The influence of technological conditions on electrical properties of MIM systems

Experimental results obtained by various authors from the sandwich cathodes of identical structure differ sometimes rather sizably. That is why we studied the connection between the technological process of cathode preparation (the change of the structure of basic electrode and the oxidation method) and the characteristics of leakage and emission currents. The measurements were performed with the thin-film sandwich cathodes of the structure Al-Al₂O₃-Au. It was found that even the small deviation from the usually used method of oxidation of the bottom aluminium electrode influences above all the negative resistance region on the leakage VA characteristic and the angular distribution of emitted electrons. The comparison and discussion of experimental values derived by various authors must be, therefore, allways carried out with regard to the method used for cathode preparation.     

Asymmetry in electrical properties of Al‐doped TiO2 film with respect to bias voltage

The energy diagram of RuO₂/Al‐doped TiO₂/RuO₂ structures was estimated from the capacitance–voltage and leakage current density–voltage curves. The Al‐doping profile in TiO₂ film was varied by changing position of the atomic layer deposition cycle of Al₂O₃ during the atomic layer deposition of 9 nm‐thick TiO₂ film. The interface between the TiO₂ film and the RuO₂ electrode containing Al‐doping layer showed a higher Schottky barrier by 0.1 eV compared with the opposite interface without the doping layer. The evolution of various leakage current profiles upon increasing the bias with opposite polarity could be well explained by the asymmetric Schottky barrier. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Sc2O3-W matrix impregnated cathode with spherical grains

Sc₂O₃-W matrix cathodes have been prepared by using a liquid-liquid doping method combined with high-temperature sintering. The microstructure and physical behavior of active substances of scandia-doped tungsten matrix and impregnated cathode has been studied by SEM and AES methods. The results show that the matrix has a homogeneous structure composed of W grains with spherical shape and superfine Sc₂O₃ particles dispersed uniformly over and among W grains. After impregnation, this Sc-type impregnated cathode has high emission capability. Space-charge-limited current density could reach 52 A/cm² at 850 °C_b. The high emission results from a Ba-Sc-O active layer with a thickness of about 80 nm, which is formed at the cathode surface during the activation period. Both the decrease of the thickness of active surface layer and the decrease of the content of Sc at the surface could lead to the degradation of current density during operation.     

Characterization of Y2O3 gate dielectric on n-GaAs substrates

Physical and electrical properties of sputtered deposited Y₂O₃ films on NH₄OH treated n-GaAs substrate are investigated. The as-deposited films and interfacial layer formation have been analyzed by using X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectroscopy (SIMS). It is found that directly deposited Y₂O₃ on n-GaAs exhibits excellent electrical properties with low frequency dispersion (<5%), hysteresis voltage (0.24 V), and interface trap density (3 × 10¹² eV⁻¹ cm⁻²). The results show that the deposition of Y₂O₃ on n-GaAs can be an effective way to improve the interface quality by the suppression on native oxides formation, especially arsenic oxide which causes Fermi level pinning at high-k/GaAs interface. The Al/Y₂O₃/n-GaAs stack with an equivalent oxide thickness (EOT) of 2.1 nm shows a leakage current density of 3.6 × 10⁻⁶ A cm⁻² at a V_FB of 1 V. While the low-field leakage current conduction mechanism has been found to be dominated by the Schottky emission, Poole-Frenkel emission takes over at high electric fields. The energy band alignment of Y₂O₃ films on n-GaAs substrate is extracted from detailed XPS measurements. The valence and conduction band offsets at Y₂O₃/n-GaAs interfaces are found to be 2.14 and 2.21 eV, respectively.     

Nanostructured oxide membranes

Porous aluminum (Al 99.99%) foil membranes prepared by electrochemical anodizing and subsequent removing the continuous barrier layer by ion-plasma irradiation are described. As a result, Al₂O₃ membranes about 2–5 μm thick with regular arrangement of channels have been obtained. The possibility has been shown of regulation of a channel diameter in a range of 20–100 nm by changing the oxidation conditions. The experimental dependences of Al and Al₂O₃ sputtering coefficients on the xenon ion energy (100–400 eV) and the angle of incidence have been obtained.     

