Unusual bismuth-containing surface layers of III-V compound semiconductors

The understanding and engineering of bismuth (Bi) containing semiconductor surfaces are signi cant in the development of novel semiconductor materials for electronic and optoelectronic devices such as high-e ciency solar cells, lasers and light emitting diodes. For example, a Bi surface layer can be used as a surfactant which oats on a III-V compound-semiconductor surface during the epitaxial growth of IIIV lms. This Bi surfactant layer improves the lm-growth conditions if compared to the growth without the Bi layer. Therefore, detailed knowledge of the properties of the Bi/III-V surfaces is needed. In this thesis, well-de ned surface layers containing Bi have been produced on various III-V semiconductor substrates. The properties of these Bi-induced surfaces have been measured by low-energy electron di raction (LEED), scanning-tunneling microscopy and spectroscopy (STM), and synchrotron-radiation photoelectron spectroscopy. The experimental results have been compared with theoretically calculated results to resolve the atomic structures of the studied surfaces. The main ndings of this research concern the determination of the properties of an unusual Bi-containing (2×1) surface structure, the discovery and characterization of a uniform pattern of Bi nanolines, and the optimization of the preparation conditions for this Bi-nanoline pattern.

SnO2, ZnO and related polycrystalline compound semiconductors: An overview and review on the voltage-dependent resistance (non-ohmic) feature

The present review describes mainly the history of SnO2-based voltage-dependent resistors, discusses the main characteristics of these polycrystalline semiconductor systems and includes a direct comparison with traditional ZnO-based voltage-dependent resistor systems to establish the differences and similarities, giving details of the basic physical principles involved with the non-ohmic properties in both polycrystalline systems. As an overview, the text also undertakes the main difficulties involved in processing SnO2- and ZnO-based non-ohmic systems, with an evaluation of the contribution of the dopants to the electronic properties and to the final microstructure and consequently to the system's non-ohmic behavior. However, since there are at least two review texts regarding ZnO-based systems [Levinson, L. M., and Philipp, H. R. Ceramic Bulletin 1985;64:639; Clarke, D. R. Journal of American Ceramic Society 1999;82:485], the main focus of the present text is dedicated to the SnO2-based varistor systems, although the basic physical principles described in the text are universally useful in the context of dense polycrystalline devices. However, the readers must be careful of how the microstructure heterogeneity and grain-boundary chemistry are capable to interfere in the global electrical response for particular systems. New perspectives for applications, commercialization and degradation studies involving SnO2-based polycrystalline non-ohmic systems are also outlined, including recent technological developments. Finally, at the end of this review a brief section is particularly dedicated to the presentation and discussions about others emerging non-ohmic polycrystalline ceramic devices (particularly based on perovskite ceramics) which must be deeply studied in the years to come, specially because some of these systems present combined high dielectric and non-ohmic properties. From both scientific and technological point of view these perovskite systems are quite interesting. (c) 2007 Elsevier Ltd. All rights reserved.

Investigation of the effects of low energy high dose ion bombardment in metals and compound semiconductors

The effect of low energy nitrogen molecular ion beam bombardment on metals and compound semiconductors has been studied, with the aim to investigate at the effects of ion and target properties. For this purpose, nitrogen ion implantation in aluminium, iron, copper, gold, GaAs and AIGaAs is studied using XPS and Angle Resolve XPS. A series of experimental studies on N+2 bombardment induced compositional changes, especially the amount of nitrogen retained in the target, were accomplished. Both monoenergetic implantation and non-monoenergetic ion implantation were investigated, using the VG Scientific ESCALAB 200D system and a d. c. plasma cell, respectively. When the samples, with the exception of gold, are exposed to air, native oxide layers are formed on the surfaces. In the case of monoenergetic implantation, the surfaces were cleaned using Ar+ beam bombardment prior to implantation. The materials were then bombarded with N2+ beam and eight sets of successful experiments were performed on each sample, using a rastered N2+ ion beam of energy of 2, 3, 4 and 5 keV with current densities of 1 μA/cm2 and 5 μA/cm22 for each energy. The bombarded samples were examined by ARXPS. After each complete implantation, XPS depth profiles were created using Ar+ beam at energy 2 ke V and current density 2 μA/cm2 . As the current density was chosen as one of the parameters, accurate determination of current density was very important. In the case of glow discharge, two sets of successful experiments were performed in each case, by exposing the samples to nitrogen plasma for the two conditions: at low pressure and high voltage and high pressure and low voltage. These samples were then examined by ARXPS. On the theoretical side, the major problem was prediction of the number of ions of an element that can be implanted in a given matrix. Although the programme is essentially on experimental study, but an attempt is being made to understand the current theoretical models, such as SATVAL, SUSPRE and TRIM. The experimental results were compared with theoretical predictions, in order to gain a better understanding of the mechanisms responsible. From the experimental results, considering possible experimental uncertainties, there is no evidence of significant variation in nitrogen saturation concentration with ion energy or ion current density in the range of 2-5 ke V, however, the retention characteristics of implantant seem to strongly depend on the chemical reactivity between ion species and target material. The experimental data suggests the presence of at least one thermal process. The discrepancy between the theoretical and experimental results could be the inability of the codes to account for molecular ion impact and thermal processes.

