The development of planar high-K/III-V p-channel MOSFETs for post-silicon CMOS

Conventional Si complementary-metal-oxide-semiconductor (CMOS) scaling is fast approaching its limits. The extension of the logic device roadmap for future enhancements in transistor performance requires non-Si materials and new device architectures. III-V materials, due to their superior electron transport properties, are well poised to replace Si as the channel material beyond the 10nm technology node to mitigate the performance loss of Si transistors from further reductions in supply voltage to minimise power dissipation in logic circuits. However several key challenges, including a high quality dielectric/III-V gate stack, a low-resistance source/drain (S/D) technology, heterointegration onto a Si platform and a viable III-V p-metal-oxide-semiconductor field-effect-transistor (MOSFET), need to be addressed before III-Vs can be employed in CMOS. This Thesis specifically addressed the development and demonstration of planar III-V p-MOSFETs, to complement the n-MOSFET, thereby enabling an all III-V CMOS technology to be realised. This work explored the application of InGaAs and InGaSb material systems as the channel, in conjunction with Al2O3/metal gate stacks, for p-MOSFET development based on the buried-channel flatband device architecture. The body of work undertaken comprised material development, process module development and integration into a robust fabrication flow for the demonstration of p-channel devices. The parameter space in the design of the device layer structure, based around the III-V channel/barrier material options of In_x≥0.53Ga_1-xAs/In_0.52Al_0.48As and In_x≥0.1Ga_1-xSb/AlSb, was systematically examined to improve hole channel transport. A mobility of 433 cm²/Vs, the highest room temperature hole mobility of any InGaAs quantum-well channel reported to date, was obtained for the In_0.85Ga_0.15As (2.1% strain) structure. S/D ohmic contacts were developed based on thermally annealed Au/Zn/Au metallisation and validated using transmission line model test structures. The effects of metallisation thickness, diffusion barriers and de-oxidation conditions were examined. Contacts to InGaSb-channel structures were found to be sensitive to de-oxidation conditions. A fabrication process, based on a lithographically-aligned double ohmic patterning approach, was realised for deep submicron gate-to-source/drain gap (L_side) scaling to minimise the access resistance, thereby mitigating the effects of parasitic S/D series resistance on transistor performance. The developed process yielded gaps as small as 20nm. For high-k integration on GaSb, ex-situ ammonium sulphide ((NH₄)₂S) treatments, in the range 1%-22%, for 10min at 295K were systematically explored for improving the electrical properties of the Al₂O₃/GaSb interface. Electrical and physical characterisation indicated the 1% treatment to be most effective with interface trap densities in the range of 4 - 10×10¹²cm^-2eV^-1 in the lower half of the bandgap. An extended study, comprising additional immersion times at each sulphide concentration, was further undertaken to determine the surface roughness and the etching nature of the treatments on GaSb. A number of p-MOSFETs based on III-V-channels with the most promising hole transport and integration of the developed process modules were successfully demonstrated in this work. Although the non-inverted InGaAs-channel devices showed good current modulation and switch-off characteristics, several aspects of performance were non-ideal; depletion-mode operation, modest drive current (I_d,sat=1.14mA/mm), double peaked transconductance (g_m=1.06mS/mm), high subthreshold swing (SS=301mV/dec) and high on-resistance (R_on=845kΩ.μm). Despite demonstrating substantial improvement in the on-state metrics of I_d,sat (11×), g_m (5.5×) and R_on (5.6×), inverted devices did not switch-off. Scaling gate-to-source/drain gap (L_side) from 1μm down to 70nm improved I_d,sat (72.4mA/mm) by a factor of 3.6 and gm (25.8mS/mm) by a factor of 4.1 in inverted InGaAs-channel devices. Well-controlled current modulation and good saturation behaviour was observed for InGaSb-channel devices. In the on-state In_0.3Ga_0.7Sb-channel (I_d,sat=49.4mA/mm, g_m=12.3mS/mm, R_on=31.7kΩ.μm) and In_0.4Ga_0.6Sb-channel (I_d,sat=38mA/mm, g_m=11.9mS/mm, R_on=73.5kΩ.μm) devices outperformed the InGaAs-channel devices. However the devices could not be switched off. These findings indicate that III-V p-MOSFETs based on InGaSb as opposed to InGaAs channels are more suited as the p-channel option for post-Si CMOS.