On the correlation between the composition of Pr doped garnet type materials and their photoluminescence properties

Lu₃(Al,Ga)₅O₁₂ and (Y,Lu)₃(Al,Mg,Si)₅O₁₂ samples doped with 1% Pr³⁺ were prepared by two aqueous sol-gel chemistry approaches, such as citrate and glycolate methods. All samples were characterised by powder X-ray diffraction (XRD), thermal quenching (TQ), fluorescence lifetime measurements and photoluminescence (PL) techniques. It turned out that the Pr³⁺ emission is very sensitive to the composition of the garnet host lattice. Lu₃Al₅O₁₂:Pr³⁺ samples showed mainly [Xe]4f¹5d¹→[Xe]4f² broad band emission in UV-blue region, whereas [Xe]4f²-[Xe]4f² line emission of Pr³⁺ dominated in Lu₃Ga₅O₁₂ samples. Modification of garnet crystals with Mg²⁺-Si⁴⁺ pair has led to generation of strong crystal field strength resulting in energy transfer from 5d to 4f orbitals. Y₃AlMg₂Si₂O₁₂ composition generated the strongest crystal field splitting out of all synthesised samples and showed practically only Pr³⁺ [Xe]4f²-[Xe]4f² line emission in the red spectral region.     

The leakage current mechanisms in the Schottky diode with a thin Al layer insertion between Al0.245Ga0.755N/GaN heterostructure and Ni/Au Schottky contact

This paper investigates the behaviour of the reverse-bias leakage current of the Schottky diode with a thin Al inserting layer inserted between Al0.245Ga0.755 N/GaN heterostructure and Ni/Au Schottky contact in the temperature range of 25-350°C. It compares with the Schottky diode without Aluminium inserting layer. The experimental results show that in the Schottky diode with Al layer the minimum point of I-V curve drifts to the minus voltage, and with the increase of temperature increasing, the minimum point of I-V curve returns the 0 point. The temperature dependence of gate-leakage currents in the novelty diode and the traditional diode are studied. The results show that the Al inserting layer introduces interface states between metal and Al0.245Ga0.755N. Aluminium reacted with oxygen formed Al2O3 insulator layer which suppresses the trap tunnelling current and the trend of thermionic field emission current. The reliability of the diode at the high temperature is improved by inserting a thin Al layer.     

Characterization of scandia doped pressed cathode fabricated by spray drying method

Scandia doped pressed cathode was prepared by a new method of spray drying combined with two-step hydrogen reduction process. The Sc₂O₃ and barium-calcium aluminate co-doped powders have sub-micrometer size in the range of 0.1-1 μm and scandium oxide and barium-calcium aluminate are distributed evenly in the powders. The cathodes sintered by powder metallurgy at 1600 °C_b have a smooth surface and sub-micrometer grain structure with homogeneous distribution of scandium, barium, calcium and aluminum which are dispersed over and among the tungsten grains. This cathode has good emission, e.g., the current density of this cathode reaches 31.50 A/cm² at 850 °C_b. After proper activation, the cathode surface is covered by a Ba-Sc-O active substances layer with a preferable atomic ratio, leading to its good emission property. The evaporation activation energy of SDP cathode with 4.58 eV is the highest among the Ba-W, M-type and SDP cathodes, and the average evaporation velocity v_t of SDP cathode with 1.28 × 10⁻⁸ g cm⁻² s⁻¹ at 1150 °C_b is the lowest one.     

Electrical properties of thin yttria-stabilized zirconia overlayers produced by atomic layer deposition for solid oxide fuel cell applications

Thin films of yttria-stabilized zirconia (YSZ) electrolyte were prepared by atomic layer deposition at 300 °C for solid oxide fuel cell (SOFC) applications. YSZ samples of 300-1000 nm thickness were deposited onto La_0.8Sr_0.2MnO₃ (LSM) cathodes. A microstructural study was performed on these samples and their electrical properties were characterised between 100 and 390 °C by impedance spectroscopy. A remarkable feature is that the as-deposited layers were already crystalline without any annealing treatment. Their resistance decreased when reducing the layer thickness; nevertheless, their conductivity and activation energy were significantly lower than those reported in the literature for bulk YSZ.     