Investigation of electrically active defects at the interface of high-k dielectrics and compound semiconductors

As silicon based devices in integrated circuits reach the fundamental limits of dimensional scaling there is growing research interest in the use of high electron mobility channel materials, such as indium gallium arsenide (InGaAs), in conjunction with high dielectric constant (high-k) gate oxides, for Metal-Oxide-Semiconductor Field Effect Transistor (MOSFET) based devices. The motivation for employing high mobility channel materials is to reduce power dissipation in integrated circuits while also providing improved performance. One of the primary challenges to date in the field of III-V semiconductors has been the observation of high levels of defect densities at the high-k/III-V interface, which prevents surface inversion of the semiconductor. The work presented in this PhD thesis details the characterization of MOS devices incorporating high-k dielectrics on III-V semiconductors. The analysis examines the effect of modifying the semiconductor bandgap in MOS structures incorporating InxGa1-xAs (x: 0, 0.15. 0.3, 0.53) layers, the optimization of device passivation procedures designed to reduce interface defect densities, and analysis of such electrically active interface defect states for the high-k/InGaAs system. Devices are characterized primarily through capacitance-voltage (CV) and conductance-voltage (GV) measurements of MOS structures both as a function of frequency and temperature. In particular, the density of electrically active interface states was reduced to the level which allowed the observation of true surface inversion behavior in the In0.53Ga0.47As MOS system. This was achieved by developing an optimized (NH4)2S passivation, minimized air exposure, and atomic layer deposition of an Al2O3 gate oxide. An extraction of activation energies allows discrimination of the mechanisms responsible for the inversion response. Finally a new approach is described to determine the minority carrier generation lifetime and the oxide capacitance in MOS structures. The method is demonstrated for an In0.53Ga0.47As system, but is generally applicable to any MOS structure exhibiting a minority carrier response in inversion.

Approximation to density functional theory for the calculation of band gaps of semiconductors

The local-density approximation (LDA) together with the half occupation (transitionstate) is notoriously successful in the calculation of atomic ionization potentials. When it comes to extended systems, such as a semiconductor infinite system, it has been very difficult to find a way to half ionize because the hole tends to be infinitely extended (a Bloch wave). The answer to this problem lies in the LDA formalism itself. One proves that the half occupation is equivalent to introducing the hole self-energy (electrostatic and exchange correlation) into the Schrodinger equation. The argument then becomes simple: The eigenvalue minus the self-energy has to be minimized because the atom has a minimal energy. Then one simply proves that the hole is localized, not infinitely extended, because it must have maximal self-energy. Then one also arrives at an equation similar to the self- interaction correction equation, but corrected for the removal of just 1/2 electron. Applied to the calculation of band gaps and effective masses, we use the self- energy calculated in atoms and attain a precision similar to that of GW, but with the great advantage that it requires no more computational effort than standard LDA.

