Synthesis and functionalization of large-area graphene and its structural, electrical and electrochemical properties has been investigated. First, the graphene films, grown by thermal chemical vapor deposition (CVD), contain three to five atomic layers of graphene, as confirmed by Raman spectroscopy and high-resolution transmission electron microscopy. Furthermore, the graphene film is treated with CF4 reactive-ion plasma to dope fluorine ions into graphene lattice as confirmed by X-ray photoelectron spectroscopy (XPS) and UV-photoemission spectroscopy (UPS). Electrochemical characterization reveals that the catalytic activity of graphene for iodine reduction enhanced with increasing plasma treatment time, which is attributed to increase in catalytic sites of graphene for charge transfer. The fluorinated graphene is characterized as a counter-electrode (CE) in a dye-sensitized solar cell (DSSC) which shows ~ 2.56% photon to electron conversion efficiency with ~11 mAcm−2 current density. Second, the large scale graphene film is covalently functionalized with HNO3 for high efficiency electro-catalytic electrode for DSSC. The XPS and UPS confirm the covalent attachment of C-OH, C(O)OH and NO3- moieties with carbon atoms through sp2-sp3 hybridization and Fermi level shift of graphene occurs under different doping concentrations, respectively. Finally, CoS-implanted graphene (G-CoS) film was prepared using CVD followed by SILAR method. The G-CoS electro-catalytic electrodes are characterized in a DSSC CE and is found to be highly electro-catalytic towards iodine reduction with low charge transfer resistance (Rct ~5.05 Wcm2) and high exchange current density (J0~2.50 mAcm-2). The improved performance compared to the pristine graphene is attributed to the increased number of active catalytic sites of G-CoS and highly conducting path of graphene. We also studied the synthesis and characterization of graphene-carbon nanotube (CNT) hybrid film consisting of graphene supported by vertical CNTs on a Si substrate. The hybrid film is inverted and transferred to flexible substrates for its application in flexible electronics, demonstrating a distinguishable variation of electrical conductivity for both tension and compression. Furthermore, both turn-on field and total emission current was found to depend strongly on the bending radius of the film and were found to vary in ranges of 0.8 – 3.1 V/μm and 4.2 – 0.4 mA, respectively.

The continued growth of the optoelectronics industry and the emergence of wearable and flexible electronics will continue to place an ever increasing pressure on replacing ITO, the most widely used transparent conducting electrode (TCE). Among the various candidates, graphene shows the highest optical transmittance in addition to promising electrical transport properties. The currently available large-scale synthesis routes of graphene result in polycrystalline samples rife with grain boundaries and other defects which limit its transport properties. Chemical doping of graphene is a viable route towards increasing its conductivity and tuning its work function. However, dopants are typically present at the surface of the graphene sheet, making them highly susceptible to degradation in environmental conditions. Few-layers graphene (FLG) is a more resilient form of graphene exhibiting higher conductivity and performance stability under stretching and bending as contrasted to single-layer graphene. In addition FLG presents the advantage of being amenable bulk doping by intercalation. Herein, we explore non-covalent doping routes of CVD FLG, such as surface doping, intercalation and combination thereof, through in-depth and systematic characterization of the electrical transport properties and energy levels shifts. The intercalation of FLG with Br2 and FeCl3 is demonstrated, showing the highest improvements of the figure of merit of TCEs of any doping scheme, which results from up to a five-fold increase in conductivity while maintaining the transmittance within 3% of that for the pristine value. Importantly the intercalation yields TCEs that are air-stable, due to encapsulation of the intercalant in the bulk of FLG. Surface doping with novel solution-processed metal-organic molecular species (n- and p-type) is demonstrated with an unprecedented range of work function modulation, resulting from electron transfer and the formation of molecular surface dipoles. However, the conductivity increases compared modestly to intercalation as the electron transfer is limited to the uppermost graphene layers. Finally, a novel and universal multi-modal doping strategy is developed, thanks to the unique platform offered by FLG, where surface and intercalation doping are combined to mutually achieve high conductivity with an extended tunability of the work function. This work presents doped-FLG as a prospective and versatile candidate among emerging TCEs, given the need for efficient and stable doping routes capable of controllably tuning its properties to meet the criteria of a broad range of applications.