A study of Eu2O3, Sc2O3 co-doped tungsten matrix impregnated cathode

Eu₂O₃ and Sc₂O₃ co-doped W matrix impregnated cathodes have been prepared by the powder metallurgy method. The constitution of active elements on activated cathode surface is analyzed by in-situ Auger electron spectroscopy. It is found that although Eu exists in the matrix, no Eu is found on the cathode surface due to the formation of a stable Eu containing compound. Sc, Ba and O diffuse to the surface of the cathode and form an active surface layer during the activation period whereas the stable Eu-compound cannot liberate free Eu, which can diffuse from the cathode to the surface. The active substance of Sc, Ba and O on the cathode surface contribute to the emission property.     

Properties of an Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/Si interface

The phase chemical composition of an Al₂O₃/Si interface formed upon molecular deposition of a 100-nm-thick Al₂O₃ layer on the Si(100) (c-Si) surface is investigated by depth-resolved ultrasoft x-ray emission spectroscopy. Analysis is performed using Al and Si L_{2, 3} emission bands. It is found that the thickness of the interface separating the c-Si substrate and the Al₂O₃ layer is approximately equal to 60 nm and the interface has a complex structure. The upper layer of the interface contains Al₂O₃ molecules and Al atoms, whose coordination is characteristic of metallic aluminum (most likely, these atoms form sufficiently large-sized Al clusters). The shape of the Si bands indicates that the interface layer (no more than 10-nm thick) adjacent to the substrate involves Si atoms in an unusual chemical state. This state is not typical of amorphous Si, c-Si, SiO₂, or SiO_x (it is assumed that these Si atoms form small-sized Si clusters). It is revealed that SiO₂ is contained in the vicinity of the substrate. The properties of thicker coatings are similar to those of the 100-nm-thick Al₂O₃ layer and differ significantly from the properties of the interfaces of Al₂O₃ thin layers.     

Role of Ti in the luminescence process of Al2O3:Si,Ti

Al₂O₃:Si,Ti, prepared under oxidizing condition at high temperature, gives PL emission around 430 nm when excited with 240 nm. The Al₂O₃:C, TL/OSL phosphor, also shows emission around 430 nm, which corresponds to characteristic emission of F-center. Thus, to identify the exact nature of luminescent center in Al₂O₃:Si,Ti, fluorescence lifetime measurement studies were carried out along with the PL,TL and OSL studies. The PL and TL in Al₂O₃:Si,Ti show emission around 430 nm and the time-resolved fluorescence studies show lifetime of about 43 μs for the 430 nm emission, which is much smaller than the reported lifetime of ∼35 ms for the 430 nm emission (F-center emission) in Al₂O₃:C phosphor. Therefore, the emission observed in Al₂O₃:Si,Ti phosphor was assigned to Ti⁴⁺ charge transfer transition. Fluorescence studies of Al₂O₃:Si,Ti do not show any traces of F and F⁺ centers. Also, Ti⁴⁺ does not show any change in the charge state after gamma-irradiation. On the basis of the above studies, a mechanism for TSL/OSL process in Al₂O₃:Si,Ti is proposed.     

Fabrication of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/Al structure by nitric acid oxidation at room temperature

A thick Al₂O₃/aluminum (Al) structure has been fabricated by oxidation of Al with 68wt% and 98wt% nitric acid (HNO₃) aqueous solutions at room temperature. Measurements of the Al₂O₃ thickness vs. the oxidation time show that reaction and diffusion are the rate-determining steps for oxidation with 68wt% and 98wt% HNO₃ solutions, respectively. Observation of transmission electron micrographs shows that the Al₂O₃ layer formed with 68wt% HNO₃ has a structure with cylindrically shaped pores vertically aligned from the Al₂O₃ surface to the Al₂O₃/Al interface. Due to the porous structure, diffusion of HNO₃ proceeds easily, resulting in the reaction-limited oxidation mechanism. In this case, the Al₂O₃/Al structure is considerably rough. The Al₂O₃ layer formed with 98wt% HNO₃ solutions, on the other hand, possesses a denser structure without pores, and the Al₂O₃/Al interface is much smoother, but the thickness of the Al₂O₃ layer formed on crystalline Al regions is much smaller than that on amorphous Al regions. Due to the relatively uniform Al₂O₃ thickness, the leakage current density flowing through the Al₂O₃ layer formed with 68wt% HNO₃ is lower than that formed with 98wt% HNO₃.     