Theory of ferromagnetism in planar heterostructures of (Mn,III)-V semiconductors

A density-functional theory of ferromagnetism in heterostructures of compound semiconductors doped with magnetic impurities is presented. The variable functions in the density-functional theory are the charge and spin densities of the itinerant carriers and the charge and localized spins of the impurities. The theory is applied to study the Curie temperature of planar heterostructures of III-V semiconductors doped with manganese atoms. The mean-field, virtual-crystal and effective-mass approximations are adopted to calculate the electronic structure, including the spin-orbit interaction, and the magnetic susceptibilities, leading to the Curie temperature. By means of these results, we attempt to understand the observed dependence of the Curie temperature of planar δ-doped ferromagnetic structures on variation of their properties. We predict a large increase of the Curie temperature by additional confinement of the holes in a δ-doped layer of Mn by a quantum well.

Ion bombardment induced compositional changes in compound semiconductor surfaces studied by XPS combined with LEISS

Surface compositional change of GaP, GaAs, GaSb, InP, InAs, InSb, GeSi and CdSe single crystals due to low keV noble gas ion beam bombardment has been investigated by combining X-ray Photoelectron Spectroscopy (XPS) and Low Energy Ion Scattering Spectroscopy (LEISS). The purpose of using this complementary analytical method is to obtain more complete experimental evidence of ion beam modification in surfaces of compound semiconductors and GeSi alloy to improve the understanding of the mechanisms responsible for these effects. Before ion bombardment the sample surfaces were analysed nondestructively by Angular Resolved XPS (ARXPS) and LEISS to get the initial distribution of surface composition. Ion bombardment experiments were carried out using 3keV argon ions with beam current of 1μA for a period of 50 minutes, compositional changes in the surfaces of compound semiconductors and GeSi alloy were monitored with normal XPS. After ion bombardment the surfaces were re-examined with ARXPS and LEISS. Both XPS and LEISS results showed clearly that ion bombardment will change the compositional distribution in the compound semiconductor and GeSi surfaces. In order to explain the observed experimental results, two major theories in this field, Sigmund linear collision cascade theory and the thermodynamic models based on bombardment induced Gibbsian surface segregation and diffusion, were investigated. Computer simulation using TRIM code was also carried out for assistance to the theoretical analysis. Combined the results obtained from XPS and LEISS analyses, ion bombardment induced compositional changes in compound semiconductor and GeSi surfaces are explained in terms of the bombardment induced Gibbsian surface segregation and diffusion.

Earth-Abundant Zinc-IV-Nitride Semiconductors

This investigation is motivated by the need for new visible frequency direct bandgap semiconductor materials that are abundant and low-cost to meet the increasing demand for optoelectronic devices in applications such as solid state lighting and solar energy conversion. Proposed here is the utilization of zinc-IV-nitride materials, where group IV elements include silicon, germanium, and tin, as earth-abundant alternatives to the more common III-nitrides in optoelectronic devices. These compound semiconductors were synthesized under optimized conditions using reactive radio frequency magnetron sputter deposition. Single phase ZnSnN₂, having limited experimental accounts in literature, is validated by identification of the wurtzite-derived crystalline structure predicted by theory through X-ray and electron diffraction studies. With the addition of germanium, bandgap tunability of ZnSn_xGe_1-xN₂ alloys is demonstrated without observation of phase separation, giving these materials a distinct advantage over In_xGa_1-xN alloys. The accessible bandgaps range from 1.8 to 3.1 eV, which spans the majority of the visible spectrum. Electron densities, measured using the Hall effect, were found to be as high as 10²² cm⁻³ and indicate that the compounds are unintentionally degenerately doped. Given these high carrier concentrations, a Burstein-Moss shift is likely affecting the optical bandgap measurements. The discoveries made in this thesis suggest that with some improvements in material quality, zinc-IV-nitrides have the potential to enable cost-effective and scalable optoelectronic devices.

Synthesis and characterization of 3d-transition metals doped ZnO thin films and nanostructures for possible spintronic applications

The objective of the present study is the formation of single phase Zn1−xTMxO thin films by PLD and increase the solubility limit of TM dopants. The TM doped ZnO nanostructures were also grown by hydrothermal method. The structural and morphological variation of ZnO:TM thin films and nanostructures with TM doping concentration is also investigated. The origin and enhancement of ferromagnetism in single phase Zn1−xTMxO thin films and nanostructures using spectroscopic techniques were also studied. The dependence of ablation parameters on the structural and optical properties of ZnO thin films were studied

