Tubular micro- and nanostructures of TCO materials grown by a vapor-solid method

Microtubes and rods with nanopipes of transparent conductive oxides (TCO), such as SnO_2, TiO_2, ZnO and In_2O_3, have been fabricated following a vapor-solid method which avoids the use of catalyst or templates. The morphology of the as-grown tubular structures varies as a function of the precursor powder and the parameters employed during the thermal treatments carried out under a controlled argon flow. These materials have been also doped with different elements of technological interest (Cr, Er, Li, Zn, Sn). Energy Dispersive X-ray Spectroscopy (EDS) measurements show that the concentration of the dopants achieved by the vapor-solid method ranges from 0.5 to _3 at.%. Luminescence of the tubes has been analyzed, with special attention paid to the influence of the dopants on their optical properties. In this work, we summarize and discuss some of the processes involved not only in the anisotropic growth of these hollow micro and nanostructures, but also in their doping.

Layered graphitic carbon host formation during liquid-free solid state growth of metal pyrophosphates

We report a successful ligand- and liquid-free solid state route to form metal pyrophosphates within a layered graphitic carbon matrix through a single step approach involving pyrolysis of previously synthesized organometallic derivatives of a cyclotriphosphazene. In this case, we show how single crystal Mn2P2O7 can be formed on either the micro- or the nanoscale in the complete absence of solvents or solutions by an efficient combustion process using rationally designed macromolecular trimer precursors, and present evidence and a mechanism for layered graphite host formation. Using in situ Raman spectroscopy, infrared spectroscopy, X-ray diffraction, high resolution electron microscopy, thermogravimetric and differential scanning calorimetric analysis, and near-edge X-ray absorption fine structure examination, we monitor the formation process of a layered, graphitic carbon in the matrix. The identification of thermally and electrically conductive graphitic carbon host formation is important for the further development of this general ligand-free synthetic approach for inorganic nanocrystal growth in the solid state, and can be extended to form a range of transition metals pyrophosphates. For important energy storage applications, the method gives the ability to form oxide and (pyro)phosphates within a conductive, intercalation possible, graphitic carbon as host–guest composites directly on substrates for high rate Li-ion battery and emerging alternative positive electrode materials

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.

Synthesis and characterization of cyclotriphosphazenes containing silicon as single solid-state precursors for the formation of silicon/phosphorus nanostructured materials

The synthesis and characterization of new organosilicon derivatives of N3P3Cl6, N3P3[NH(CH2)3Si(OEt)3]6 (1), N3P3[NH(CH2)3Si(OEt)3]3[NCH3(CH2)3CN]3 (2), and N3P3[NH(CH2)3Si(OEt)3]3[HOC6H4(CH2)CN]3 (3) are reported. Pyrolysis of 1, 2, and 3 in air and at several temperatures results in nanostructured materials whose composition and morphology depend on the temperature of pyrolysis and the substituents of the phosphazenes ring. The products stem from the reaction of SiO2 with P2O5, leading to either crystalline Si5(PO4)6O, SiP2O7 or an amorphous phase as the glass Si5(PO4)6O/3SiO2·2P2O5, depending on the temperature and nature of the trimer precursors. From 1 at 800 °C, core−shell microspheres of SiO2 coated with Si5(PO4)6O are obtained, while in other cases, mesoporous or dense structures are observed. Atomic force microscopy examination after deposition of the materials on monocrystalline silicon wafers evidences morphology strongly dependent on the precursors. Isolated islands of size ∼9 nm are observed from 1, whereas dense nanostructures with a mean height of 13 nm are formed from 3. Brunauer−Emmett−Teller measurements show mesoporous materials with low surface areas. The proposed growth mechanism involves the formation of cross-linking structures and of vacancies by carbonization of the organic matter, where the silicon compounds nucleate. Thus, for the first time, unique silicon nanostructured materials are obtained from cyclic phosphazenes containing silicon.