Effect of surface roughness on the development of protective Al2O3 on Fe-10Al (at.%) alloys containing 0-10 at.% Cr

The effect of alloy surface roughness, achieved by different degrees of surface polishing, on the development of protective alumina layer on Fe-10 at.% Al alloys containing 0, 5, and 10 at.% Cr was investigated during oxidation at 1000 °C in 0.1 MPa oxygen. For alloys that are not strong Al₂O₃ formers (Fe-10Al and Fe-5Cr-10Al), the rougher surfaces increased Fe incorporation into the overall surface layer. On the Fe-10Al, more iron oxides were formed in a uniform layer of mixed aluminum- and iron-oxides since the layer was thicker. On the Fe-5Cr-10Al, more iron-rich nodules developed on an otherwise thin Al₂O₃ surface layer. These nodules nucleated preferentially along surface scratch marks but not on alloy grain boundaries. For the strong Al₂O₃-forming Fe-10Cr-10Al alloy, protective alumina surface layers were observed regardless of the surface roughness. These results indicate that the formation of a protective Al₂O₃ layer on Fe-Cr-Al surfaces is not dictated by Al diffusion to the surface. More cold-worked surfaces caused an enhanced Fe diffusion, hence produced more Fe-rich oxides during the early stage of oxidation.     

Energy distribution of electrons emitted from Al-Al2O3-Al system

On sandwich cathodes of the Al-Al₂O₃-Al structure were measured both the VA characteristics of leakage and emission currents and the distribution of emitted electrons according to a normal energy componentN(W _x ) for various voltages thicknesses of dielectric and upper metal films, and various voltages superimposed on cathode (leakage voltage). On the basis of experimental dependences obtained, the influence of single parts of the system on the transported electrons has been discussed. Three groups of distribution ofN(W _x ) were found differing in their form on the one hand and in their position in the energy band diagram of the studied system, on the other one. The dependence of the distribution width and the position of its maximum on the thickness of the dielectric layer and electric field intensity was followed. To describe the processes in a dielectric layer a model assuming the random collision processes has been applied. All three groups of measured distributions may be expressed by a single equation of the typeN(W _x )=N ₀(W _x ). P(z). D(W), except a small number of cases where the influence of the upper electrode barrier due to higher voltages on cathode is not taken into account and thus theD(W) term need not be considered.     

Determination of the Al content in aluminum‐modified SiO2 stationary phases using X‐ray scattering spectroscopy

This paper describes the determination of aluminum in the presence of silica using a method based on X‐ray scattering spectrometry coupled with chemometric tools (principal component analysis and partial least squares) that treat samples according to their Al concentrations. Samples were prepared by mixing Al and Si oxides. X‐ray spectra of all samples, including pure oxides of aluminum and silicon, were submitted to the chemometric tools. Principal component analysis results show that it is possible to classify three subgroups of Al (low, medium and high Al content), whereas partial least squares 1 was used to construct calibration and cross‐validation models for Al in the presence of Si. The method is simple, fast, does not require sample dissolution prior to analysis, is of low cost and can be applied as a routine procedure. The method was used to quantify Al in some chromatographic stationary phases covered with a layer of Al₂O₃. Good correlations with low errors were obtained. Copyright © 2013 John Wiley & Sons, Ltd.     

