Degradation and breakdown characteristics of thin MgO dielectric layers

MgO has been suggested as a possible high-k dielectric for future complementary metal-oxide semiconductor processes. In this work, the time dependent dielectric breakdown (TDDB) characteristics of 20 nm MgO films are discussed. Stress induced leakage current measurements indicate that the low measured Weibull slopes of the TDDB distributions for both n-type and p-type devices cannot be attributed to a lower trap generation rate than for SiO2. This suggests that much fewer defects are required to trigger breakdown in MgO under voltage stress than is the case for SiO2 or other metal-oxide dielectrics. This in turn explains the progressive nature of the breakdown in these films which is observed both in this work and elsewhere. The reason fewer defects are required is attributed to the morphology of the films

Anodic formation and characterization of nanoporous InP in aqueous KOH electrolytes

The anodic behavior of highly doped (> 1018 cm-3) n-InP in aqueous KOH was investigated. Electrodes anodized in the absence of light in 2- 5 mol dm-3 KOH at a constant potential of 0.5- 0.75 V (SCE), or subjected to linear potential sweeps to potentials in this range, were shown to exhibit the formation of a nanoporous subsurface region. Both linear sweep voltammograms and current-time curves at constant potential showed a characteristic anodic peak, corresponding to formation of the nanoporous region. No porous region was formed during anodization in 1 mol dm-3 KOH. The nanoporous region was examined using transmission electron microscopy and found to have a thickness of some 1- 3 μm depending on the anodization conditions and to be located beneath a thin (typically ∼40 nm), dense, near-surface layer. The pores varied in width from 25 to 75 nm and both the pore width and porous region thickness were found to decrease with increasing KOH concentration. The porosity was approximately 35%. The porous layer structure is shown to form by the localized penetration of surface pits into the InP, and the dense, near-surface layer is consistent with the effect of electron depletion at the surface of the semiconductor

Formation of nanoporous InP by electrochemical anodization

Porous InP layers can be formed electrochemically on (100) oriented n- InP substrates in aqueous KOH. A nanoporous layer is obtained underneath a dense near-surface layer and the pores appear to propagate from holes through the near-surface layer. In the early stages of the anodization transmission electron microscopy (TEM) clearly shows individual porous domains which appear to have a square-based pyramidal shape. Each domain appears to develop from an individual surface pit which forms a channel through this near-surface layer. We suggest that the pyramidal structure arises as a result of preferential pore propagation along the directions. AFM measurements show that the density of surface pits increases with time. Each of these pits acts as a source for a pyramidal porous domain. When the domains grow, the current density increases correspondingly. Eventually, the domains meet forming a continuous porous layer, the interface between the porous and bulk InP becomes relatively flat and its total effective surface area decreases resulting in a decrease in the current density. Numerical models of this process have been developed. Current-time curves at constant potential exhibit a peak and porous layers are observed to form beneath the electrode surface. The density of pits formed on the surface increases with time and approaches a plateau value

A mechanistic study of anodic formation of porous InP

When porous InP is anodically formed in KOH electrolytes, a thin layer ~40 nm in thickness, close to the surface, appears to be unmodified. We have investigated the earlier stages of the anodic formation of porous InP in 5 mol dm-3 KOH. TEM clearly shows individual porous domains which appear triangular in cross-section and square in plan view. The crosssections also show that the domains are separated from the surface by a ~40 nm thick, dense InP layer. It is concluded that the porous domains have a square-based pyramidal shape and that each one develops from an individual surface pit which forms a channel through this near-surface layer. We suggest that the pyramidal structure arises as a result of preferential pore propagation along the directions. AFM measurements show that the density of surface pits increases with time. Each of these pits acts as a source for a pyramidal porous domain, and these domains eventually form a continuous porous layer. This implies that the development of porous domains beneath the surface is also progressive in nature. Evidence for this was seen in plan view TEM images. Merging of domains continues to occur at potentials more anodic than the peak potential, where the current is observed to decrease. When the domains grow, the current density increases correspondingly. Eventually, domains meet, the interface between the porous and bulk InP becomes relatively flat and its total effective surface area decreases resulting in a decrease in the current density. Quantitative models of this process are being developed

Pitting and porous layer formation on n-InP anodes

Surface pitting occurs when InP electrodes are anodized in KOH electrolytes at concentrations in the range 2 - 5 mol dm-3. The process has been investigated using atomic force microscopy (AFM) and the results correlated with cross-sectional transmission electron microscopy (TEM) and electroanalytical measurements. AFM measurements show that pitting of the surface occurs and the density of pits is observed to increase with time under both potentiodynamic and potentiostatic conditions. This indicates a progressive pit nucleation process and implies that the development of porous domains beneath the surface is also progressive in nature. Evidence for this is seen in plan view TEM images in which individual domains are seen to be at different stages of development. Analysis of the cyclic voltammograms of InP electrodes in 5 mol dm-3 KOH indicates that, above a critical potential for pit formation, the anodic current is predominantly time dependent and there is little differential dependence of the current on potential. Thus, pores continue to grow with time when the potential is high enough to maintain depletion layer breakdown conditions

