/Si) substrates both with and without a Pb(Zr_0.52Ti_0.48)O₃ (PZT) interfacial layer were investigated. Perovskite and pyrochlore coexistence was observed for PMN-PT thin films without a PZT interfacial layer. Interestingly, most of the pyrochlore phase was observed in single-coated films and in the first layer of multi-coated films. The pyrochlore phase exhibited grains with an average size of about 25 nm, which is smaller than those of the perovskite phase (about 90 nm). In contrast, for PMN-PT thin films grown on a PZT interfacial layer, the formation of a pyrochlore phase at the interface between PMN-PT layers and the substrate is completely suppressed. Moreover, small grains are not observed in the films with a PZT interfacial layer. The measured polarization-electric field (P-E) hysteresis loops of PMN-PT films with and without PZT layers indicate that enhanced electrical properties can be obtained when a PZT interfacial layer is used. These enhanced properties include an increase in the value of remanent polarization P_r from 2.7 to 5.8 μC/cm² and a decrease in the coercive field E_c from 60.5 to 28.0 kV/cm.     

Preparation and characterization of Nb2O5-Al2O3 composite oxide formed by cathodic electroplating and anodizing

Al foil was coated with niobium oxide by cathodic electroplating and anodized in a neutral boric acid solution to achieve high capacitance in a thin film capacitor. X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) revealed the niobium oxide layer on Al to be a hydroxide-rich amorphous phase. The film was crystalline and had stoichiometric stability after annealing at temperatures up to 600 °C followed by anodizing at 500 V, and the specific capacitance of the Nb₂O₅-Al₂O₃ composite oxide was approximately 27% higher than that of Al₂O₃ without a Nb₂O₅ layer. The capacitance was quite stable to the resonance frequency. Overall, the Nb₂O₅-Al₂O₃ composite oxide film is a suitable material for thin film capacitors.     

Pentacene thin-film transistors and inverters with plasma-enhanced atomic-layer-deposited Al2O3 gate dielectric

The performances of pentacene thin-film transistor with plasma-enhanced atomic-layer-deposited (PEALD) 150 nm thick Al₂O₃ dielectric are reported. Saturation mobility of 0.38 cm²/V s, threshold voltage of 1 V, subthreshold swing of 0.6 V/decade, and on/off current ratio of about 10⁸ have been obtained. Both depletion and enhancement mode inverter have been realized with the change of treatment method of hexamethyldisilazane on PEALD Al₂O₃ gate dielectric. Full swing depletion mode inverter has been demonstrated at input voltages ranging from 5 V to − 5 V at supply voltage of − 5 V.     

Mechanical properties and microstructure of Al2O3/TiAl in situ composites doped with Cr2O3

Al₂O₃/TiAl composites were successfully fabricated from powder mixtures of Ti, Al, TiO₂ and Cr₂O₃ by a hot-press-assisted exothermic dispersion method. The effect of the Cr₂O₃ addition on the microstructures and mechanical properties of Al₂O₃/TiAl composites was characterized, and the results showed that the Rockwell hardness, flexural strength and fracture toughness of the composites increased as the Cr₂O₃ content increased. When the Cr₂O₃ content was 2.5 wt%, the flexural strength and the fracture toughness attained peak values of 925 MPa and 8.55 MPa m^1/2, respectively. This improvement of mechanical properties was due to the more homogeneous and finer microstructure developed from the addition of Cr₂O₃ and an increase in the ratio of α₂-Ti₃Al to γ-TiAl matrix phases.     

Fabrication of nanostructure Al2O3/ZrO2 (Y2O3) eutectic by combustion synthesis melt-casting under ultra-high gravity

A novel method for preparing Al₂O₃/ZrO₂ (Y₂O₃) eutectic was developed by combining combustion synthesis with melt-casting under ultra-high gravity (CSMC-UHG). The application of UHG = 800 g resulted in a high relative density of 99.8%, and an orientation-growth along the UHG direction. The microstructure was composed of aligned growth regimes containing a triangular dispersion of orderly ZrO₂ rods in Al₂O₃ matrix with a spacing of 300 nm. The eutectic had a high fracture toughness up to 17.9 MPa·m^1/2, which was mainly attributed to the nanostructure and the elastic bridge effects of the aligned ZrO₂ rods.     

