Development of a triple stage heat transformer for the recycling of low temperature heat energy

Absorption heat transformers are thermodynamic systems which are capable of recycling industrial waste heat energy by increasing its temperature. Triple stage heat transformers (TAHTs) can increase the temperature of this waste heat by up to approximately 145˚C. The principle factors influencing the thermodynamic performance of a TAHT and general points of operating optima were identified using a multivariate statistical analysis, prior to using heat exchange network modelling techniques to dissect the design of the TAHT and systematically reassemble it in order to minimise internal exergy destruction within the unit. This enabled first and second law efficiency improvements of up to 18.8% and 31.5% respectively to be achieved compared to conventional TAHT designs. The economic feasibility of such a thermodynamically optimised cycle was investigated by applying it to an oil refinery in Ireland, demonstrating that in general the capital cost of a TAHT makes it difficult to achieve acceptable rates of return. Decreasing the TAHT's capital cost may be achieved by redesigning its individual pieces of equipment and reducing their size. The potential benefits of using a bubble column absorber were therefore investigated in this thesis. An experimental bubble column was constructed and used to track the collapse of steam bubbles being absorbed into a hotter lithium bromide salt solution. Extremely high mass transfer coefficients of approximately 0.0012m/s were observed, showing significant improvements over previously investigated absorbers. Two separate models were developed, namely a combined heat and mass transfer model describing the rate of collapse of the bubbles, and a stochastic model describing the hydrodynamic motion of the collapsing vapour bubbles taking into consideration random fluctuations observed in the experimental data. Both models showed good agreement with the collected data, and demonstrated that the difference between the solution's temperature and its boiling temperature is the primary factor influencing the absorber's performance.

Nanowires for 3d silicon interconnection – low temperature compliant nanowire-polymer film for z-axis interconnect

Semiconductor chip packaging has evolved from single chip packaging to 3D heterogeneous system integration using multichip stacking in a single module. One of the key challenges in 3D integration is the high density interconnects that need to be formed between the chips with through-silicon-vias (TSVs) and inter-chip interconnects. Anisotropic Conductive Film (ACF) technology is one of the low-temperature, fine-pitch interconnect method, which has been considered as a potential replacement for solder interconnects in line with continuous scaling of the interconnects in the IC industry. However, the conventional ACF materials are facing challenges to accommodate the reduced pad and pitch size due to the micro-size particles and the particle agglomeration issue. A new interconnect material - Nanowire Anisotropic Conductive Film (NW-ACF), composed of high density copper nanowires of ~ 200 nm diameter and 10-30 µm length that are vertically distributed in a polymeric template, is developed in this work to tackle the constrains of the conventional ACFs and serves as an inter-chip interconnect solution for potential three-dimensional (3D) applications.

Experimental study of quantum dot and dash lasers

Quantum dashes are elongated quantum dots. Polarized edge-photovoltage and spontaneous emission spectroscopy are used to study the anisotropy of optical properties in 1.5μm InGaAsP and AlGaInAs-based quantum dash lasers. Strain, which causes TM-polarized transitions to be suppressed at the band edge, coupled with carrier confinement and dash shape leads to an enhancement of the optical properties for light polarized along the dash long axis, in excellent agreement with theoretical results. An analysis of the integrated facet and spontaneous emission rate with total current and temperature reveals that, in both undoped and p-doped InGaAsP-based quantum dash lasers at room temperature, the threshold current and its temperature dependence remain dominated by Auger recombination. We also identify two processes which can limit the output power and propose that the effects of the dopant in p-doped InGaAsP-based lasers dominate at low temperature but decrease with increasing temperature. A high threshold current density in undoped AlGaInAs-based quantum dash laser samples studied, which degrade rapidly at low temperature, is not due to intrinsic carrier recombination processes. 1.3μm GaAs-based quantum dots lasers have been widely studied, but there remains issues as to the nature of the electronic structure. Polarized edge-photovoltage spectroscopy is used to investigate the energy distribution and nature of the energy states in InAs/GaAs quantum dot material. A non-negligible TM-polarized transition, which is often neglected in calculations and analyses, is measured close to the main TE-polarized ground state transition. Theory is in very good agreement with the experimental results and indicates that the measured low-energy TM-polarized transition is due to the strong spatial overlap between the ground state electron and the light-hole component of a low-lying excited hole state. Further calculations suggest that the TM-polarized transition reduces at the band edge as the quantum dot aspect ratio decreases.