Nanoporous domains in n-InP anodized in KOH

A model of porous structure growth in semiconductors based on propagation of pores along the A directions has been developed. The model predicts that pores originating at a surface pit lead to porous domains with a truncated tetrahedral shape. SEM and TEM were used to examine cross- sections of n-InP electrodes in the early stages of anodization in aqueous KOH and showed that pores propagate along the A directions. Domain outlines observed in both TEM and SEM images are in excellent agreement with the model. The model is further supported by plan-view TEM and surface SEM images. Quantitative measurements of aspect ratios of the observed domains are in excellent agreement with the predicted values

Effect of electrolyte concentration on anodic nanoporous layer growth for n-InP in aqueous KOH

The surface morphology and sub-surface porous structure of (100) n-InP following anodization in 1 - 10 mol dm-3 aqueous KOH were studied using linear sweep voltammetry (LSV) in combination with scanning electron microscopy (SEM) and transmission electron microscopy (TEM). LSV of n-InP in 10 mol dm-3 KOH showed a single anodic current peak at 0.41 V. As the concentration of electrolyte was decreased, the peak increased in current density and charge and shifted to more positive potentials; eventually individual peaks were no longer discernable. Porous layers were observed in SEM cross-sections following linear potential sweeps and the porous layer thickness increased significantly with decreasing KOH concentration, reaching a maximum value at ~2.2 mol dm-3. At concentrations less than 1.8 mol dm-3 the layer thickness decreased sharply, pore diameters became wider and pore walls became narrower until eventually, at 1.1 mol dm-2 or lower, no porous layers were observed. It was also observed that the pore width increased and the inter-pore spacing decreased with decreasing concentration. It is proposed that preferential pore propagation occurs along directions, contrary to previous suggestions, and that the resulting anoporous domains, initially formed, have triangular cross-sections when viewed in one of the {110} cleavage planes, ‘dove-tail’ crosssections viewed in the orthogonal {110} cleavage plane and square profiles when viewed in the (100) plane of the electrode surface

A study of anodic films on n-InP by spectroscopic ellipsometry and atomic force microscopy

The growth of anodic films on n-InP in 1 mol dm-1 KOH is investigated under potential sweep conditions. At lower potentials a thin surface film is formed and a peak is observed on the current-voltage curve. Ellipsometric measurements show that this film increases in thickness with increasing potential but the observed thickness values are significantly less than the corresponding coulometrically estimated values. This indicates that much of the charge passed is not involved in the formation of a surface film but presumably in the formation of soluble anodic reaction products. Cyclic voltammograms show that a current peak is also observed on the reverse sweep and ellipsometric measurements show that the anodic film thickness also increases during the reverse sweep until the peak potential is reached. Atomic force microscopy (AFM) shows that the surface becomes smoother as the potential is increased. We attribute this to the formation of nuclei at lower potentials, which coalesce as the layer becomes thicker. Electron diffraction and x-ray photoelectron spectroscopy (XPS) analysis show that the surface film is predominantly In2O3 with no evidence of InPO4

Anodic behavior of InP: film growth, porous structures and current oscillations.

We review our recent work on the anodization of InP in KOH electrolytes. The anodic oxidation processes are shown to be remarkably different in different concentrations of KOH. Anodization in 2 - 5 mol dm-3 KOH electrolytes results in the formation of porous InP layers but, under similar conditions in a 1 mol dm-3 KOH, no porous structure is evident. Rather, the InP electrode is covered with a thin, compact surface film at lower potentials and, at higher potentials, a highly porous surface film is formed which cracks on drying. Anodization of electrodes in 2 - 5 mol dm-3 KOH results in the formation of porous InP under both potential sweep and constant potential conditions. The porosity is estimated at ~65%. A thin layer (~ 30 nm) close to the surface appears to be unmodified. It is observed that this dense, near-surface layer is penetrated by a low density of pores which appear to connected it to the electrolyte. Well-defined oscillations are observed when InP is anodized in both the KOH and (NH4)2S. The charge per cycle remains constant at 0.32 C cm-2 in (NH4)2S but increases linearly with potential in KOH. Although the characteristics of the oscillations in the two systems differ, both show reproducible and well-behaved values of charge per cycle

Preferential <111>A pore propagation mechanism in n-InP anodized in KOH

This paper describes the formation of pores during the anodization of n-InP in aqueous KOH. The pores propagate preferentially along the A crystallographic directions and form truncated tetrahedral domains. A model is presented that explains preferential A pore propagation and the uniform diameters of pores. The model outlines how pores can deviate from the A directions and from their characteristic diameters. It also details the effect of variation of carrier concentration on the dimensions of the porous structures