Finite difference calculations of permeability in large domains in a wide porosity range.

Determining effective hydraulic, thermal, mechanical and electrical properties of porous materials by means of classical physical experiments is often time-consuming and expensive. Thus, accurate numerical calculations of material properties are of increasing interest in geophysical, manufacturing, bio-mechanical and environmental applications, among other fields. Characteristic material properties (e.g. intrinsic permeability, thermal conductivity and elastic moduli) depend on morphological details on the porescale such as shape and size of pores and pore throats or cracks. To obtain reliable predictions of these properties it is necessary to perform numerical analyses of sufficiently large unit cells. Such representative volume elements require optimized numerical simulation techniques. Current state-of-the-art simulation tools to calculate effective permeabilities of porous materials are based on various methods, e.g. lattice Boltzmann, finite volumes or explicit jump Stokes methods. All approaches still have limitations in the maximum size of the simulation domain. In response to these deficits of the well-established methods we propose an efficient and reliable numerical method which allows to calculate intrinsic permeabilities directly from voxel-based data obtained from 3D imaging techniques like X-ray microtomography. We present a modelling framework based on a parallel finite differences solver, allowing the calculation of large domains with relative low computing requirements (i.e. desktop computers). The presented method is validated in a diverse selection of materials, obtaining accurate results for a large range of porosities, wider than the ranges previously reported. Ongoing work includes the estimation of other effective properties of porous media.

Resistivity image beneath an area of active methane seeps in the west Svalbard continental slope

The Arctic continental margin contains large amounts of methane in the form of methane hydrates. The west Svalbard continental slope is an area where active methane seeps have been reported near the landward limit of the hydrate stability zone. The presence of bottom simulating reflectors (BSR) on seismic reflection data in water depths greater than 600 m suggests the presence of free gas beneath gas hydrates in the area. Resistivity obtained from marine controlled source electromagnetic (CSEM) data provides a useful complement to seismic methods for detecting shallow hydrate and gas as they are more resistive than surrounding water saturated sediments. We acquired two CSEM lines in the west Svalbard continental slope, extending from the edge of the continental shelf (250 m water depth) to water depths of around 800 m. High resistivities (5-12 Ωm) observed above the BSR support the presence of gas hydrate in water depths greater than 600 m. High resistivities (3-4 Ωm) at 390-600 m water depth also suggest possible hydrate occurrence within the gas hydrate stability zone (GHSZ) of the continental slope. In addition, high resistivities (4-8 Ωm) landward of the GHSZ are coincident with high-amplitude reflectors and low velocities reported in seismic data that indicate the likely presence of free gas. Pore space saturation estimates using a connectivity equation suggest 20-50% hydrate within the lower slope sediments and less than 12% within the upper slope sediments. A free gas zone beneath the GHSZ (10-20% gas saturation) is connected to the high free gas saturated (10-45%) area at the edge of the continental shelf, where most of the seeps are observed. This evidence supports the presence of lateral free gas migration beneath the GHSZ towards the continental shelf.

