Effects of Si,Mn, and water vapour on the microstructure of protective scales grown on Fe–20Cr in CO2 gas

Abstract

Model alloys Fe–20Cr–0.5Si and Fe–20Cr–2Mn (wt-%) were exposed to Ar–20CO₂ and Ar–20CO₂–20H₂O at either 818 or 650°C. In dry gas, protective scales on Fe–20Cr–0.5Si consisted of an outer Cr₂O₃ layer and an inner SiO₂ layer. In wet gas, additional chromia whiskers were formed on top of the duplex scale. Chromia grains formed in wet gas were much smaller than those in dry gas. A TEM analysis revealed that phase constitutions of the protective scale on Fe–20Cr–2Mn were not uniform: Mn₃O₄ and MnCr₂O₄ above alloy grain boundaries and Mn₃O₄, Cr₂O₃ and MnCr₂O₄ on alloy grains. Formation of different oxides and morphologies are discussed in terms of changes in diffusion paths and thermodynamics caused by the presence of carbon and hydrogen.     

Segregation and Local Structure at Grain Boundaries in SiO2-Doped Tetragonal ZrO2 Polycrystalline Materials

SiO₂ doping in Y₂O₃ stabilized tetragonal ZrO₂ (TZP) materials introduced significant change in mechanical properties around 0.3 wt.% doping level [1]. In order to understand the influence of grain boundary structure and chemistry by doping, high purity undoped and SiO₂-doped 3Y-TZP samples were studied using high-resolution and analytical TEM. Typical grain boundary structures are different for the two types of samples, while amorphous film was not observed at most grain boundaries. A new EDS analysis method was introduced to detect the weak Si and Y signals which overlap with the predominent Zr peaks. It revealed that Si segregation to the grain boundary saturates at 12 at./nm² (or 1.5 monolayer of SiO₂) when the SiO₂ doping level reached and surpassed 0.3 wt.%. It is the segregated atoms which enhanced the grain boundary diffusivity and therefore altered the deformation mechanism.     

Abnormal dielectric behaviors in Mn-doped CaCu3Ti4O12 ceramics and their response mechanism

Mn-doped CaCu₃Ti₄O₁₂ (CCTO) polycrystalline ceramics have been prepared by the conventional solid state sintering. Our results indicate that 10% Mn doping can decrease the dielectric permittivity in CaCu₃Ti₄O₁₂ by about 2 orders of magnitude (from 10⁴ to 10²). The grain and grain boundary activation energies show an obvious increase from 0.054 eV to 0.256 eV, and decrease from 0.724 eV to 0.258 eV with increasing the Mn doping concentration, respectively, which may be caused by the variation of Cu and Ti valence states in the CCTO samples evidenced by the X-ray absorption spectra. The similar grain and grain boundary activation energies result in invalidation of the internal boundary layer capacitance effect for the 10% Mn-doped CCTO sample, and thus result in the dramatic decrease of dielectric permittivity.     

Characterization of Chromia Scales Grown on Pure Chromium in Different Oxidizing Atmospheres

Abstract

Scanning electron microscopy, X-ray diffraction, photoelectrochemistry and microphotoelectrochemistry have been used to characterize thin chromia scales, in the micrometer range, grown on pure chromium at 900°C in oxygen and in water vapour. The duplex structure formed, more easily observable in water vapour grows by the opposite transport of chromium and of oxide/hydroxide ions. The external chromia subscale exhibits the usually reported 3.5 eV bandgap whereas the internal subscale presents a reduced gap possibly due to impurity contribution. Imaging the photocurrent generated in this subscale allows the observation of good metal-oxide interface properties of samples grown in H₂O, whereas samples grown in O₂, (liable to cracking during cooling), exhibit partially disrupted zones.     

On the surface analysis of copper oxides: the difficulty in detecting Cu3O2

The existence of Cu₃O₂, a gross defect structure of Cu₂O, has been documented experimentally since the early 1960s. However, discussions of the oxidation of copper often neglect the importance of this phase; in fact, it is often omitted entirely from such discussions. This results from the difficulty in determining the chemical state during sputter depth profiling and relying on techniques that have difficulty providing chemical state information. The occurrence of sputter reduction during the depth profiling of copper oxide layers has been demonstrated with XPS depth profiles on a series of copper samples oxidized, for varying lengths of time, in air at a temperature of either 423 or 523 K. Under these conditions, a thin layer of CuO/Cu(OH)₂ terminates the oxide layers. Beneath this layer, the presence of Cu₃O₂ is expected on the samples prepared at 423 K. However, immediately upon the beginning of sputtering, only Cu¹⁺ is detected in the oxide layers. A zone of constant Cu:O ratio of (approximately ∼1.5) is found throughout most of the oxide layer even though Cu²⁺ is not detected. On the samples prepared at 523 K, the presence of CuO is anticipated. However, Cu²⁺ is not detected after sputtering is initiated and a region of constant Cu:O ratio of ca. 1.5 is detected. The inherent difficulties involved in investigating oxide layer growth and vertical oxide layer structure using sputter depth profiling are discussed in light of this experimental data.     