Simultaneous observation of current oscillations and porous film growth during anodization of InP

The observation of spontaneous oscillations in current during the anodization of InP in relatively high concentrations of KOH electrolytes is reported. Oscillations were observed under potential sweep and constant potential conditions. Well-defined oscillations are observed during linear potential sweeps of InP in 5 mol dm-3 KOH to potentials above ∼1.7 V (SCE) at scan rates in the range of 50 to 500 mV s-1. The oscillations observed exhibit an asymmetrical current versus potential profile, and the charge per cycle was found to increase linearly with potential. More complex oscillatory behavior was observed under constant potential conditions. Periodic damped oscillations are observed in high concentrations of electrolyte whereas undamped sinusoidal oscillations are observed in relatively lower concentrations. In both cases, the anodization of InP results in porous InP formation, and the current in the oscillatory region corresponds to the cyclical effective area changes due to pitting dissolution of the InP surface with the coincidental growth of a thick porous In2O3 film.

Epitaxial growth of visible to infra-red transparent conducting In2O3 nanodot dispersions and reversible charge storage as a Li-ion battery anode

Unique bimodal distributions of single crystal epitaxially grown In2O3 nanodots on silicon are shown to have excellent IR transparency greater than 87% at IR wavelengths up to 4 μm without sacrificing transparency in the visible region. These broadband antireflective nanodot dispersions are grown using a two-step metal deposition and oxidation by molecular beam epitaxy, and backscattered diffraction confirms a dominant (111) surface orientation. We detail the growth of a bimodal size distribution that facilitates good surface coverage (80%) while allowing a significant reduction in In2O3 refractive index. This unique dispersion offers excellent surface coverage and three-dimensional volumetric expansion compared to a thin film, and a step reduction in refractive index compared to bulk active materials or randomly porous composites, to more closely match the refractive index of an electrolyte, improving transparency. The (111) surface orientation of the nanodots, when fully ripened, allows minimum lattice mismatch strain between the In2O3 and the Si surface. This helps to circumvent potential interfacial weakening caused by volume contraction due to electrochemical reduction to lithium, or expansion during lithiation. Cycling under potentiodynamic conditions shows that the transparent anode of nanodots reversibly alloys lithium with good Coulombic efficiency, buffered by co-insertion into the silicon substrate. These properties could potentially lead to further development of similarly controlled dispersions of a range of other active materials to give transparent battery electrodes or materials capable of non-destructive in situ spectroscopic characterization during charging and discharging.

Growth, Characterization, and Properties of Hybrid Graphene-Carbon Nanotube Films and Related Carbon Nanostructures

Graphene, first isolated in 2004 and the subject of the 2010 Nobel Prize in physics, has generated a tremendous amount of research interest in recent years due to its incredible mechanical and electrical properties. However, difficulties in large-scale production and low as-prepared surface area have hindered commercial applications. In this dissertation, a new material is described incorporating the superior electrical properties of graphene edge planes into the high surface area framework of carbon nanotube forests using a scalable and reproducible technology.

The objectives of this research were to investigate the growth parameters and mechanisms of a graphene-carbon nanotube hybrid nanomaterial termed “graphenated carbon nanotubes” (g-CNTs), examine the applicability of g-CNT materials for applications in electrochemical capacitors (supercapacitors) and cold-cathode field emission sources, and determine materials characteristics responsible for the superior performance of g-CNTs in these applications. The growth kinetics of multi-walled carbon nanotubes (MWNTs), grown by plasma-enhanced chemical vapor deposition (PECVD), was studied in order to understand the fundamental mechanisms governing the PECVD reaction process. Activation energies and diffusivities were determined for key reaction steps and a growth model was developed in response to these findings. Differences in the reaction kinetics between CNTs grown on single-crystal silicon and polysilicon were studied to aid in the incorporation of CNTs into microelectromechanical systems (MEMS) devices. To understand processing-property relationships for g-CNT materials, a Design of Experiments (DOE) analysis was performed for the purpose of determining the importance of various input parameters on the growth of g-CNTs, finding that varying temperature alone allows the resultant material to transition from CNTs to g-CNTs and finally carbon nanosheets (CNSs): vertically oriented sheets of few-layered graphene. In addition, a phenomenological model was developed for g-CNTs. By studying variations of graphene-CNT hybrid nanomaterials by Raman spectroscopy, a linear trend was discovered between their mean crystallite size and electrochemical capacitance. Finally, a new method for the calculation of nanomaterial surface area, more accurate than the standard BET technique, was created based on atomic layer deposition (ALD) of titanium oxide (TiO2).