Aluminum nanoholes for optical biosensing

Sub-wavelength diameter holes in thin metal layers can exhibit remarkable optical features that make them highly suitable for (bio)sensing applications. Either as efficient light scattering centers for surface plasmon excitation or metal-clad optical waveguides, they are able to form strongly localized optical fields that can effectively interact with biomolecules and/or nanoparticles on the nanoscale. As the metal of choice, aluminum exhibits good optical and electrical properties, is easy to manufacture and process and, unlike gold and silver, its low cost makes it very promising for commercial applications. However, aluminum has been scarcely used for biosensing purposes due to corrosion and pitting issues. In this short review, we show our recent achievements on aluminum nanohole platforms for (bio)sensing. These include a method to circumvent aluminum degradation—which has been successfully applied to the demonstration of aluminum nanohole array (NHA) immunosensors based on both, glass and polycarbonate compact discs supports—the use of aluminum nanoholes operating as optical waveguides for synthesizing submicron-sized molecularly imprinted polymers by local photopolymerization, and a technique for fabricating transferable aluminum NHAs onto flexible pressure-sensitive adhesive tapes, which could facilitate the development of a wearable technology based on aluminum NHAs.

Hydrogeophysical Characterization of Anisotropy in the Biscayne Aquifer Using Geophysical Methods

The anisotropy of the Biscayne Aquifer which serves as the source of potable water for Miami-Dade County was investigated by applying geophysical methods. Electrical resistivity imaging, self potential and ground penetration radar techniques were employed in both regional and site specific studies. In the regional study, electrical anisotropy and resistivity variation with depth were investigated with azimuthal square array measurements at 13 sites. The observed coefficient of electrical anisotropy ranged from 1.01 to 1.36. The general direction of measured anisotropy is uniform for most sites and trends W-E or SE-NW irrespective of depth. Measured electrical properties were used to estimate anisotropic component of the secondary porosity and hydraulic anisotropy which ranged from 1 to 11% and 1.18 to 2.83 respectively. 1-D sounding analysis was used to models the variation of formation resistivity with depth. Resistivities decreased from NW (close to the margins of the everglades) to SE on the shores of Biscayne Bay. Porosity calculated from Archie's law, ranged from 18 to 61% with higher values found along the ridge. Higher anisotropy, porosities and hydraulic conductivities were on the Atlantic Coastal Ridge and lower values at low lying areas west of the ridge. The cause of higher anisotropy and porosity is attributed to higher dissolution rates of the oolitic facies of the Miami Formation composing the ridge. The direction of minimum resistivity from this study is similar to the predevelopment groundwater flow direction indicated in published modeling studies. Detailed investigations were carried out to evaluate higher anisotropy at West Perrine Park located on the ridge and Snapper Creek Municipal well field where the anisotropy trend changes with depth. The higher anisotropy is attributed to the presence of solution cavities oriented in the E-SE direction on the ridge. Similarly, the change in hydraulic anisotropy at the well field might be related to solution cavities, the surface canal and groundwater extraction wells.

Cálculo de constantes ópticas de películas delgadas de Cu3BiS3 a través del método de Wolfe

Se calculó la obtención de las constantes ópticas usando el método de Wolfe. Dichas contantes: coeficiente de absorción (α), índice de refracción (n) y espesor de una película delgada (d ), son de importancia en el proceso de caracterización óptica del material. Se realizó una comparación del método del Wolfe con el método empleado por R. Swanepoel. Se desarrolló un modelo de programación no lineal con restricciones, de manera que fue posible estimar las constantes ópticas de películas delgadas semiconductoras, a partir únicamente, de datos de transmisión conocidos. Se presentó una solución al modelo de programación no lineal para programación cuadrática. Se demostró la confiabilidad del método propuesto, obteniendo valores de α = 10378.34 cm−1, n = 2.4595, d =989.71 nm y Eg = 1.39 Ev, a través de experimentos numéricos con datos de medidas de transmitancia espectral en películas delgadas de Cu3BiS3.