The excellent corrosion resistance of stainless steels arises from the presence of a passive film on its surface. Above 10.5wt% Cr a chromium oxide of 1-3 nm is formed on the surface of the metal that in case of damage will reform and hinder further dissolution of the metal. However, the passivity of the stainless steel can be altered by material factors and external factors; such as the composition of the underlying phases, external loads or thermal treatments. In this work the local electrochemical techniques Scanning Vibrating Electrode Technique (SVET) and Scanning Kelvin Probe Force Microscopy (SKPFM) and the local characterization techniques X-ray Photoelectron Spectroscopy (XPS) and Auger Electron Spectroscopy (AES) have been used to investigate corrosion phenomena of stainless alloys based on measurements of corrosion current density, work function, thickness and composition of the oxide. The effect on work function of the thickness of the passive film and composition of the underlying phases was investigated for 301LN austenitic stainless steel (Paper I) and a heat treated superduplex 25Cr7Ni type stainless steel (Paper II). It was shown that the work function can be an indicator of corrosion resistance of the phases in the microstructure, and that the composition of the underlying phases had a greater effect on the work function than the thickness of the passive film. External factors such mechanical deformation (Paper I) and welding (Paper III) altered the passivity of the steel and work function. It was found that plastic deformation decreased irreversibly the work function, whereas elastic deformation did not have any permanent effect. Thermal oxides affected the passivity of stainless steels welded joints and were detrimental for its corrosion resistance. Anodic activity, observed with SVET, and pitting corrosion were detected at the heat tint and attributed to the interaction between the composition and the thickness of the oxide. Brushing combined with pickling was recommended for recovering the passivity of stainless steels. / <p>QC 20160516</p>

This communication will demonstrate the existence of a thermodynamic molecular switch in the pairwise, sequence-specific hydrophobic interaction of Ile-Ile, Leu-Ile, Val-Leu, or Ala-Leu over the temperature range of 273-333 K reported by Nemethy and Scheraga in 1962. Based on Chun's development of the Planck-Benzinger methodology, the change in inherent chemical bond energy at 0 K, ΔH°(T0), is 3.0 kcal mol-1 for Ile-Ile, 2.4 for Leu-Ile, 1.8 for Val-Leu, and 1.2 kcal mol-1 for Ala-Leu. The value of ΔH°(T0) decreases as the length of the hydrophobics side chain decreases. It is clear that the strength and stability of the hydrophobic interaction is determined by the packing density of the side chains, with Ala-Leu being the most stable. At , the thermal agitation energy, ∫0T ΔCp°(T)dT, is about five times greater than ΔH°(T0) in each case. Additionally, the thermal agitation energy for the same series, evaluated at , decreases in the same order, that is, as the length of the side chain decreases. This pairwise, sequence-specific hydrophobic interaction is highly similar in its thermodynamic behavior to that of other biological systems, except that the negative Gibbs free energy change minimum at occurs at a considerably higher temperature, 355 K compared to about 300 K. The melting temperature, , is also high, 470K compared to 343 K in a biological system. The implication is that the negative Gibbs free energy minimum at a well-defined >Ts> has it origin in the hydrophobic interactions, which are highly dependent on details of molecular structure. In addition to the four specific dipeptide interactions described, we have shown in our unpublished work the existence of a thermodynamic molecular switch in the interactions of 32 dipeptides wherein a change of sign in ΔCp°(T)reaction leads to a true negative minimum in the Gibbs free energy of reaction, and hence, a maximum in the related Keq. Indeed, all interacting biological systems that we have thus far examined using the Planck-Benzinger approach point to the universality of thermodynamic molecular switches.

No description available.

No description available.