Experimental analysis of novel telecom source materials and devices

Incumbent telecommunication lasers emitting at 1.5 µm are fabricated on InP substrates and consist of multiple strained quantum well layers of the ternary alloy InGaAs, with barriers of InGaAsP or InGaAlAs. These lasers have been seen to exhibit very strong temperature dependence of the threshold current. This strong temperature dependence leads to a situation where external cooling equipment is required to stabilise the optical output power of these lasers. This results in a significant increase in the energy bill associated with telecommunications, as well as a large increase in equipment budgets. If the exponential growth trend of end user bandwidth demand associated with the internet continues, these inefficient lasers could see the telecommunications industry become the dominant consumer of world energy. For this reason there is strong interest in developing new, much more efficient telecommunication lasers. One avenue being investigated is the development of quantum dot lasers on InP. The confinement experienced in these low dimensional structures leads to a strong perturbation of the density of states at the band edge, and has been predicted to result in reduced temperature dependence of the threshold current in these devices. The growth of these structures is difficult due to the large lattice mismatch between InP and InAs; however, recently quantum dots elongated in one dimension, known as quantum dashes, have been demonstrated. Chapter 4 of this thesis provides an experimental analysis of one of these quantum dash lasers emitting at 1.5 µm along with a numerical investigation of threshold dynamics present in this device. Another avenue being explored to increase the efficiency of telecommunications lasers is bandstructure engineering of GaAs-based materials to emit at 1.5 µm. The cause of the strong temperature sensitivity in InP-based quantum well structures has been shown to be CHSH Auger recombination. Calculations have shown and experiments have verified that the addition of bismuth to GaAs strongly reduces the bandgap and increases the spin orbit splitting energy of the alloy GaAs1−xBix. This leads to a bandstructure condition at x = 10 % where not only is 1.5 µm emission achieved on GaAs-based material, but also the bandstructure of the material can naturally suppress the costly CHSH Auger recombination which plagues InP-based quantum-well-based material. It has been predicted that telecommunications lasers based on this material system should operate in the absence of external cooling equipment and offer electrical and optical benefits over the incumbent lasers. Chapters 5, 6, and 7 provide a first analysis of several aspects of this material system relevant to the development of high bismuth content telecommunication lasers.

MOVPE growth and characterization of Al(Ga)N and InAlN/AlGaN quantum wells for UV LED applications

