Browsing by Subject "Core-shell"
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Item Confined electron systems in Si-Ge nanowire heterostructures(2011-08) Dillen, David Carl; Tutuc, Emanuel, 1974-; Banerjee, Sanjay K.Semiconductor nanowire field-effect transistors (NWFET) have been recognized as a possible alternative to silicon-based CMOS technology as traditional scaling limits are neared. The core-shell nanowire structure, in particular, also allows for the enhancement of carrier mobility through radial band engineering. In this thesis, we have evaluated the possibility of electron confinement in strained Si-Si1-xGex core-shell nanowire heterostructures. Cylindrical strain distribution was calculated analytically for structures of various dimensions and shell compositions. The strain-induced conduction band edge shift of each region was found using k•p theory coupled with a coordinate system shift to account for strain. A positive conduction band offset of up to 200 meV was found for a Si-Si0.2Ge0.8 structure. We have also designed and characterized a modulation doping scheme for p-type, Ge-SiGe core-shell NWFETs. Finite element simulations of hole density versus radial position were done for different combinations of dopant position and concentration. Three modulation doped nanowire samples, each with a different boron doping density in the shell, were grown using a combined vapor-liquid-solid and chemical vapor deposition process. Low temperature current-voltage measurements of bottom- and top-gate samples indicate that hole mobility is limited by the proximity of charged impurities.Item High performance germanium nanowire field-effect transistors and tunneling field-effect transistors(2010-12) Nah, Junghyo, 1978-; Tutuc, Emanuel, 1974-; Banerjee, Sanjay K.; Lee, Jack C.; Dodabalapur, Ananth; Register, Leonard F.; Shi, LiThe scaling of metal-oxide-semiconductor (MOS) field-effect transistors (FETs) has continued for over four decades, providing device performance gains and considerable economic benefits. However, continuing this scaling trend is being impeded by the increase in dissipated power. Considering the exponential increase of the number of transistors per unit area in high speed processors, the power dissipation has now become the major challenge for device scaling, and has led to tremendous research activity to mitigate this issue, and thereby extend device scaling limits. In such efforts, non-planar device structures, high mobility channel materials, and devices operating under different physics have been extensively investigated. Non-planar device geometries reduce short-channel effects by enhancing the electrostatic control over the channel. The devices using high mobility channel materials such as germanium (Ge), SiGe, and III-V can outperform Si MOSFETs in terms of switching speed. Tunneling field-effect transistors use interband tunneling of carriers rather than thermal emission, and can potentially realize low power devices by achieving subthreshold swings below the thermal limit of 60 mV/dec at room temperature. In this work, we examine two device options which can potentially provide high switching speed combined with reduced power, namely germanium nanowire (NW) field-effect transistors (FETs) and tunneling field-effect transistors (TFETs). The devices use germanium (Ge) – silicon-germanium (Si[subscript x]Ge[subscript 1-x]) core-shell nanowires (NWs) as channel material for the realization of the devices, synthesized using a 'bottom-up' growth process. The device design and material choice are motivated by enhanced electrostatic control in the cylindrical geometry, high hole mobility, and lower bandgap by comparison to Si. We employ low energy ion implantation of boron and phosphorous to realize highly doped contact regions, which in turn provide efficient carrier injection. Our Ge-Si[subscript x]Ge[subscript 1-x] core-shell NW FETs and NW TFETs were fabricated using a conventional CMOS process and their electrical properties were systematically characterized. In addition, TCAD (Technology computer-aided design) simulation is also employed for the analysis of the devices.Item Strain and modulation doping in epitaxial Si/Ge core-shell nanowire heterostructures(2015-12) Dillen, David Carl; Tutuc, Emanuel, 1974-; Banerjee, Sanjay K; Dodabalapur, Ananth; Yu, Edward T; Korgel, Brian AFor over five decades, silicon based electronics relied on scaling of individual field-effect transistors (FETs) for improvements in integrated circuit performance. Recently, however, further enhancement of packing density and switching speed was limited by the increase in power consumption of short channel devices. New materials and device geometries were introduced to help expand CPU performance while also decreasing power dissipation. Semiconducting nanowires have also been recognized for potential applications as channel material in highly scaled FETs. These structures present opportunities for strain and energy band engineering through the use of radial, or core-shell, heterostructures. To fully exploit the benefits of radial heterostructures, however, requires knowledge of elastic strain distributions and energy band alignments, necessitating the development of new characterization methods. This is especially true in Si/Ge material systems, where a large lattice mismatch over 4% is possible. In this thesis, we grow Si/Ge core-shell nanowires and demonstrate multiple techniques to characterize the nanoscale heterostructure, including strain measurements and extraction of valence band offsets. We grow Ge-SixGe1-x core-shell nanowires and measure the elastic strain using Raman spectroscopy. The Ge core’s Raman spectrum is consistent with a compressive strain in this region due to lattice mismatch with the SixGe1-x shell. The strain distribution and expected Raman peak positions are calculated using continuum elasticity models and lattice dynamic theory, finding excellent agreement to experimental data. We also demonstrate radial modulation doping in Ge-SixGe1-x core-shell nanowire heterostructures by doping a portion of the SixGe1-x shell with boron during growth. The modulation doped nanowire FETs show an enhanced low temperature hole mobility and also a decoupling of transport between core and shell. Through comparison to finite-element