Organic functionalisation, doping and characterisation of semiconductor surfaces for future CMOS device applications

Organic Functionalisation, Doping and Characterisation of Semiconductor Surfaces for Future CMOS Device Applications Semiconductor materials have long been the driving force for the advancement of technology since their inception in the mid-20th century. Traditionally, micro-electronic devices based upon these materials have scaled down in size and doubled in transistor density in accordance with the well-known Moore’s law, enabling consumer products with outstanding computational power at lower costs and with smaller footprints. According to the International Technology Roadmap for Semiconductors (ITRS), the scaling of metal-oxide-semiconductor field-effect transistors (MOSFETs) is proceeding at a rapid pace and will reach sub-10 nm dimensions in the coming years. This scaling presents many challenges, not only in terms of metrology but also in terms of the material preparation especially with respect to doping, leading to the moniker “More-than-Moore”. Current transistor technologies are based on the use of semiconductor junctions formed by the introduction of dopant atoms into the material using various methodologies and at device sizes below 10 nm, high concentration gradients become a necessity. Doping, the controlled and purposeful addition of impurities to a semiconductor, is one of the most important steps in the material preparation with uniform and confined doping to form ultra-shallow junctions at source and drain extension regions being one of the key enablers for the continued scaling of devices. Monolayer doping has shown promise to satisfy the need to conformally dope at such small feature sizes. Monolayer doping (MLD) has been shown to satisfy the requirements for extended defect-free, conformal and controllable doping on many materials ranging from the traditional silicon and germanium devices to emerging replacement materials such as III-V compounds This thesis aims to investigate the potential of monolayer doping to complement or replace conventional doping technologies currently in use in CMOS fabrication facilities across the world.

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.

Effect of reaction mechanism on precursor exposure time in atomic layer deposition of silicon oxide and silicon nitride

Atomic layer deposition (ALD) of highly conformal, silicon-based dielectric thin films has become necessary because of the continuing decrease in feature size in microelectronic devices. The ALD of oxides and nitrides is usually thought to be mechanistically similar, but plasma-enhanced ALD of silicon nitride is found to be problematic, while that of silicon oxide is straightforward. To find why, the ALD of silicon nitride and silicon oxide dielectric films was studied by applying ab initio methods to theoretical models for proposed surface reaction mechanisms. The thermodynamic energies for the elimination of functional groups from different silicon precursors reacting with simple model molecules were calculated using density functional theory (DFT), explaining the lower reactivity of precursors toward the deposition of silicon nitride relative to silicon oxide seen in experiments, but not explaining the trends between precursors. Using more realistic cluster models of amine and hydroxyl covered surfaces, the structures and energies were calculated of reaction pathways for chemisorption of different silicon precursors via functional group elimination, with more success. DFT calculations identified the initial physisorption step as crucial toward deposition and this step was thus used to predict the ALD reactivity of a range of amino-silane precursors, yielding good agreement with experiment. The retention of hydrogen within silicon nitride films but not in silicon oxide observed in FTIR spectra was accounted for by the theoretical calculations and helped verify the application of the model.

Kinetics and coverage dependent reaction mechanisms of the copper atomic layer deposition from copper dimethylamino-2-propoxide and diethylzinc

Atomic layer deposition (ALD) has been recognized as a promising method to deposit conformal and uniform thin film of copper for future electronic devices. However, many aspects of the reaction mechanism and the surface chemistry of copper ALD remain unclear. In this paper, we employ plane wave density functional theory (DFT) to study the transmetalation ALD reaction of copper dimethylamino-2-propoxide [Cu(dmap)2] and diethylzinc [Et2Zn] that was realized experimentally by Lee et al. [ Angew. Chem., Int. Ed. 2009, 48, 4536−4539]. We find that the Cu(dmap)2 molecule adsorbs and dissociates through the scission of one or two Cu–O bonds into surface-bound dmap and Cu(dmap) fragments during the copper pulse. As Et2Zn adsorbs on the surface covered with Cu(dmap) and dmap fragments, butane formation and desorption was found to be facilitated by the surrounding ligands, which leads to one reaction mechanism, while the migration of ethyl groups to the surface leads to another reaction mechanism. During both reaction mechanisms, ligand diffusion and reordering are generally endothermic processes, which may result in residual ligands blocking the surface sites at the end of the Et2Zn pulse, and in residual Zn being reduced and incorporated as an impurity. We also find that the nearby ligands play a cooperative role in lowering the activation energy for formation and desorption of byproducts, which explains the advantage of using organometallic precursors and reducing agents in Cu ALD. The ALD growth rate estimated for the mechanism is consistent with the experimental value of 0.2 Å/cycle. The proposed reaction mechanisms provide insight into ALD processes for copper and other transition metals.