GaInAsP-basierende Resonatorstrukturen

Physikalische Grundlagenforschung und anwendungsorientierte physikalische Forschung auf den Gebieten nanoskaliger kristalliner und amorpher fester Körper haben in vielfacher Weise eine große Bedeutung. Neben dem Verständnis für die Struktur der Materie und die Wechselwirkung von Objekten von der Größe einiger Atome ist die Erkenntnis über die physikalischen Eigenschaften nanostrukturierter Systeme von hohem Interesse. Diese Forschung eröffnet die Möglichkeit, die mit der Mikroelektronik begonnene Miniaturisierung fortzusetzen und wird darüber hinaus neue Anwendungsfelder eröffnen. Das Erarbeiten der physikalischen Grundlagen der Methoden zur Herstellung und Strukturierung ist dabei zwingend notwendig, da hier Wirkungsprinzipien dominieren, die erst bei Strukturgrößen im Nanometerbereich auftreten oder hinreichend stark ausgeprägt sind. Insbesondere Halbleitermaterialien sind hier von großem Interesse. Die in dieser Arbeit untersuchten Resonatorstrukturen, die auf dem kristallinen Verbindungshalbleitermaterial GaInAsP/InP basieren, erschließen wichtige Anwendungsfelder im Bereich der optischen Datenübertragung sowie der optischen Sensorik. Hergestellt wird das Halbleitermaterial mit der Metallorganischen Gasphasenepitaxie. Die experimentell besimmten Kenngrößen lassen Rückschlüsse auf die Güte der Materialien, die quantenmechanischen Wirkungsprinzipien und die Bauelementcharakteristik zu und führen zu optimal angepassten Kristallstrukturen. Auf Basis dieser optimierten Materialien wurde ein durchstimmbarer Fabry-Perot-Filter hergestellt, der aus einer Kombination aus InP-Membranen und Luftspalten besteht und elektromechanisch aktuiert werden kann. Das GaInAsP dient hierbei als wenige hundert nm dicke Opferschicht, die ätztechnisch hochselektiv beseitigt wird. Die Qualität der Grenzflächen zum InP ist entscheidend für die Qualität der freigeätzten Kavitäten und damit für die mechanische Gesamtstabilität der Struktur. Der in dieser Arbeit beschriebene Filter hat eine Zentralwellenlänge im Bereich von 1550 nm und weist einen Durchstimmbereich von 221 nm auf. Erzielt wurde dieser Wert durch ein konsistentes Modell der wirkenden Verspannungskomponenten und einer optimierten epitaktischen Kontrolle der Verspannungsparameter. Das realisierte Filterbauelement ist vielversprechend für den Einsatz in der optischen Kommunikation im Bereich von WDM (wavelength division multiplexing) Anwendungen. Als weitere Resonatorstrukur wurde ein Asymmetrisch gekoppelter Quantenfilm als optisch aktives Medium, bestehend aus GaInAsP mit variierender Materialkomposition und Verspannung, untersucht, um sein Potential für eine breitbandige Emission zu untersuchen und mit bekannten Modellen zu vergleichen. Als Bauelementdesign wurde eine kantenemittierende Superlumineszenzleuchtdiode gewählt. Das Ergebnis ist eine Emissionskurve von 100 nm, die eine höhere Unabhängigkeit vom Injektionsstrom aufweist als andere bekannte Konzepte. Die quantenmechanischen Wirkungsprinzipien - im wesentlichen die Kopplung der beiden asymmetrischen Potentialtöpfe und die damit verbundene Kopplung der Wellenfunktionen - werden qualitativ diskutiert. Insgesamt bestätigt sich die Eignung des Materials GaInAsP auch für neuartige, qualitativ höchst anspruchsvolle Resonatorstrukturen und die Bedeutung der vorgestellten und untersuchten Resonatorkonzepte. Die vorgestellten Methoden, Materialien und Bauelemente liefern aufgrund ihrer Konzeption und der eingehenden experimentellen Untersuchungen einen Beitrag sowohl zu den zugrunde liegenden mechanischen, optoelektronischen und quantenmechanischen Wirkungsprinzipien der Strukturen, als auch zur Realisierung neuer optoelektronischer Bauelemente.