Microstructure and electrical properties of Al2O3-ZrO2 composite films for gate dielectric applications

Al₂O₃-ZrO₂ composite films were fabricated on Si by ultrahigh vacuum electron-beam coevaporation. The crystallization temperature, surface morphology, structural characteristics and electrical properties of the annealed films are investigated. Our results indicate that the amorphous and mixed structure is maintained up to an annealing temperature of 900 °C, which is much higher than that of pure ZrO₂ film, and the interfacial oxide layer thickness does not increase after annealing at 900 °C. However, a portion of the Al₂O₃-ZrO₂ film becomes polycrystalline after 1000 °C annealing and interfacial broadening is observed. Possible explanations are given to explain our observations. A dielectric constant of 20.1 is calculated from the 900 °C-annealed ZrO₂-Al₂O₃ film based on high-frequency capacitance-voltage measurements. This dielectric characteristic shows an equivalent oxide thickness (EOT) as low as 1.94 nm. An extremely low leakage current density of ∼2×10⁻⁷ A/cm² at a gate voltage of 1 V and low interface state density are also observed in the dielectric film.     

Synthesis and characterization of Ca3Co4O9 thin films prepared by sol-gel spin-coating technique on Al2O3(001)

Ca₃Co₄O₉ thin films are deposited on Al₂O₃(001) substrates using a sol-gel spin-coating process. X-ray diffraction shows that the film exhibits a single phase of Ca₃Co₄O₉ with the (00l) planes parallel to the film surface. The temperature dependence of magnetic susceptibility showed as expected the existence of two magnetic transitions similar to those observed in bulk samples: a ferrimagnetic and a spin-state transition around 19 and 375 K, respectively. At 5 K the magnetization curves along the c-axis of the Al₂O₃(001) show that the remanent magnetization and coercive field are close to those obtained for films grown by pulsed laser deposition, which evidences the interest to use such an easy technique to grow complex thin films oxides.     

Conducting and topographic AFM analysis of Hf-doped and Al-doped Ta2O5 films

A conductive atomic force microscopy (C-AFM) has been used to study conductivity and electrical degradation of ultrathin (4 nm) Hf- and Al-doped Ta₂O₅ at the nanometer scale. The hardness testing has been also performed using the force measuring ability of the AFM. Since the size of the analyzed area is very small, features which are not visible by macroscopic tests are observed: extremely low leakage current (~ pA) up to significantly higher than the fields during standard current-voltage measurements; charge trapping/detrapping processes manifesting as current peaks at pre-breakdown voltages. Hf and Al addition improves the local conductivity of Ta₂O₅, provokes modification of the leakage current mechanism, and is effective in extending the potential of pure Ta₂O₅ as a high-k material at the nanoscale. The results point to a decisive role of the type of the dopant on the electrical and mechanical properties of the films and their local response to short term microwave irradiation. Hf-doped Ta₂O₅ exhibits excellent electrical stability and high hardness. Al doping provides more plastic films with large electrical inhomogeneities; the microwave treatment at room temperature is a way to improve these parameters to a level comparable to those of Hf-doped films.     

Multiferroic properties of BiFeO3/Bi4Ti3O12 double-layered thin films fabricated by chemical solution deposition

Multiferroic BiFeO₃/Bi₄Ti₃O₁₂ (BFO/BTO) double-layered film was fabricated on a Pt(111)/Ti/SiO₂/Si(100) substrate by a chemical solution deposition method. The effect of an interfacial BTO layer on electrical and magnetic properties of BFO was investigated by comparing those of pure BFO and BTO films prepared by the same condition. The X-ray diffraction result showed that no additional phase was formed in the double-layered film, except BFO and BTO phases. The remnant polarization (2P_r) of the double-layered film capacitor was 100 μC/cm² at 250 kV/cm, which is much larger than that of the pure BFO film capacitor. The magnetization-magnetic field hysteresis loop revealed weak ferromagnetic response with remnant magnetization (2M_r) of 0.4 kA/m. The values of dielectric constant and dielectric loss of the double-layered film capacitor were 240 and 0.03 at 100 kHz, respectively. Leakage current density measured from the double-layered film capacitor was 6.1 × 10^− 7 A/cm² at 50 kV/cm, which is lower than the pure BFO and BTO film capacitors.     