First principles simulation of amorphous silicon bulk, interfaces, and nanowires for photovoltaics

Amorphous silicon has become the material of choice for many technologies, with major applications in large area electronics: displays, image sensing and thin film photovoltaic cells. This technology development has occurred because amorphous silicon is a thin film semiconductor that can be deposited on large, low cost substrates using low temperature. In this thesis, classical molecular dynamics and first principles DFT calculations have been performed to generate structural models of amorphous and hydrogenated amorphous silicon and interfaces of amorphous and crystalline silicon, with the ultimate aim of understanding the photovoltaic properties of core-shell crystalline amorphous Si nanowire structures. We have shown, unexpectedly, from the simulations, that our understanding of hydrogenated bulk a-Si needs to be revisited, with our robust finding that when fully saturated with hydrogen, bulk a-Si exhibits a constant optical energy gap, irrespective of the hydrogen concentration in the sample. Unsaturated a-Si:H, with a lower than optimum hydrogen content, shows a smaller optical gap, that increases with hydrogen content until saturation is reached. The mobility gaps obtained from an analysis of the electronic states show similar behavior. We also obtained that the optical and mobility gaps show a volcano curve as the H content is varied from 7% (undersaturation) to 18% (mild oversaturation). In the case of mild over saturation, the mid-gap states arise exclusively from an increase in the density of strained Si-Si bonds. Analysis of our structures shows the extra H atoms in this case form a bridge between neighboring silicon atoms which increases the corresponding Si-Si distance and promotes bond length disorder in the sample. That has the potential to enhance the Staebler-Wronski effect. Planar interface models of amorphous-crystalline silicon have been generated in Si (100), (110) and (111) surfaces. The interface models are characterized by structure, RDF, electronic density of states and optical absorption spectrum. We find that the least stable (100) surface will result in the formation of the thickest amorphous silicon layer, while the most stable (110) surface forms the smallest amorphous region. We calculated for the first time band offsets of a-Si:H/c-Si heterojunctions from first principles and examined the influence of different surface orientations and amorphous layer thickness on the offsets and implications for device performance. The band offsets depend on the amorphous layer thickness and increase with thickness. By controlling the amorphous layer thickness we can potentially optimise the solar cell parameters. Finally, we have successfully generated different amorphous layer thickness of the a-Si/c-Si and a-Si:H/c-Si 5 nm nanowires from heat and quench. We perform structural analysis of the a-Si-/c-Si nanowires. The RDF, Si-Si bond length distributions, and the coordination number distributions of amorphous regions of the nanowires reproduce similar behaviour compared to bulk amorphous silicon. In the final part of this thesis we examine different surface terminating chemical groups, -H, - OH and –NH2 in (001) GeNW. Our work shows that the diameter of Ge nanowires and the nature of surface terminating groups both play a significant role in both the magnitude and the nature of the nanowire band gaps, allowing tuning of the band gap by up to 1.1 eV. We also show for the first time how the nanowire diameter and surface termination shifts the absorption edge in the Ge nanowires to longer wavelengths. Thus, the combination of nanowire diameter and surface chemistry can be effectively utilised to tune the band gaps and thus light absorption properties of small diameter Ge nanowires.

Precursor adsorption on copper surfaces as the first step during the deposition of copper: a density functional study with van der Waals correction

Copper dimethylamino-2-propoxide [Cu(dmap)2] is used as a precursor for low-temperature atomic layer deposition (ALD) of copper thin films. Chemisorption of the precursor is the necessary first step of ALD, but it is not known in this case whether there is selectivity for adsorption sites, defects, or islands on the substrate. Therefore, we study the adsorption of the Cu(dmap)2 molecule on the different sites on flat and rough Cu surfaces using PBE, PBE-D3, optB88-vdW, and vdW-DF2 methods. We found the relative order of adsorption energies for Cu(dmap)2 on Cu surfaces is Eads (PBE-D3) > Eads (optB88-vdW) > Eads (vdW-DF2) > Eads (PBE). The PBE and vdW-DF2 methods predict one chemisorption structure, while optB88-vdW predicts three chemisorption structures for Cu(dmap)2 adsorption among four possible adsorption configurations, whereas PBE-D3 predicts a chemisorbed structure for all the adsorption sites on Cu(111). All the methods with and without van der Waals corrections yield a chemisorbed molecule on the Cu(332) step and Cu(643) kink because of less steric hindrance on the vicinal surfaces. Strong distortion of the molecule and significant elongation of Cu–N bonds are predicted in the chemisorbed structures, indicating that the ligand–Cu bonds break during the ALD of Cu from Cu(dmap)2. The molecule loses its initial square-planar structure and gains linear O–Cu–O bonding as these atoms attach to the surface. As a result, the ligands become unstable and the precursor becomes more reactive to the coreagent. Charge redistribution mainly occurs between the adsorbate O–Cu–O bond and the surface. Bader charge analysis shows that electrons are donated from the surface to the molecule in the chemisorbed structures, so that the Cu center in the molecule is partially reduced.