Hall Effect and transient surface photovoltage (SPV) study of Cu3BiS3 thin films

Se presentan las propiedades eléctricas del compuesto Cu3BiS3 depositado por co-evaporación. Este es un nuevo compuesto que puede tener propiedades adecuadas para ser utilizado como capa absorbente en celdas solares. Las muestras fueron caracterizadas a través de medidas de efecto Hall y fotovoltaje superficial transiente (SPV). A través de medidas de efecto Hall se encontró que la concentración de portadores de carga n es del orden de 1016 cm-3 independiente de la relación de masas de Cu/Bi. También se encontró que la movilidad de este compuesto (μ del orden de 4 cm2V -1s-1) varía de acuerdo con los mecanismos de transporte que la gobiernan en dependencia con la temperatura. A partir de las medidas de SPV se encontró alta densidad de defectos superficiales, defectos que son pasivados al superponer una capa buffer sobre el compuesto Cu3BiS3.

Plasma polymer-coated on nanoparticles to improve dielectric and electrical insulation properties of nanocomposites

Polymeric nanocomposites have been shown to possess superior electrical insulation properties compared to traditional filled-resins. However, poor dispersion uniformity and insufficient filler-matrix interaction can adversely affect insulation properties of nanocomposites. In this study, the use of plasma polymerization is proposed to coat poly(ethylene oxide) polymer layers on silica nanoparticles. It is shown that better dispersion is achieved and C-O bonds are created between the surface functional groups of the nanoparticles and the host epoxy polymer. Electrical insulation tests demonstrate that the nanocomposites with plasma polymerized silica nanoparticles feature better resistance against electrical treeing, lower dielectric constant, and also mitigated space charge built-up. Therefore, plasma polymerization offers a promising fabrication technique to further improve the synthesis of nanocomposite dielectrics with superior electrical insulation properties.

Nitrogen-doped graphene films from chemical vapor deposition of pyridine: Influence of process parameters on the electrical and optical properties

Graphene films were produced by chemical vapor deposition (CVD) of pyridine on copper substrates. Pyridine-CVD is expected to lead to doped graphene by the insertion of nitrogen atoms in the growing sp2 carbon lattice, possibly improving the properties of graphene as a transparent conductive film. We here report on the influence that the CVD parameters (i.e., temperature and gas flow) have on the morphology, transmittance, and electrical conductivity of the graphene films grown with pyridine. A temperature range between 930 and 1070 °C was explored and the results were compared to those of pristine graphene grown by ethanol-CVD under the same process conditions. The films were characterized by atomic force microscopy, Raman and X-ray photoemission spectroscopy. The optical transmittance and electrical conductivity of the films were measured to evaluate their performance as transparent conductive electrodes. Graphene films grown by pyridine reached an electrical conductivity of 14.3 × 105 S/m. Such a high conductivity seems to be associated with the electronic doping induced by substitutional nitrogen atoms. In particular, at 930 °C the nitrogen/carbon ratio of pyridine-grown graphene reaches 3%, and its electrical conductivity is 40% higher than that of pristine graphene grown from ethanol-CVD.

Phase conversions in calcium manganites with changing Ca/Mn ratios and their influence on the electrical transport properties

The phase-interconversions between the spinel-, brownmillerite-, defect rocksalt and perovskite-type structures have been investigated by way of (i) introducing deficiency in A-sites in CaxMn2-xO3 (0.05 <= x <= 1) i.e., by varying Ca/Mn ratio from 0.025 to 1 and (ii) nonstoichiometric CaMnO3-delta (CMO) with 0.02 <= delta <= 1. The temperature dependence of resistivity (rho-T) have been investigated on nonstoichiometric CaMnO3-delta (undoped) as well as the CMO substituted with donor impurities such as La3+, Y3+, Bi3+ or acceptor such as Na1+ ion at the Ca-site. The rho-T characteristics of nonstoichiometric CaMnO3-delta is strongly influenced by oxygen deficiency, which controls the concentration of Mn3+ ions and, in turn, affects the resistivity, rho. The results indicated that the substitution of aliovalent impurities at Ca-site in CaMnO3 has similar effects as of CaMnO3-delta ( undoped) annealed in atmospheres of varying partial pressures whereby electron or hole concentration can be altered, yet the doped samples can be processed in air or atmospheres of higher P-O2. The charge transport mechanisms of nonstoichiometric CaMnO3-delta as against the donor or acceptor doped CaMnO3 (sintered in air, P-O2 similar to 0.2 atm) have been predicted. The rho (T) curves of both donor doped CaMnO3 as well as non-stoichiometric CaMnO3-delta, is predictable by the small polaron hopping (SPH) model, which changes to the variable range hopping (VRH) at low temperatures whereas the acceptor doped CaMnO3 exhibited an activated semiconducting hopping ( ASH) throughout the measured range of temperature (10-500 K).