Growth characteristics and electrical properties of La2O3 gate oxides grown by thermal and plasma-enhanced atomic layer deposition

We comparatively investigated thermal and plasma-enhanced atomic layer deposition (T-ALD and PE-ALD, respectively) of lanthanium oxide (La₂O₃) films using tris(isopropyl-cyclopentadienyl)lanthanum [La(iPrCp)₃] as a La precursor. H₂O and O₂ plasma were used as reactants for T-ALD and PE-ALD La₂O₃, respectively. Both of the processes exhibited ALD mode growth with good self-saturation behavior and produced pure La₂O₃ films. However, PE-ALD La₂O₃ showed higher growth rate and dielectric constant value than those of T-ALD La₂O₃. In addition, lower leakage current density and interface state density were observed for PE-ALD La₂O₃, compared to those of the T-ALD La₂O₃. These experimental results indicate that the PE-ALD La₂O₃ process using La(iPrCp)₃ precursor can be one of the viable options applicable into future microelectronic industry.     

Thickness dependence of high-k materials on the characteristics of MAHONOS structured charge trap flash memory

The electrical characteristics of tunnel barrier engineered charge trap flash (TBE-CTF) memory of MAHONOS (Metal/Al₂O₃/HfO₂/SiO₂/Si₃N₄/SiO₂/Si) structure were investigated. The stack of SiO₂/Si₃N₄/SiO₂ films were used as engineered tunnel barrier, HfO₂ and Al₂O₃ films were used as charge trap layer and blocking oxide layer, respectively. For comparison, the electrical characteristics of MONOS (Metal/SiO₂/Si₃N₄/SiO₂/Si), MONONOS (Metal/SiO₂/Si₃N₄/SiO₂/Si₃N₄/SiO₂/Si), and MAHOS (Metal/Al₂O₃/HfO₂/SiO₂/Si) were also evaluated. The energy band diagram was designed by using the quantum-mechanical tunnel model (QM) and then the CTF memory devices were fabricated. As a result, the optimized thickness combination of MAHONOS structure was confirmed. The tunnel barrier engineered MAHONOS CTF memory showed a considerable enhancement of program/erase (P/E) speeds, retention time and endurance characteristics.     

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.     

Thermal-stress stability of yttrium oxide as a buffer layer of metal-ferroelectric-insulator-semiconductor field effect transistor

The effect of thermal stress on the electrical properties of ferroelectric/semiconductor structure was investigated when introducing Y₂O₃ film as a barrier layer in the structure. Two different thermal stress states could be obtained by fast (400 °C/min) or slow (30 °C/min) cooling of sputter-deposited Y₂O₃ films on silicon wafer from 800 °C. The formation of interfacial layer containing Y-Si-O and SiO₂ layers while annealing could be characterized by using a spectroscopic ellipsometry. The introduction of strain-induced defects from thermal stress of the fast cooled sample showed a soft breakdown at low applying voltage. In the capacitance-voltage relation, a flat band voltage shift, hysteresis, and stretch-out phenomena were also observed. Nd₂Ti₂O₇ was spin deposited using sol-gel procedure on the Y₂O₃/Si to form a metal-ferroelectric-insulator field effect transistor structured sample. These Nd₂Ti₂O₇/Y₂O₃/Si samples were also furnace-annealed at 800 °C and cooled down to room temperature fast or slowly. One order lower value of leakage current, 1E−8 A/cm² was observed with these samples when comparing with the Y₂O₃/Si samples. A soft breakdown of the fast cooled sample seemed to have the same origin as the fast cooled Y₂O₃/Si sample, i.e., the strain-induced defects in the interfacial layer containing Y-Si-O and SiO₂ phases. Hysteretic gaps of the Nd₂Ti₂O₇/Y₂O₃/Si samples showed a possibility to be used as a memory window for ferroelectric gate.     