Effect of Nb2O5 on the microstructure and mechanical properties of TiAl based composites produced by hot pressing

In situ composites of TiAl reinforced with Al₂O₃ particles are successfully synthesized from an elemental powder mixture of Ti, Al and Nb₂O₅ by the hot-press-assisted reaction synthesis (HPRS) method. The as-prepared composites are mainly composed of TiAl, Al₂O₃, NbAl₃, as well as small amounts of the Ti₃Al phase. The in situ formed fine Al₂O₃ particles tend to disperse on the matrix grain boundaries of TiAl resulting in an excellent combination of matrix grain refinement and uniform Al₂O₃ distribution in the composites. The Rockwell hardness and densities of TiAl based composites increase gradually with increasing Nb₂O₅ content, and the flexural strength and fracture toughness of the composites have the maximum values of 634 MPa and 9.78 MPa m^1/2, respectively, when the Nb₂O₅ content reaches 6.62 wt.%. The strengthening mechanism was also discussed.     

Properties of La-substituted Na0.5Bi4.5Ti4O15 ferroelectric thin films

Ferroelectric Na_0.5La_0.5Bi₄Ti₄O₁₅ (NaLaBTi) thin films were prepared by a chemical solution deposition method. The NaLaBTi thin films annealed at 750 °C under oxygen atmosphere were randomly oriented polycrystalline. Electrical properties of the NaLaBTi thin films were compared to Na_0.5Bi_4.5Ti₄O₁₅ thin films and better properties were observed in the NaLaBTi thin films. Remnant polarization (2P_r) and coercive electric field (2E_c) were 43 µC/cm² and 204 kV/cm at an applied electric field of 478 kV/cm, respectively. Leakage current density was 1.95 × 10^− 6 A/cm² at 100 kV/cm. Dielectric constant and dielectric loss were 805 and 0.05 at 1 kHz, respectively. Switchable polarization was suppressed by 15% after 1.44 × 10¹⁰ switching cycles.     

Preparation and properties of nano-SiC strengthening Al2O3 composite ceramics

The processing and mechanical behaviors of Al₂O₃-xwt.%SiC (x = 1, 2, 5, ASx) nano-composites prepared by the in situ synthesis of SiC from polycarbosilane (PCS) were investigated. The composites were densified by hot pressing. The microstructure and mechanical properties of the sintered composites were analyzed. The results showed that a fully dense structure was obtained when a few nano-SiC were doped and that the fracture toughness and strength were highly improved compared with those of monolithic Al₂O₃. The fracture toughness reached 5.1 MPa m^1/2 in AS2 composite. The maximum flexural strength was 516 MPa obtained in AS1 composite.     

Dependence of Zr content on electrical properties of Bi3.15Nd0.85Ti3-xZrxO12 thin films synthesized by chemical solution deposition (CSD)

The Bi_3.15Nd_0.85Ti_3-xZr_xO₁₂ (BNTZ) thin films with Zr content (x = 0, 0.05, 0. 1, 0.15, and 0.2) were prepared on Pt/Ti/SiO₂/Si (100) substrates by chemical solution deposition (CSD) technique. The crystal structures of BNTZ films were analyzed by X-ray diffraction (XRD). The effects of Zr contents on the ferroelectric, dielectric properties, and leakage current of BNTZ films were thoroughly investigated. The XRD results demonstrated that all the films possessed a single phase bismuth-layered structure and exhibited the highly preferred (117) orientation. Among these films, the film with Zr content x = 0.1 held the maximum remanent polarization (2P_r) of 50.21 μC/cm² and a low coercive field (2E_c) of 210 kV/cm.     

Element distribution and phase constitution of Al2O3-TiC/W18Cr4V vacuum diffusion bonded joint

Vacuum diffusion bonding between Al₂O₃-TiC ceramic composites and W18Cr4V tungsten-based tool alloy has been carried out by using Ti/Cu/Ti multi-interlayer. Element distribution near the Al₂O₃-TiC/W18Cr4V interface was discussed and fracture morphology was analyzed using electron probe microanalysis. Additionally, phase constitutions of the Al₂O₃-TiC/W18Cr4V joint were determined by X-ray diffraction. The results indicate that Ti-rich layers are formed near both Al₂O₃-TiC and W18Cr4V. The Ti-rich layer near Al₂O₃-TiC helps to wet the Al₂O₃-TiC surface. The Ti-rich layer near W18Cr4V can restrain the formation of Fe-Ti intermetallic compounds in the diffusion transition zone. Residual Cu in the diffusion transition zone can act as a stress releasing zone. The structures of interfacial phases are identified as follows: Al₂O₃-TiC/TiO + Ti₃Al/Cu + CuTi/TiC layer/mixed layer of Fe₃W₃C, Cr₂₃C₆ and α-Fe/W18Cr4V. The fracture morphology of Al₂O₃-TiC/W18Cr4V joint appears brittle features and the failure occurs within the Al₂O₃-TiC ceramic.