High Indium Concentration InGaN/GaN Grown on Sapphire Substrate by MOCVD

The InGaN system provides the opportunity to fabricate light emitting devices over the whole visible and ultraviolet spectrum due to band-gap energies E[subscript g] varying between 3.42 eV for GaN and 1.89 eV for InN. However, high In content in InGaN layers will result in a significant degradation of the crystalline quality of the epitaxial layers. In addition, unlike other III-V compound semiconductors, the ratio of gallium to indium incorporated in InGaN is in general not a simple function of the metal atomic flux ratio, f[subscript Ga]/f[subscript In]. Instead, In incorporation is complicated by the tendency of gallium to incorporate preferentially and excess In to form metallic droplets on the growth surface. This phenomenon can definitely affect the In distribution in the InGaN system. Scanning electron microscopy, room temperature photoluminescence, and X-ray diffraction techniques have been used to characterize InGaN layer grown on InN and InGaN buffers. The growth was done on c-plane sapphire by MOCVD. Results showed that green emission was obtained which indicates a relatively high In incorporation.

Synthesis and surface modification of semiconductor nanocrystals

The last decade has witnessed an exponential growth of activities in the field of nanoscience and nanotechnology worldwide, driven both by the excitement of understanding new science and by the potential hope for applications and economic impacts. The largest activity in this field up to date has been in the synthesis and characterization of new materials consisting of particles with dimensions in the order of a few nanometers, so-called nanocrystalline materials. [1-8] Semiconductor nanomaterials such as III/V or II/VI compound semiconductors exhibit strong quantum confinement behavior in the size range from 1 to 10 nm. Therefore, preparation of high quality semiconductor nanocrystals has been a challenge for synthetic chemists, leading to the recent rapid progress in delivering a wide variety of semiconducting nanomaterials. Semiconductor nanocrystals, also called quantum dots, possess physical properties distinctly different from those of the bulk material. Typically, in the size range from 1 to 10 nm, when the particle size is changed, the band gap between the valence and the conduction band will change, too. In a simple approximation a particle in a box model has been used to describe the phenomenon[9]: at nanoscale dimensions the degenerate energy states of a semiconductor separate into discrete states and the system behaves like one big molecule. The size-dependent transformation of the energy levels of the particles is called “quantum size-effect”. Quantum confinement of both the electron and hole in all three dimensions leads to an increase in the effective bandgap of the material with decreasing crystallite size. Consequently, both the optical absorption and emission of semiconductor nanaocrystals shift to the blue (higher energies) as the size of the particles gets smaller. This color tuning is well documented for CdSe nanocrystals whose absorption and emission covers almost the whole visible spectral range. As particle sizes become smaller the ratio of surface atoms to those in the interior increases, which has a strong impact on particle properties, too. Prominent examples are the low melting point [8] and size/shape dependent pressure resistance [10] of semiconductor nanocrystals. Given the size dependence of particle properties, chemists and material scientists now have the unique opportunity to change the electronic and chemical properties of a material by simply controlling the particle size. In particular, CdSe nanocrystals have been widely investigated. Mainly due to their size-dependent optoelectronic properties [11, 12] and flexible chemical processibility [13], they have played a distinguished role for a number of seminal studies [11, 12, 14, 15]. Potential technical applications have been discussed, too. [8, 16-27] Improvement of the optoelectronic properties of semiconductor nanocrystals is still a prominent research topic. One of the most important approaches is fabricating composite type-I core-shell structures which exhibit improved properties, making them attractive from both a fundamental and a practical point of view. Overcoating of nanocrystallites with higher band gap inorganic materials has been shown to increase the photoluminescence quantum yields by eliminating surface nonradiative recombination sites. [28] Particles passivated with inorganic shells are more robust than nanocrystals covered by organic ligands only and have greater tolerance to processing conditions necessary for incorporation into solid state structures or for other applications. Some examples of core-shell nanocrystals reported earlier include CdS on CdSe [29], CdSe on CdS, [30], ZnS on CdS, [31] ZnS on CdSe[28, 32], ZnSe on CdSe [33] and CdS/HgS/CdS [34]. The characterization and preparation of a new core-shell structure, CdSe nanocrystals overcoated by different shells (CdS, ZnS), is presented in chapter 