The study of III-nitride materials (InN, GaN and AlN) gained huge research momentum after breakthroughs in the production light emitting diodes (LEDs) and laser diodes (LDs) over the past two decades. Last year, the Nobel Prize in Physics was awarded jointly to Isamu Akasaki, Hiroshi Amano and Shuji Nakamura for inventing a new energy efficient and environmental friendly light source: blue light-emitting diode (LED) from III-nitride semiconductors in the early 1990s. Nowadays, III-nitride materials not only play an increasingly important role in the lighting technology, but also become prospective candidates in other areas, for example, the high frequency (RF) high electron mobility transistor (HEMT) and photovoltaics. These devices require the growth of high quality III-nitride films, which can be prepared using metal organic vapour phase epitaxy (MOVPE). The main aim of my thesis is to study and develop the growth of III-nitride films, including AlN, u-AlGaN, Si-doped AlGaN, and InAlN, serving as sample wafers for fabrication of ultraviolet (UV) LEDs, in order to replace the conventional bulky, expensive and environmentally harmful mercury lamp as new UV light sources. For application to UV LEDs, reducing the threading dislocation density (TDD) in AlN epilayers on sapphire substrates is a key parameter for achieving high-efficiency AlGaNbased UV emitters. In Chapter 4, after careful and systematic optimisation， a working set of conditions, the screw and edge type dislocation density in the AlN were reduced to around 2.2×108 cm-2 and 1.3×109 cm-2 , respectively, using an optimized three-step process, as estimated by TEM. An atomically smooth surface with an RMS roughness of around 0.3 nm achieved over 5×5 µm 2 AFM scale. Furthermore, the motion of the steps in a one dimension model has been proposed to describe surface morphology evolution, especially the step bunching feature found under non-optimal conditions. In Chapter 5, control of alloy composition and the maintenance of compositional uniformity across a growing epilayer surface were demonstrated for the development of u-AlGaN epilayers. Optimized conditions (i.e. a high growth temperature of 1245 °C) produced uniform and smooth film with a low RMS roughness of around 2 nm achieved in 20×20 µm 2 AFM scan. The dopant that is most commonly used to obtain n-type conductivity in AlxGa1-xN is Si. However, the incorporation of Si has been found to increase the strain relaxation and promote unintentional incorporation of other impurities (O and C) during Si-doped AlGaN growth. In Chapter 6, reducing edge-type TDs is observed to be an effective appoach to improve the electric and optical properties of Si-doped AlGaN epilayers. In addition, the maximum electron concentration of 1.3×1019 cm-3 and 6.4×1018 cm-3 were achieved in Si-doped Al0.48Ga0.52N and Al0.6Ga0.4N epilayers as measured using Hall effect. Finally, in Chapter 7, studies on the growth of InAlN/AlGaN multiple quantum well (MQW) structures were performed, and exposing InAlN QW to a higher temperature during the ramp to the growth temperature of AlGaN barrier (around 1100 °C) will suffer a significant indium (In) desorption. To overcome this issue, quasi-two-tempeature (Q2T) technique was applied to protect InAlN QW. After optimization, an intense UV emission from MQWs has been observed in the UV spectral range from 320 to 350 nm measured by room temperature photoluminescence.

On the microstructure, growth pattern and original porosity of belemnite rostra: insights from calcitic Jurassic belemnites

Calcitic belemnite rostra are usually employed to perform paleoenvironmental studies based on geochemical data. However, several questions, such as their original porosity and microstructure, remain open, despite they are essential to make accurate interpretations based on geochemical analyses.This paper revisits and enlightens some of these questions. Petrographic data demonstrate that calcite crystals of the rostrum solidum of belemnites grow from spherulites that successively develop along the apical line, resulting in a “regular spherulithic prismatic” microstructure. Radially arranged calcite crystals emerge and diverge from the spherulites: towards the apex, crystals grow until a new spherulite is formed; towards the external walls of the rostrum, the crystals become progressively bigger and prismatic. Adjacent crystals slightly vary in their c-axis orientation, resulting in undulose extinction. Concentric growth layering develops at different scales and is superimposed and traversed by a radial pattern, which results in the micro-fibrous texture that is observed in the calcite crystals in the rostra.Petrographic data demonstrate that single calcite crystals in the rostra have a composite nature, which strongly suggests that the belemnite rostra were originally porous. Single crystals consistently comprise two distinct zones or sectors in optical continuity: 1) the inner zone is fluorescent, has relatively low optical relief under transmitted light (TL) microscopy, a dark-grey color under backscatter electron microscopy (BSEM), a commonly triangular shape, a “patchy” appearance and relatively high Mg and Na contents; 2) the outer sector is non-fluorescent, has relatively high optical relief under TL, a light-grey color under BSEM and low Mg and Na contents. The inner and fluorescent sectors are interpreted to have formed first as a product of biologically controlled mineralization during belemnite skeletal growth and the non-fluorescent outer sectors as overgrowths of the former, filling the intra- and inter-crystalline porosity. This question has important implications for making paleoenvironmental and/or paleoclimatic interpretations based on geochemical analyses of belemnite rostra.Finally, the petrographic features of composite calcite crystals in the rostra also suggest the non-classical crystallization of belemnite rostra, as previously suggested by other authors.

