Wet-chemical etching of the barrier oxide layer of anodic aluminum oxide (AAO) was systematically investigated by using scanning electron microscopy (SEM), secondary ion mass spectrometry (SIMS), and a newly devised experimental setup that allows accurate in situ determination of the pore opening point during chemical etching of the barrier oxide layer. We found that opening of the barrier oxide layer by wet-chemical etching can be significantly influenced by anodization time (tanodi). According to secondary ion mass spectrometry (SIMS) analysis, porous anodic aluminum oxide (AAO) samples formed by long-term anodization contained a lower level of anionic impurity in the barrier oxide layer compared to the short-term anodized one and consequently exhibited retarded opening of the barrier oxide layer during the wet-chemical etching. The observed compositional dependence on the anodization time (tanodi) in the barrier oxide layer is attributed to the progressive decrease of the electrolyte concentration upon anodization. The etching rate of the outer pore wall at the bottom part is lower than that of the one at the top part due to the lower level of impurity content in that region. This indicates that a concentration gradient of anionic impurity in the outer pore wall oxide may be established along both the vertical and radial directions of cylindrical pores. Apart from the effect of electrolyte concentration on the chemical composition of the barrier oxide layer, significantly decreased current density arising from the lowered concentration of electrolyte during the long-term anodization (~120 h) was found to cause disordering of pores. The results of the present work are expected to provide viable information not only for practical applications of nanoporous AAO in nanotechnology but also for thorough understanding of the self-organized formation of oxide nanopores during anodization.
Oxygen vacancies (V(O)) have profound effects on the physical and chemical performance of devices based on oxide materials. This is particularly true in the case of oxide-based resistive random access memories, in which memory switching operation under an external electrical stimulus is closely associated with the migration and ordering of the oxygen vacancies in the oxide material. In this paper, we report on a reliable approach to in situ control of the oxygen vacancies in TiOx films. Our strategy for tight control of the oxygen vacancy is based on the utilization of plasma-enhanced atomic layer deposition of titanium oxide under precisely regulated decomposition of the precursor molecules (titanium (IV) tetraisopropoxide, Ti[OCH(CH₃)₂]₄) by plasma-activated reactant mixture (N₂+O₂). From the various spectroscopic and microstructural analyses by using Rutherford backscattering spectrometry, x-ray photoelectron spectroscopy, high-resolution transmission electron microscopy, confocal Raman spectroscopy, and spectroscopic ellipsometry, we found that the precursor decomposition power (R(F)) of plasma-activated reactant mixture determines not only the oxygen vacancy concentration but also the crystallinity of the resulting TiO(x) film: nanocrystalline anatase TiO(x) with fewer oxygen vacancies under high R(F), while amorphous TiOx with more oxygen vacancies under low RF. Enabled by our controlling capability over the oxygen vacancy concentration, we were able to thoroughly elucidate the effect of oxygen vacancies on the resistive switching behavior of TiO(x)-based memory capacitors (Pt/TiO(x)/Pt). The electrical conduction behavior at the high resistance state could be explained within the framework of the trap-controlled space-charge-limited conduction with two characteristic transition voltages. One is the voltage (V(SCL)) for the transition from Ohmic conduction to space-charge-limited conduction, and the other is the voltage (V(TFL)) for transition from space-charge-limited conduction to trap-filled-limited conduction. In this work, we have disclosed for the first time the dependence of these two characteristic transition voltages (i.e., V(SCL) and V(TFL)) on the oxygen vacancy concentration.
The measurement of layer thickness by compositional secondary ion mass spectrometry (SIMS) depth profiling is investigated for Si/Ge multilayer films using an oxygen ion beam. The original SIMS depth profiles were converted into compositional depth profiles by the relative sensitivity factors of Si and Ge derived from a Si52.4Ge47.6 alloy reference film. The locations of the interfaces in the Si/Ge multilayer films could be well determined by 50 at% definition where the relative composition of the constituent layer elements drops or rises to 50 at%. The layer thicknesses of Si and Ge of a test Si/Ge multilayer film were determined by the sputtering rates of Si and Ge determined from a reference Si/Ge multilayer film. Although the difference between the measured and the actual thicknesses is increased as the ion energy is increased, the layer thicknesses determined at low ion energies were very close to the actual values.
Active doping of B was observed in nanometer silicon layers confined in SiO(2) layers by secondary ion mass spectrometry (SIMS) depth profiling analysis and confirmed by Hall effect measurements. The uniformly distributed boron atoms in the B-doped silicon layers of [SiO(2) (8 nm)/B-doped Si(10 nm)](5) films turned out to be segregated into the Si/SiO(2) interfaces and the Si bulk, forming a distinct bimodal distribution by annealing at high temperature. B atoms in the Si layers were found to preferentially substitute inactive three-fold Si atoms in the grain boundaries and then substitute the four-fold Si atoms to achieve electrically active doping. As a result, active doping of B is initiated at high doping concentrations above 1.1 × 10(20) atoms cm( - 3) and high active doping of 3 × 10(20) atoms cm( - 3) could be achieved. The active doping in ultra-thin Si layers was implemented for silicon quantum dots (QDs) to realize a Si QD solar cell. A high energy-conversion efficiency of 13.4% was realized from a p-type Si QD solar cell with B concentration of 4 × 10(20) atoms cm( - 3).
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