4. Type-I core-shell structures as mentioned above greatly improve the photoluminescence quantum yield and chemical and photochemical stability of nanocrystals. The emission wavelengths of type-I core/shell nanocrystals typically only shows a small red-shift when compared to the plain core nanocrystals. [30, 31, 35] In contrast to type-I core-shell nanocrystals, only few studies have been conducted on colloidal type-II core/shell structures [36-38] which are characterized by a staggered alignment of conduction and valence bands giving rise to a broad tunability of absorption and emission wavelengths, as was shown for CdTe/CdSe core-shell nanocrystals. [36] The emission of type-II core/shell nanocrystals mainly originates from the radiative recombination of electron-hole pairs across the core-shell interface leading to a long photoluminescence lifetime. Type-II core/shell nanocrystals are promising with respect to photoconduction or photovoltaic applications as has been discussed in the literature.[39] Novel type-II core-shell structures with ZnTe cores are reported in chapter 5. The recent progress in the shape control of semiconductor nanocrystals opens new fields of applications. For instance, rod shaped CdSe nanocrystals can enhance the photo-electro conversion efficiency of photovoltaic cells, [40, 41] and also allow for polarized emission in light emitting diodes. [42, 43] Shape control of anisotropic nanocrystals can be achieved by the use of surfactants, [44, 45] regular or inverse micelles as regulating agents, [46, 47] electrochemical processes, [48] template-assisted [49, 50] and solution-liquid-solution (SLS) growth mechnism. [51-53] Recently, formation of various CdSe nanocrystal shapes has been reported by the groups of Alivisatos [54] and Peng, [55] respectively. Furthermore, it has been reported by the group of Prasad [56] that noble metal nanoparticles can induce anisotropic growth of CdSe nanocrystals at lower temperatures than typically used in other methods for preparing anisotropic CdSe structures. Although several approaches for anisotropic crystal growth have been reported by now, developing new synthetic methods for the shape control of colloidal semiconductor nanocrystals remains an important goal. Accordingly, we have attempted to utilize a crystal phase control approach for the controllable synthesis of colloidal ZnE/CdSe (E = S, Se, Te) heterostructures in a variety of morphologies. The complex heterostructures obtained are presented in chapter 6. The unique optical properties of nanocrystals make them appealing as in vivo and in vitro fluorophores in a variety of biological and chemical investigations, in which traditional fluorescence labels based on organic molecules fall short of providing long-term stability and simultaneous detection of multiple emission colours [References]. The ability to prepare water soluble nanocrystals with high stability and quantum yield has led to promising applications in cellular labeling, [57, 58] deep-tissue imaging, [59, 60] and assay labeling [61, 62]. Furthermore, appropriately solubilized nanocrystals have been used as donors in fluorescence resonance energy transfer (FRET) couples. [63-65] Despite recent progress, much work still needs to be done to achieve reproducible and robust surface functionalization and develop flexible (bio-) conjugation techniques. Based on multi-shell CdSe nanocrystals, several new solubilization and ligand exchange protocols have been developed which are presented in chapter 7. The organization of this thesis is as follows: A short overview describing synthesis and properties of CdSe nanocrystals is given in chapter 2. Chapter 3 is the experimental part providing some background information about the optical and analytical methods used in this thesis. The following chapters report the results of this work: synthesis and characterization of type-I multi-shell and type-II core/shell nanocrystals are described in chapter 4 and chapter 5, respectively. In chapter 6, a high–yield synthesis of various CdSe architectures by crystal phase control is reported. Experiments about surface modification of nanocrystals are described in chapter 7. At last, a short summary of the results is given in chapter 8.

Synthesis and characterization of GaAsSb-capped InAs-based QDIPs

Quantum dot infrared photodetectors (QDIPs) are very attractive for infrared imaging applications due to its promising features such as high temperature operation, normal incidence response and low dark current [1]. However, the key issue is to obtain a high quality active region which requires a structural optimization of the nanostructures. With using GaAsSb capping layer, the optical properties, such as the PL intensity and its full width at half maximum (FWHM), of InAs QDs have been improved in the range between 1.15 and 1.5 m, because of the reduction of the compressive strain in QDs and the increment of QD height [2]. In this work, we have demonstrated strong and narrow intraband photoresponse spectra from GaAsSb-capped InAs-based QDIPs

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.