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.

Electrical properties of platinum interconnects deposited by electron beam induced deposition of the carbon-free precursor, Pt(PF3)4

Comprehensive analysis of the electrical properties, structure and composition of Pt interconnects, developed via mask-less, electron beam induced deposition of the carbon-free Pt precursor, Pt(PF3)4, is presented. The results demonstrate significantly improved electrical performance in comparison with that generated from the standard organometallic precursor, (CH3)3Pt(CpCH3). In particular, the Pt interconnects exhibited perfect ohmic behavior and resistivity that can be diminished to 0.24 × 10−3 Ω cm, which is only one order of magnitude higher than bulk Pt, in comparison to 0.2 Ω cm for the standard carbon-containing interconnects. A maximum current density of 1.87 × 107 A cm−2 was achieved for the carbon-free Pt, compared to 9.44 × 105 A cm−2 for the standard Pt precursor. The enhanced electrical properties of the as-deposited materials can be explained by the absence of large amounts of carbon impurities, and their further improvement by postdeposition annealing in N2. In-situ TEM heating experiments confirmed that the annealing step induces sintering of the Pt nanocrystals and improved crystallinity, which contributes to the enhanced electrical performance. Alternative annealing under reducing conditions resulted in improved performance of the standard Pt interconnects, while the carbon-free deposit suffered electrical and structural breakage due to formation of larger Pt islands

Supercapattery based on binder-free Co3 (PO4)2·8H2O multilayer nano/microflakes on nickel foam

A binder-free cobalt phosphate hydrate (Co3(PO4)2·8H2O) multilayer nano/microflake structure is synthesized on nickel foam (NF) via a facile hydrothermal process. Four different concentrations (2.5, 5, 10, and 20 mM) of Co2+ and PO4–3 were used to obtain different mass loading of cobalt phosphate on the nickel foam. The Co3(PO4)2·8H2O modified NF electrode (2.5 mM) shows a maximum specific capacity of 868.3 C g–1 (capacitance of 1578.7 F g–1) at a current density of 5 mA cm–2 and remains as high as 566.3 C g–1 (1029.5 F g–1) at 50 mA cm–2 in 1 M NaOH. A supercapattery assembled using Co3(PO4)2·8H2O/NF as the positive electrode and activated carbon/NF as the negative electrode delivers a gravimetric capacitance of 111.2 F g–1 (volumetric capacitance of 4.44 F cm–3). Furthermore, the device offers a high specific energy of 29.29 Wh kg–1 (energy density of 1.17 mWh cm–3) and a specific power of 4687 W kg–1 (power density of 187.5 mW cm–3).

Theory and optimisation of 1.3 and 1.55 μm (Al)InGaAs metamorphic quantum well lasers

The use of InGaAs metamorphic buffer layers (MBLs) to facilitate the growth of lattice-mismatched heterostructures constitutes an attractive approach to developing long-wavelength semiconductor lasers on GaAs substrates, since they offer the improved carrier and optical confinement associated with GaAs-based materials. We present a theoretical study of GaAs-based 1.3 and 1.55 μm (Al)InGaAs quantum well (QW) lasers grown on InGaAs MBLs. We demonstrate that optimised 1.3 μm metamorphic devices offer low threshold current densities and high differential gain, which compare favourably with InP-based devices. Overall, our analysis highlights and quantifies the potential of metamorphic QWs for the development of GaAs-based long-wavelength semiconductor lasers, and also provides guidelines for the design of optimised devices.

Effects of alternating current voltage amplitude and oxide capacitance on mid-gap interface state defect density extractions in In0.53Ga 0.47As capacitors