Development and characterisation of solution processed vanadium oxide and transparent metal oxide thin films

Metal oxide thin films are important for modern electronic devices ranging from thin film transistors to photovoltaics and functional optical coatings. Solution processed techniques allow for thin films to be rapidly deposited over a range of surfaces without the extensive processing of comparative vapour or physical deposition methods. The production of thin films of vanadium oxide prepared through dip-coating was developed enabling a greater understanding of the thin film formation. Mechanisms of depositing improved large area uniform coverage on a number of technologically relevant substrates were examined. The fundamental mechanism for polymer-assisted deposition in improving thin film surface smoothness and long range order has been delivered. Different methods were employed for adapting the alkoxide based dip-coating technique to produce a variety of amorphous and crystalline vanadium oxide based thin films. Using a wide range of material, spectroscopic and optical measurement techniques the morphology, structure and optoelectronic properties of the thin films were studied. The formation of pinholes on the surface of the thin films, due to dewetting and spinodal effects, was inhibited using the polymer assisted deposition technique. Uniform thin films with sub 50 nm thicknesses were deposited on a variety of substrates controlled through alterations to the solvent-alkoxide dilution ratios and employing polymer assisted deposition techniques. The effects of polymer assisted deposition altered the crystallized VO thin films from a granular surface structure to a polycrystalline structure composed of high density small in-plane grains. The formation of transparent VO based thin film through Si and Na substrate mediated diffusion highlighted new methods for material formation and doping.

Carrier momentum relaxation in highly doped polar semiconductors and semiconductor heterostructures

Highly doped polar semiconductors are essential components of today’s semiconductor industry. Most strikingly, transistors in modern electronic devices are polar semiconductor heterostructures. It is important to thoroughly understand carrier transport in such structures. In doped polar semiconductors, collective excitations of the carriers (plasmons) and the atoms (polar phonons) couple. These coupled collective excitations affect the electrical conductivity, here quantified through the carrier mobility. In scattering events, the carriers and the coupled collective modes transfer momentum between each other. Carrier momentum transferred to polar phonons can be lost to other phonons through anharmonic decay, resulting in a finite carrier mobility. The plasmons do not have a decay mechanism which transfers carrier momentum irretrievably. Hence, carrier-plasmon scattering results in infinite carrier mobility. Momentum relaxation due to either carrier–plasmon scattering or carrier–polar-phonon scattering alone are well understood. However, only this thesis manages to treat momentum relaxation due to both scattering mechanisms on an equal footing, enabling us to properly calculate the mobility limited by carrier–coupled plasmon–polar phonon scattering. We achieved this by solving the coupled Boltzmann equations for the carriers and the collective excitations, focusing on the “drag” term and on the anharmonic decay process of the collective modes. Our approach uses dielectric functions to describe both the carrier-collective mode scattering and the decay of the collective modes. We applied our method to bulk polar semiconductors and heterostructures where various polar dielectrics surround a semiconducting monolayer of MoS2, where taking plasmons into account can increase the mobility by up to a factor 15 for certain parameters. This screening effect is up to 85% higher than if calculated with previous methods. To conclude, our approach provides insight into the momentum relaxation mechanism for carrier–coupled collective mode scattering, and better tools for calculating the screened polar phonon and interface polar phonon limited mobility.

Bottom-up growth of fully transparent contact layers of indium tin oxide nanowires for light-emitting devices

Thin layers of indium tin oxide are widely used as transparent coatings and electrodes in solar energy cells, flat-panel displays, antireflection coatings, radiation protection and lithium-ion battery materials, because they have the characteristics of low resistivity, strong absorption at ultraviolet wavelengths, high transmission in the visible, high reflectivity in the far-infrared and strong attenuation in the microwave region. However, there is often a trade-off between electrical conductivity and transparency at visible wavelengths for indium tin oxide and other transparent conducting oxides. Here, we report the growth of layers of indium tin oxide nanowires that show optimum electronic and photonic properties and demonstrate their use as fully transparent top contacts in the visible to near-infrared region for light-emitting devices.

Electron beam induced electronic transport in alkyl amine-intercalated VOx nanotubes

The electron beam induced electronic transport in primary alkyl amine-intercalated V2O5 nanotubes is investigated where the organic amine molecules are employed as molecular conductive wires to an aminosilanized substrate surface and contacted to Au interdigitated electrode contacts. The results demonstrate that the high conductivity of the nanotubes is related to the non-resonant tunnelling through the amine molecules and a reduced polaron hopping conduction through the vanadium oxide itself. Both nanotube networks and individual nanotubes exhibit similarly high conductivities where the minority carrier transport is bias dependent and nanotube diameter invariant.

Photonic packaging: transforming silicon photonic integrated circuits into photonic devices

Dedicated multi-project wafer (MPW) runs for photonic integrated circuits (PICs) from Si foundries mean that researchers and small-to-medium enterprises (SMEs) can now afford to design and fabricate Si photonic chips. While these bare Si-PICs are adequate for testing new device and circuit designs on a probe-station, they cannot be developed into prototype devices, or tested outside of the laboratory, without first packaging them into a durable module. Photonic packaging of PICs is significantly more challenging, and currently orders of magnitude more expensive, than electronic packaging, because it calls for robust micron-level alignment of optical components, precise real-time temperature control, and often a high degree of vertical and horizontal electrical integration. Photonic packaging is perhaps the most significant bottleneck in the development of commercially relevant integrated photonic devices. This article describes how the key optical, electrical, and thermal requirements of Si-PIC packaging can be met, and what further progress is needed before industrial scale-up can be achieved.