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.

Nanoporous InP: anodic formation and growth mechanism in aqueous electrolytes

Porous 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 that 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 <100> 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. 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. Porous layers are also observed in highly doped InP but are not observed in wafers with doping densities below ~5 × 1017 cm-3. Numerical models of this process have been developed invoking a mechanism of directional selectivity of pore growth preferentially along the <100> lattice directions. Manipulation of the parameters controlling these curves shows that the fall-off in current is controlled by the rate of diffusion of electrolyte through the pore structure with the final decline in current being caused by the termination of growth at the pore tips through the formation of passivating films or some other irreversible modification of the pore tips.