This work looks at the effect on mid-gap interface state defect density estimates for In0.53Ga0.47As semiconductor capacitors when different AC voltage amplitudes are selected for a fixed voltage bias step size (100 mV) during room temperature only electrical characterization. Results are presented for Au/Ni/Al2O3/In0.53Ga0.47As/InP metal–oxide–semiconductor capacitors with (1) n-type and p-type semiconductors, (2) different Al2O3 thicknesses, (3) different In0.53Ga0.47As surface passivation concentrations of ammonium sulphide, and (4) different transfer times to the atomic layer deposition chamber after passivation treatment on the semiconductor surface—thereby demonstrating a cross-section of device characteristics. The authors set out to determine the importance of the AC voltage amplitude selection on the interface state defect density extractions and whether this selection has a combined effect with the oxide capacitance. These capacitors are prototypical of the type of gate oxide material stacks that could form equivalent metal–oxide–semiconductor field-effect transistors beyond the 32 nm technology node. The authors do not attempt to achieve the best scaled equivalent oxide thickness in this work, as our focus is on accurately extracting device properties that will allow the investigation and reduction of interface state defect densities at the high-k/III–V semiconductor interface. The operating voltage for future devices will be reduced, potentially leading to an associated reduction in the AC voltage amplitude, which will force a decrease in the signal-to-noise ratio of electrical responses and could therefore result in less accurate impedance measurements. A concern thus arises regarding the accuracy of the electrical property extractions using such impedance measurements for future devices, particularly in relation to the mid-gap interface state defect density estimated from the conductance method and from the combined high–low frequency capacitance–voltage method. The authors apply a fixed voltage step of 100 mV for all voltage sweep measurements at each AC frequency. Each of these measurements is repeated 15 times for the equidistant AC voltage amplitudes between 10 mV and 150 mV. This provides the desired AC voltage amplitude to step size ratios from 1:10 to 3:2. Our results indicate that, although the selection of the oxide capacitance is important both to the success and accuracy of the extraction method, the mid-gap interface state defect density extractions are not overly sensitive to the AC voltage amplitude employed regardless of what oxide capacitance is used in the extractions, particularly in the range from 50% below the voltage sweep step size to 50% above it. Therefore, the use of larger AC voltage amplitudes in this range to achieve a better signal-to-noise ratio during impedance measurements for future low operating voltage devices will not distort the extracted interface state defect density.

Assessing charge contribution from thermally treated Ni foam as current collectors for Li-ion batteries

In this report we have investigated the use of Ni foam substrates as anode current collectors for Li-ion batteries. As the majority of reports in the literature focus on hydrothermal formation of materials on Ni foam followed by a high temperature anneal/oxidation step, we probed the fundamental electrochemical responses of as received Ni foam substrates and those subjected to heating at 100°C, 300°C and 450°C. Through cyclic voltammetry and galvanostatic testing, it is shown that the as received and 100°C annealed Ni foam show negligible electrochemical activity. However, Ni foams heated to higher temperature showed substantial electrochemical contributions which may lead to inflated capacities and incorrect interpretations of CV responses for samples subjected to high temperature anneals. XRD, XPS and SEM analyses clearly illustrate that the formation of electrochemically active NiO nanoparticles on the surface of the foam is responsible for this behavior. To further investigate the contribution of the oxidized Ni foam to the overall electrochemical response, we formed Co3O4 nanoflowers directly on Ni foam at 450°C and showed that the resulting electrochemical response was dominated by NiO after the first 10 charge/discharge cycles. This report highlights the importance of assessing current collector activity for active materials grown on transition metal foam current collectors for Li-ion applications.

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.

The structural conversion from α-AgVO3 to β-AgVO3: Ag nanoparticle decorated nanowires with application as cathode materials for Li-ion batteries

The majority of electrode materials in batteries and related electrochemical energy storage devices are fashioned into slurries via the addition of a conductive additive and a binder. However, aggregation of smaller diameter nanoparticles in current generation electrode compositions can result in non-homogeneous active materials. Inconsistent slurry formulation may lead to inconsistent electrical conductivity throughout the material, local variations in electrochemical response, and the overall cell performance. Here we demonstrate the hydrothermal preparation of Ag nanoparticle (NP) decorated α-AgVO3 nanowires (NWs) and their conversion to tunnel structured β-AgVO3 NWs by annealing to form a uniform blend of intercalation materials that are well connected electrically. The synthesis of nanostructures with chemically bound conductive nanoparticles is an elegant means to overcome the intrinsic issues associated with electrode slurry production, as wire-to-wire conductive pathways are formed within the overall electrode active mass of NWs. The conversion from α-AgVO3 to β-AgVO3 is explained in detail through a comprehensive structural characterization. Meticulous EELS analysis of β-AgVO3 NWs offers insight into the true β-AgVO3 structure and how the annealing process facilitates a higher surface coverage of Ag NPs directly from ionic Ag content within the α-AgVO3 NWs. Variations in vanadium oxidation state across the surface of the nanowires indicate that the β-AgVO3 NWs have a core–shell oxidation state structure, and that the vanadium oxidation state under the Ag NP confirms a chemically bound NP from reduction of diffused ionic silver from the α-AgVO3 NWs core material. Electrochemical comparison of α-AgVO3 and β-AgVO3 NWs confirms that β-AgVO3 offers improved electrochemical performance. An ex situ structural characterization of β-AgVO3 NWs after the first galvanostatic discharge and charge offers new insight into the Li+ reaction mechanism for β-AgVO3. Ag+ between the van der Waals layers of the vanadium oxide is reduced during discharge and deposited as metallic Ag, the vacant sites are then occupied by Li+.