Motivated by problems in logistics, image recognition, and statistics, we consider the server allocation problem. In this problem, we are given $k$ servers (with capacities) and $n$ requests, which are points in a metric space. A server serves a request by moving to the request location, and the goal is to serve all requests while minimizing the total movement of servers, subject to the constraint that the number of requests served by a server cannot exceed its capacity. When the server capacity is $1$, and for the Euclidean metric, the problem reduces to the Euclidean bipartite matching problem. When the capacity is $infty$, suppose we are also provided with the order in which requests are to be served, the problem is the $k$-first come first served routing problem. We also consider a generalization of the $k$-first come first served routing problem to the taxi allocation problem, where each request is associated with a pickup location, dropoff location, and pickup time, and the server's velocity is also given as input. We present new algorithms for the Euclidean bipartite matching problem, showing improvements over existing algorithms. In particular, for two point sets $A, B subset mathbb{R}^d$ with $|A| = |B| = n$ and dimension $d > 1$ being constant, we developed: begin{itemize} item A faster algorithm that computes an $varepsilon$-approximate minimum-cost perfect matching in $O(n(varepsilon^{-O(d^3)}loglog n + varepsilon^{-O(d)}log^4 nlog^5log n))$ time. This is an improvement over previous algorithms, which took $n(varepsilon^{-1}log n)^{Omega(d)}$ time. item An algorithm that boosts the accuracy of any $varepsilon$-additive approximation algorithm, achieving an expected additive error of $min{varepsilon, (dloglog n)w^*}$ from the optimal matching cost $w^*$ in $O(T(n, varepsilon/d)loglog n)$ time, where $T(n, varepsilon)$ is the time complexity of any given $eps$-additive approximation algorithm. end{itemize} For the $k$-first come first served routing problem, we present the following results. begin{itemize} item The online version of the $k$-first come first served routing problem is the celebrated $k$-server problem. The best-known online algorithm for this problem is the Work Function algorithm. We present a new implementation of the work function algorithm, where processing the $i$th request takes $O((i+k)^2)$ time, improving on the previous methods that take $Omega(k(i+k)^2)$ time. item For the offline setting, we show that the $k$-first come first served routing problem and the taxi allocation problem can be reduced to the minimum-cost bipartite matching problem. Using this reduction, begin{itemize} item we develop a time-based divide-and-conquer algorithm to obtain an optimal solution in $tilde{O}(kn^2)$ time, which can be further improved to $tilde{O}(kn)$ when the requests and servers are in two-dimensional Euclidean space, and, item we apply a recently presented geometric divide-and-conquer algorithm to obtain an optimal solution for the taxi routing problem in a two-dimensional Euclidean space. As a result, we obtain significant empirical performance improvements for the taxi allocation problem in a two-dimensional space where the cost of moving from one location to another is lower bounded by the Euclidean cost. end{itemize} end{itemize} / Doctor of Philosophy / In the server allocation problem, we are given n requests and k servers, both as points in a space. A server can serve a request by moving to the request location, and each request can be served by exactly one server. The objective is to optimize the allocation of servers to requests such that the total distance traveled by the servers is minimized. In this thesis, we present efficient algorithms for three specific problems in the server allocation problem framework. First, we consider the case when the servers are restricted to serving up to one request each. This problem reduces to the well-known minimum cost maximum cardinality bipartite matching problem. When the underlying distance is Euclidean, this problem is called the Euclidean bipartite matching problem. We present two efficient algorithms that improve the state-of-the-art for the Euclidean bipartite matching problem. Second, we consider the case when the servers can handle multiple requests. Assuming the requests are given as ordered sequences, a server can serve a subsequence of the request sequence. We devise two efficient algorithms for this problem and show empirical performance improvements on the New York Taxi data set. Third, we consider the scenario when the requests appear in an online fashion such that on the arrival of each request, a server must be allocated to it immediately and irrevocably. This problem is the celebrated k-server problem. The work function algorithm is an online algorithm that solves the k-server problem with the best-known competitive ratio. We present a new, faster implementation of the work function algorithm.