Electrical and mechanical properties of diluted magnetic semiconductor Zn1-xMnxS nanocrystalline films

Nanostructured Zn1-xMnxS films (0 less-than-or-equals, slant x less-than-or-equals, slant 0.25) were deposited on glass substrates by simple resistive thermal evaporation technique. All the films were deposited at 300 K in a vacuum of 2*10-6 m bar. All the films temperature dependence of resistivity revealed semiconducting behaviour of the samples. Hot probe test revealed that all the samples exhibited n-type conductivity. The nanohardness of the films ranges from 4.7 to 9.9 GPa, Young's modulus value ranging 69.7-94.2 GPa.

Electrical, structural and magnetic properties of polyaniline/pTSA-TiO2 nanocomposites

Polyaniline (PANI)/para-toluene sulfonic acid (pTSA) and PANI/pTSA-TiO2 composites were prepared using chemical method and characterized by infrared spectroscopy (IR), powder X-ray diffraction (XRD), scanning electron microscopy (SEM). The electrical conductivity and magnetic properties were also measured. In corroboration with XRD, the micrographs of SEM indicated the homogeneous dispersion of TiO nanoparticles in bulk PANI/pTSA matrix. Conductivity of the PANI/pTSA-TiO2 was higher than the PAN[/pTSA, and the maximum conductivity obtained was 9.48 (S/cm) at 5 wt% of TiO2. Using SQUID magnetometer, it was found that PANI/pTSA was either paramagnetic or weakly ferromagnetic from 300 K down to 5 K with H-C approximate to 30 Oe and M-r approximate to 0.015 emu/g. On the other hand,PANI/pTSA-TiO2 was diamagnetic from 300 K down to about 50 K and below which it was weakly ferromagnetic. Furthermore, a nearly temperature-independent magnetization was observed in both the cases down to 50 K and below which the magnetization increased rapidly (a Curie like susceptibility was observed). The Pauli susceptibility (chi(pauli)) was calculated to be about 4.8 X 10(-5) and 1.6 x 10(-5)emug(-1) Oe(-1) K for PANI/pTSA and PANI/pTSA-TiO2, respectively.

Single layer bismuth iodide: Computational exploration of structural, electrical, mechanical and optical properties

Layered graphitic materials exhibit new intriguing electronic structure and the search for new types of two-dimensional (2D) monolayer is of importance for the fabrication of next generation miniature electronic and optoelectronic devices. By means of density functional theory (DFT) computations, we investigated in detail the structural, electronic, mechanical and optical properties of the single-layer bismuth iodide (BiI3) nanosheet. Monolayer BiI3 is dynamically stable as confirmed by the computed phonon spectrum. The cleavage energy (Ecl) and interlayer coupling strength of bulk BiI3 are comparable to the experimental values of graphite, which indicates that the exfoliation of BiI3 is highly feasible. The obtained stress-strain curve shows that the BiI3 nanosheet is a brittle material with a breaking strain of 13%. The BiI3 monolayer has an indirect band gap of 1.57 eV with spin orbit coupling (SOC), indicating its potential application for solar cells. Furthermore, the band gap of BiI3 monolayer can be modulated by biaxial strain. Most interestingly, interfacing electrically active graphene with monolayer BiI3 nanosheet leads to enhanced light absorption compared to that in pure monolayer BiI3 nanosheet, highlighting its great potential applications in photonics and photovoltaic solar cells.