Stress development and relaxation in Al2O3 during early stage oxidation of β-NiAl

Abstract

Using a glancing synchrotron X-ray beam (Advanced Photon Source, Beamline 12BM, Argonne National Laboratory), Debye-Scherrer diffraction patterns from thermally grown oxides on NiAl samples were recorded during oxidation at 1000 or 1100°C in air. The diffraction patterns were analyzed to determine strain and phase changes in the oxide scale as it developed and evolved. Strain was obtained from measurements of the elliptical distortion of the Debye-Scherrer rings, where data from several rings of a single phase were used. Results were obtained from α-Al₂O₃ as well as from the transition alumina, in this case θ-Al₂O₃, which formed during the early stage. Compressive stress was found in the first-formed transition alumina, but the initial stress in α-Al₂O₃ was tensile, with a magnitude high enough to cause Al₂O₃ fracture. New α-Al₂O₃ patches nucleated at the scale/alloy interface and spread laterally and upward. This transformation not only puts the alpha alumina in tension, but can also cause the transition alumina to be in tension. After a complete α-Al₂O₃ layer formed at the interface, the strain level in α-Al₂O₃ became compressive, reaching a steady state level around –75 MPa at 1100°C. To study a specimen’s response to stress perturbation, samples with different thickness, after several hours of oxidation at 1100°C, were quickly cooled to 950°C to impose a compressive thermal stress in the scale. The rate of stress relaxation was the same for 1 and 3.5 mm thick samples, having a strain rate of ～1×10^?8/s. This behavior indicates that oxide creep is the major stress relaxation mechanism.     

Oxidation mechanism of Ni–20Cr thin strips and effect of a mechanical loading

Abstract

The oxidation behaviour of Ni-20Cr foils of 200 μm thickness was studied in air at 600°C and 900°C. The oxide morphology and nature were determined by SEM and TEM. The scales formed at all temperatures were complex, with an outer NiO layer and an intermediate layer of equiaxed NiO, NiCr₂O₄ and Cr₂O₃ grains. At 600°C, internal oxidation of chromium occurred in the substrate while a continuous Cr₂O₃ layer was observed at 900°C. The effect of a tensile load on the oxidation kinetics and mechanism of Ni–20Cr alloy was also examined. The results indicated that applying a tensile load did not modify the oxide nature and morphology but induced an increase of the oxidation rate, promoting the formation of internal oxidation at 600°C, and of a NiCr₂O₄ layer at 900°C.     

Blue PL and EL emissions from Bi-activated binary oxide thin-film phosphors

The photoluminescent (PL) and electroluminescent (EL) characteristics in the thin films of various Bi-activated binary oxide phosphors have been investigated. La₂O₃:Bi, Gd₂O₃:Bi and Y₂O₃:Bi phosphor thin films were prepared on thick BaTiO₃ ceramic sheet substrates by r.f. magnetron sputtering depositions followed by postannealing. Intense blue PL emissions were observed from all Bi-activated binary oxide phosphor thin films postannealed at a high temperature. Blue, whitish blue-green or blue-green emissions were observed from thin-film electroluminescent (TFEL) devices fabricated with a La₂O₃:Bi, a Gd₂O₃:Bi or a Y₂O₃:Bi thin-film emitting layer, respectively. In addition, high luminance with good color purity in blue EL was obtained in a TFEL device using a La₂O₃:Bi thin film prepared under optimized conditions.     

Synthesis of GaN nanorods by ammoniating Ga2O3 films on In2O3 layer deposited on Si (111) substrates

GaN nanorods were synthesized by ammoniating Ga₂O₃/In₂O₃ thin films deposited on Si (111) with magnetron sputtering. X-ray diffraction, Scanning electronic microscope and high-resolution TEM results show that they are GaN single crystals, the sizes of which vary from 2 to 7 μm in length and 200 to 300 nm in diameter. In₂O₃ middle layer plays an important role in the GaN nanorod growth.     

Ni-Al-O diffusion barrier layer for high-κ metal-oxide-semiconductor capacitor

Using amorphous Ni-Al-O (a-Ni-Al-O) thin film as the intermediate layer, poly-crystalline Er₂O₃ thin film was grown on a-Ni-Al-O/Si (p-type) via laser molecular beam epitaxy, forming the Er₂O₃/Ni-Al-O gate stack. It was found that the mean dielectric constant of the Er₂O₃/Ni-Al-O gate stack with an equivalent oxide thickness of 1.5 nm is about 17-23, the interfacial states density is about 3.16 × 10¹² cm⁻² and the stack gate leakage current density is as small as 4.1 × 10^− 6 A/cm². Furthermore, The insertion of the Ni-Al-O thin film between the Er₂O₃ gate dielectric and p-Si substrate prevents the oxygen from being out-diffused, which significantly improved the stability of gate stack, showing that the Er₂O₃/Ni-Al-O gate stack thin film could be used as an ideal gate oxide layer for the future Metal Oxide Semiconductor Field Effect Transistors.     