Scandate cathode under various processing stages: scandia nano-powder, tungsten scandia mix powder, sintered and impregnated pellets, were characterized with techniques that included electron microscopy, EDS, XPS, and work function measurements. The size and shape uniformity of nano-scale scandia particles changed from round to square and polyhedron during heat treatment. Reduction in size and improvement in size uniformity as heat treating temperature increased were observed. When determining the highest Sc coverage, three assessment methods were used and with their combined results, it was concluded that set VII had the highest Sc at%. In the sintered pellets, it was observed with SEM that more initial scandia coverage in the mix powder sets corresponded to a larger number of scandia particles distributed over the tungsten surface. The structure of the cross section made on pellet surface was porous which was expected in any functional cathode. Kelvin probe measurements revealed that work function values of sintered pellets were similar and decreased by approximately 0.6 eV after the impregnation. A cross section on the impregnated pellet surface revealed that the pores that existed in sintered pellets were gone and filled with impregnated materials that emerged to the surface during impregnation.

<p>The development and implementation of a metal gate technology (alloy, compound, or silicide) into metal-oxide-semiconductor field effect transistors (MOSFETs) is necessary to extend the life of planar CMOS devices and enable further downscaling. This thesis examines possible metal gate materials for improving the performance of the gate stack and discusses process integration as well as improved electrical and physical measurement methodologies, tested on capacitor structures and transistors. </p><p>By using reactive PVD and gradually increasing the N₂/Ar flow ratio, it was found that the work function (on SiO₂) of the TiN_x and ZrN_x metal systems could be modulated ~0.7 eV from low near nMOS work functions to high pMOS work functions. After high-temperature anneals corresponding to junction activation, both metals systems reached mid-gap work function values. The mechanisms behind the work function changes are explained with XPS data and discussed in terms of metal gradients and Fermi level pinning due to extrinsic interface states.</p><p>A modified scheme for improved Fowler-Nordheim tunnelling is also shown, using degenerately doped silicon substrates. In that case, the work functions of ALD/PVD TaN were accurately determined on both SiO₂ and HfO₂ and benchmarked against IPE (Internal Photoemission) results. KFM (Kelvin Force Microscopy) was also used to physically measure the work functions of PVD TiN and Mo deposited on SiO₂; the results agreed well with <i>C-V</i> and <i>I-V</i> data.</p><p>Finally, an appealing combination of novel materials is demonstrated with ALD TiN/Al₂O₃/HfAlO_x/Al₂O₃/strained-SiGe surface channel pMOS devices. The drive current and transconductance were measured to be 30% higher than the Si reference, clearly demonstrating increased mobility and the absence of polydepletion. Finally, using similarly processed transistors with Al₂O₃ dielectric instead, low-temperature water vapour annealing was shown to improve the device characteristics by reducing the negative charge within the ALD Al₂O₃.</p>

The development and implementation of a metal gate technology (alloy, compound, or silicide) into metal-oxide-semiconductor field effect transistors (MOSFETs) is necessary to extend the life of planar CMOS devices and enable further downscaling. This thesis examines possible metal gate materials for improving the performance of the gate stack and discusses process integration as well as improved electrical and physical measurement methodologies, tested on capacitor structures and transistors. By using reactive PVD and gradually increasing the N2/Ar flow ratio, it was found that the work function (on SiO2) of the TiNx and ZrNx metal systems could be modulated ~0.7 eV from low near nMOS work functions to high pMOS work functions. After high-temperature anneals corresponding to junction activation, both metals systems reached mid-gap work function values. The mechanisms behind the work function changes are explained with XPS data and discussed in terms of metal gradients and Fermi level pinning due to extrinsic interface states. A modified scheme for improved Fowler-Nordheim tunnelling is also shown, using degenerately doped silicon substrates. In that case, the work functions of ALD/PVD TaN were accurately determined on both SiO2 and HfO2 and benchmarked against IPE (Internal Photoemission) results. KFM (Kelvin Force Microscopy) was also used to physically measure the work functions of PVD TiN and Mo deposited on SiO2; the results agreed well with C-V and I-V data. Finally, an appealing combination of novel materials is demonstrated with ALD TiN/Al2O3/HfAlOx/Al2O3/strained-SiGe surface channel pMOS devices. The drive current and transconductance were measured to be 30% higher than the Si reference, clearly demonstrating increased mobility and the absence of polydepletion. Finally, using similarly processed transistors with Al2O3 dielectric instead, low-temperature water vapour annealing was shown to improve the device characteristics by reducing the negative charge within the ALD Al2O3.