calculations, we extract the valence band offset at the core-shell interface. Lastly, we grow coherently strained Si-SixGe1-x core-shell nanowires and characterize the structure using Raman spectroscopy. We first optimize the Si nanowire growth process to favor the diamond crystal structure and to minimize sidewall coverage by Au catalyst, followed by epitaxial growth of the SixGe1-x shell using the Si nanowire as substrate. Raman measurements on core-shell samples indicate a tensile strain in the Si core and a compressive strain in the SixGe1-x shell, both consistent with calculations of the strain and the strain-induced shift of the Raman peaks in this structure.Item Synthesis and characterization of nano- structured electrocatalysts for oxygen reduction reaction in fuel cells(2013-05) Cochell, Thomas Jefferson; Manthiram, ArumugamProton exchange membrane fuel cells (PEMFCs) and direct methanol fuel cells (DMFCs) are two types of low-temperature fuel cells (LTFCs) that operate at temperatures less than 100 °C and are appealing for portable, transportation, and stationary applications. However, commercialization has been hampered by several problems such as cost, efficiency, and durability. New electrocatalysts must be developed that have higher oxygen reduction reaction (ORR) activity, lower precious metal loadings, and improved durability to become commercially viable. This dissertation investigates the development and use of new electrocatalysts for the ORR. Core-shell (shell@core) Pt@Pd[subscript x]Cu[subscript y]/C electrocatalysts, with a range of initial compositions, were synthesized to result in a Pt-rich shell atop a Pd[subscript x]C[subscript y]-rich core. The interaction between core and shell resulted in a delay in the onset of Pt-OH formation, accounting in a 3.5-fold increase in Pt-mass activity compared to Pt/C. The methanol tolerance of the core-shell Pt@PdCu₅/C was found to decrease with increasing Pt-shell coverage due to the negative potential shift in the CO oxidation peak. It was discovered that Cu leached out from the cathode has a detrimental effect on membrane-electrode assembly performance. A spray-assisted impregnation method was developed to reduce particle size and increase dispersion on the support in a consistent manner for a Pd₈₈W₁₂/C electrocatalyst. The spray-assisted method resulted in decreased particle size, improved dispersion and more uniform drying compared to a conventional method. These differences resulted in greater performance during operation of a single DMFC and PEMFC. Additionally, Pd₈₈W₁₂/C prepared by spray-assisted impregnation showed DMFC performance similar to Pt/C with similar particle size in the kinetic region while offering improved methanol tolerance. Pd₈₈W₁₂/C also showed comparable maximum power densities and activities normalized by cost in a PEMFC. Lastly, the activation of aluminum as an effective reducing agent for the wet- chemical synthesis of metallic particles by pitting corrosion was explored along with the control of particle morphology. It was found that atomic hydrogen, an intermediate, was the actual reducing agent, and a wide array of metals could be produced. The particle size and dispersion of Pd/C produced using Al was controlled using PVP and FeCl₂ as stabilizers. The intermetallic Cu₂Sb was similarly prepared with a 20 nm crystallite size for potential use in lithium-ion battery anodes. Lastly, it was found that the shape of Pd produced with Al as a reducing agent could be controlled to prepare 10 nm cubes enclosed by (100) facets with potentially high activity for the ORR.Item Theoretical study of correlation between structure and function for nanoparticle catalysts(2014-12) Zhang, Liang, 1986; Henkelman, GraemeThe science and technology of catalysis is more important today than at any other time in our history due to the grand energy and environment challenges we are facing. With the explosively growth of computation power nowadays, computer simulation can play an increasingly important role in the design of new catalysts, avoiding the costly trail-and-error attempts and facilitating the development cycle. The goal to inverse design of new materials with desired catalytic property was once far off, but now achievable. The major focus of this dissertation is to find the general rules that govern the catalytic performance of a nanoparticle as the function of its structure. Three types of multi-metallic nanoparticles have been investigated in this dissertation, core-shell, random alloy and alloy-core@shell. Significant structural rearrangement was found on Au@Pt and Pd@Pt nanoparticle, which is responsible for a dramatic improvement in catalytic performance. Nonlin- ear binding trends were found and modeled for random alloy nanoparticles, providing a prescription for tuning catalytic activity through alloying. Studies of ORR on Pd/Au random alloy NP and hydrogenation reaction on Rh/Ag random alloy NP revealed that binding on individual ensemble should be in- vestigated when large disparity of adsorbate affinity is presented between two alloying elements. In the alloy-core@shell system, I demostrated a general linear correlations between the adsorbate binding energy to the shell of an alloy-core@shell nanoparticle and the composition of the core. This relation- ship allows for interpolation of the properties of single-core@shell particles and an approach for tuning the catalytic activity of the particle. A series of promising catalysts were then predicted for ORR, HER and CO oxidation. As a first attempt to bridge the material gap, bimetallic nano clus- ter supported on CeO₂(111) was investigated for CO oxidation. A strong support-metal interaction induces a preferential segregation of the more reac- tive element to the NC-CeO₂ perimeter, generating an interface with the Au component. (Au-Cu)/CeO₂ was found to be optimal for catalyzing CO oxida- tion via a bifunctional mechanism. O₂ preferentially binds to the Cu-rich sites whereas CO binds to the Au-rich sites. A method called distributed replica dynamics (DRD) is proposed at last to utilize enormous distributed computing resources for molecular dynamics simulations of rare-event in chemical reac- tions. High efficiency can be achieved with an appropriate choice of N [subscript rep] and t [subscript rep] for long-time MD simulation.