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.     

Application of fracture mechanics tofailure analysis and to residual life assessment of components operating at high temperatures

Abstract

MCrAlY overlay coatings have been successfully used as a means of improving the oxidation performance of gas turbine blades operating at elevated temperatures. However, depletion of aluminium can limit the ability of such coatings to form a protective oxide layer should spallation of the original α-Al₂O₃ oxide layer occur under thermal cycling conditions. It is the objective of the current research to evaluate the potential of NiAl₃ as a reservoir phase for a NiCrAlY overlay coating on a IN738LC superalloy substrate at 1,100°C in air. The morphologies and microstructures of the conventional NiCrAlY and NiAl3-modified NiCrAlY overlay coatings in the as-sprayed and oxidised conditions were characterised using SEM, EDX and XRD techniques.     

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.     

First-principles study on electronic structure, phase stability, and optical properties of In2X2O7 (X═C, Si, Ge or Sn)

In₂Ge₂O₇ and In₂Si₂O₇ are commonly used as scintillation materials. More studies on In₂X₂O₇ (X═C, Si, Ge, or Sn) are important to explore the possibility of using these materials for optoelectronic devices. This work presents results dealing with structural properties, electronic structure, chemical bonding, carrier effective masses, and optical spectra of polymorphs of In₂X₂O₇ obtained from first-principles calculations. The monoclinic phase of In₂Ge₂O₇, cubic and monoclinic phases of In₂Si₂O₇, as well as cubic phase of In₂Sn₂O₇ are known in scientific literature. From the total energy calculations at high pressure/strain we have found that the monoclinic phase of In₂Si₂O₇, In₂Ge₂O₇, and In₂Sn₂O₇ can be transformed into the cubic phase. The cubic phase of In₂Ge₂O₇ and In₂Sn₂O₇ is found to be more stable than the monoclinic phase. However, the monoclinic phase of In₂C₂O₇ and In₂Si₂O₇ is more stable than the cubic phase. The phase stability study suggests that In₂C₂O₇ is not stable, and that it might dissociate into corresponding binary oxides. Effective masses of electrons and holes have been estimated. Analysis of optical properties shows that in Si solar cells In₂Si₂O₇ and In₂Sn₂O₇ can be used as antireflection coating layer.     

The effect of H2-anneal on the adhesion of Al2O3 scales on a Fe3Al-based alloy

Abstract

The cyclic (1,100°C, air) and isothermal (1,000°C, O₂) oxidation behavior of a Fe-28Al-5Cr (at%) alloy, with and without a prior H₂-anneal heat treatment at 1,200°C for 100 h, was studied. Changes in interfacial chemistry were evaluated using Scanning Auger Microscopy after removal of the oxide film in ultra high vacuum. This was achieved by making a scratch on the specimen surface, which caused spallation of the film at various locations along the scratch. The scale thickness and the temperature drop at which spallation took place during cooling were utilized to semi-quantitatively compare the adherence of the scales. Porosity at the scale–alloy interface and the scale microstructure were determined from scanning electron microscope observations. It was found that H₂-anneal greatly improved scale adhesion and resulted in a pore-free and sulfur-free interface. The effects were similar to that of a 0.1 at% Zr-containing alloy, except that the improvement in scale adhesion was not as great as that from Zr doping. This implies that oxide/alloy interfaces are not intrinsically strong and the effect of reactive elements, such as Zr, is more than preventing impurity from segregating to the interface. Results are also compared with the effect of H₂-anneal on other model alloys, such as NiCrAl, FeCrAl and NiAl, and on single crystal superalloys.     

Oxide and interface charges in thin SiO2 films thermally grown on RF plasma hydrogenated silicon

A study of the defect centres, related to oxide charge and interface traps, induced in thin SiO₂ layer by technological procedures has been made. Thermal oxidation of Si was performed in dry O₂ at a temperature of 850°C. The Si cleaning procedures included dry hydrogen plasma treatment at different substrate temperatures and standard RCA wet cleaning. Characterization of defects was performed by analyzing the frequency dispersion of the capacitance-voltage characteristics. The origin of the defects was assessed by analysis of the IR spectra through computer simulation of the oxide structure and AFM images.