Crack propagation in non-homogenous materials: Evaluation of mixed-mode SIFs, T-stress and kinking angle using a variant EFG method

A new variant of the Element-Free Galerkin (EFG) method, that combines the diffraction method, to characterize the crack tip solution, and the Heaviside enrichment function for representing discontinuity due to a crack, has been used to model crack propagation through non-homogenous materials. In the case of interface crack propagation, the kink angle is predicted by applying the maximum tangential principal stress (MTPS) criterion in conjunction with consideration of the energy release rate (ERR). The MTPS criterion is applied to the crack tip stress field described by both the stress intensity factor (SIF) and the T-stress, which are extracted using the interaction integral method. The proposed EFG method has been developed and applied for 2D case studies involving a crack in an orthotropic material, crack along an interface and a crack terminating at a bi-material interface, under mechanical or thermal loading; this is done to demonstrate the advantages and efficiency of the proposed methodology. The computed SIFs, T-stress and the predicted interface crack kink angles are compared with existing results in the literature and are found to be in good agreement. An example of crack growth through a particle-reinforced composite materials, which may involve crack meandering around the particle, is reported.

Epitaxial growth of molecular crystals on van der Waals substrates for high-performance organic electronics

Epitaxial van der Waals (vdW) heterostructures of organic and layered materials are demonstrated to create high-performance organic electronic devices. High-quality rubrene films with large single-crystalline domains are grown on h-BN dielectric layers via vdW epitaxy. In addition, high carrier mobility comparable to free-standing single-crystal counterparts is achieved by forming interfacial electrical contacts with graphene electrodes.

Device Physics of Two-Dimensional Crystalline Materials

Thesis (Ph.D.)--University of Washington, 2016-07

Growth and application of planar III-V semiconductor nanowires grown with MOCVD

The semiconductor nanowire has been widely studied over the past decade and identified as a promising nanotechnology building block with application in photonics and electronics. The flexible bottom-up approach to nanowire growth allows for straightforward fabrication of complex 1D nanostructures with interesting optical, electrical, and mechanical properties. III-V nanowires in particular are useful because of their direct bandgap, high carrier mobility, and ability to form heterojunctions and have been used to make devices such as light-emitting diodes, lasers, and field-effect transistors. However, crystal defects are widely reported for III-V nanowires when grown in the common out-of-plane <111>B direction. Furthermore, commercialization of nanowires has been limited by the difficulty of assembling nanowires with predetermined position and alignment on a wafer-scale. In this thesis, planar III-V nanowires are introduced as a low-defect and integratable nanotechnology building block grown with metalorganic chemical vapor deposition. Planar GaAs nanowires grown with gold seed particles self-align along the <110> direction on the (001) GaAs substrate. Transmission electron microscopy reveals that planar GaAs nanowires are nearly free of crystal defects and grow laterally and epitaxially on the substrate surface. The nanowire morphology is shown to be primarily controlled through growth temperature and an ideal growth window of 470 +\- 10 °C is identified for planar GaAs nanowires. Extension of the planar growth mode to other materials is demonstrated through growth of planar InAs nanowires. Using a sacrificial layer, the transfer of planar GaAs nanowires onto silicon substrates with control over the alignment and position is presented. A metal-semiconductor field-effect transistor fabricated with a planar GaAs nanowire shows bulk-like low-field electron transport characteristics with high mobility. The aligned planar geometry and excellent material quality of planar III-V nanowires may lead to highly integrated III-V nanophotonics and nanoelectronics.