A combined SIMS-ISS study of the high-Tc superconducting compound YBa2Cu3-yAlyOx

Secondary ion yields, secondary ion-energy spectra and ion-scattering spectra for high-T _c superconducting compound YBa₂Cu_3–y Al _y O _x have been studied as a function of Al content (y = 0–0.8). In accordance with data known from literature, it was shown by Secondary-Ion Mass Spectrometry (SIMS) that Al doping of YBaCuO results in the selective substitution of Cu1 atoms with Al atoms. The correlated non-monotonic variations of the secondary-ion yield, the most probable secondary ion energy and the scattered ion yield for Y and Ba were observed with a growth of Al concentration and were explained in terms of the modification of local composition and electronic structure in the vicinity of these atoms. The kinetics of secondary-ion emission during sputtering of the original surface layer degraded under air exposure has also been measured for the YBaCuAlO samples. It was found that the ion currents ratio Ba⁺/BaOH⁺ may characterize the level of degradation and the oxygen concentration in Cul-O layers     

X-ray photoelectron spectroscopy of nano-multilayered Zr-O/Al-O coatings deposited by cathodic vacuum arc plasma

Nano-multilayered Zr-O/Al-O coatings with alternating Zr-O and Al-O layers having a bi-layer period of 6-7 nm and total coating thickness of 1.0-1.2 μm were deposited using a cathodic vacuum arc plasma process on rotating Si substrates. Plasmas generated from two cathodes, Zr and Al, were deposited simultaneously in a mixture of Ar and O₂ background gases. The Zr-O/Al-O coatings, as well as bulk ZrO₂ and Al₂O₃ reference samples, were studied using X-ray photoelectron spectroscopy (XPS). The XPS spectra were analyzed on the surface and after sputtering with a 4 kV Ar⁺ ion gun. High resolution angle resolved spectra were obtained at three take-off angles: 15°, 45° and 75° relative to the sample surface.It was shown that preferential sputtering of oxygen took place during XPS of bulk reference ZrO₂ samples, producing ZrO and free Zr along with ZrO₂ in the XPS spectra. In contrast, no preferential sputtering was observed with Al₂O₃ reference samples. The Zr-O/Al-O coatings contained a large amount of free metals along with their oxides. Free Zr and Al were observed in the coating spectra both before and after sputtering, and thus cannot be due solely to preferential sputtering.Transmission electron microscopy revealed that the Zr-O/Al-O coatings had a nano-multilayered structure with well distinguished alternating layers. However, both of the alternating layers of the coating contained of a mixture of aluminum and zirconium oxides and free Al and Zr metals. The concentration of Zr and Al changed periodically with distance normal to the coating surface: the Zr maximum coincided with the Al minimum and vice versa. However the concentration of Zr in both alternating layers was significantly larger than that of Al. Despite the large free metal concentration, the Knoop hardness, 21.5 GPa, was relatively high, which might be attributed to super-lattice formation or formation of a metal-oxide nanocomposite within the layers.     

Fluorination of Al2O3 blocking layer for improving the performance of metal‐oxide‐nitride‐oxide‐silicon flash memory

The characteristics of Al₂O₃ film grown by atomic‐layer deposition as blocking layer with and without fluorine plasma treatment were investigated based on a capacitor structure of Al/Al₂O₃/TaON/SiO₂/Si. The physical structure was studied by transmission electron microscopy, and the chemical composition of the blocking layer was analyzed by X‐ray photoelectron spectroscopy and secondary ion mass spectroscopy. Moreover, the surface roughness of the blocking layer was investigated by atomic force microscopy. Compared with a capacitor with Al₂O₃ blocking layer, the one with fluorinated Al₂O₃ displayed higher programming/erasing speeds, better endurance property and better charge retention characteristic because the fluorination could reduce excess oxygen and traps in the blocking layer, thus forming a larger barrier height at the interface between the charge‐trapping layer and the blocking layer. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Correlation between Al2O3 particles and interface of Al-Al2O3 coatings by cold spray

Al-Al₂O₃ composite coatings with different Al₂O₃ particle shapes were prepared on Si and Al substrate by cold spray. The powder compositions of metal (Al) and ceramic (Al₂O₃) having different sizes and agglomerations were varied into ratios of 10:1 wt% and 1:1 wt%. Al₂O₃ particles were successfully incorporated into the soft metal matrix of Al. It was found that crater formation between the coatings and substrate, which is typical characteristic signature of cold spray could be affected by initial starting Al₂O₃ particles. In addition, when the large hard particles of fused Al₂O₃ were employed, the deep and big craters were generated at the interface between coatings and hard substrates. In the case of pure soft metal coating such as Al on hard substrate, it is very hard to get proper adhesion due to lack of crater formation. Therefore, the composite coating would have certain advantages.