A multi-scale approach to shaping carbon nanotube structures for hollow microneedles

The concept of a carbon nanotube microneedle array is explored in this thesis from multiple perspectives including microneedle fabrication, physical aspects of transdermal delivery, and in vivo transdermal drug delivery experiments. Starting with standard techniques in carbon nanotube (CNT) fabrication, including catalyst patterning and chemical vapor deposition, vertically-aligned carbon nanotubes are utilized as a scaffold to define the shape of the hollow microneedle. Passive, scalable techniques based on capillary action and unique photolithographic methods are utilized to produce a CNT-polymer composite microneedle. Specific examples of CNT-polyimide and CNT-epoxy microneedles are investigated. Further analysis of the transport properties of polymer resins reveals general requirements for applying arbitrary polymers to the fabrication process.

The bottom-up fabrication approach embodied by vertically-aligned carbon nanotubes allows for more direct construction of complex high-aspect ratio features than standard top-down fabrication approaches, making microneedles an ideal application for CNTs. However, current vertically-aligned CNT fabrication techniques only allow for the production of extruded geometries with a constant cross-sectional area, such as cylinders. To rectify this limitation, isotropic oxygen etching is introduced as a novel fabrication technique to create true 3D CNT geometry. Oxygen etching is utilized to create a conical geometry from a cylindrical CNT structure as well as create complex shape transformations in other CNT geometries.

CNT-polymer composite microneedles are anchored onto a common polymer base less than 50 µm thick, which allows for the microneedles to be incorporated into multiple drug delivery platforms, including modified hypodermic syringes and silicone skin patches. Cylindrical microneedles are fabricated with 100 µm outer diameter and height of 200-250 µm with a central cavity, or lumen, diameter of 30 µm to facilitate liquid drug flow. In vitro delivery experiments in swine skin demonstrate the ability of the microneedles to successfully penetrate the skin and deliver aqueous solutions.

An in vivo study was performed to assess the ability of the CNT-polymer microneedles to deliver drugs transdermally. CNT-polymer microneedles are attached to a hand actuated silicone skin patch that holds a liquid reservoir of drugs. Fentanyl, a potent analgesic, was administered to New Zealand White Rabbits through 3 routes of delivery: topical patch, CNT-polymer microneedles, and subcutaneous hypodermic injection. Results demonstrate that the CNT-polymer microneedles have a similar onset of action as the topical patch. CNT-polymer microneedles were also vetted as a painless delivery approach compared to hypodermic injection. Comparative analysis with contemporary microneedle designs demonstrates that the delivery achieved through CNT-polymer microneedles is akin to current hollow microneedle architectures. The inherent advantage of applying a bottom-up fabrication approach alongside similar delivery performance to contemporary microneedle designs demonstrates that the CNT-polymer composite microneedle is a viable architecture in the emerging field of painless transdermal delivery.

1.55-mu m InGaAs/InGaAlAs MQW vertical-cavity surface-emitting lasers with InGaAlAs/InP distributed Bragg reflectors

High-performance InGaAs/InGaAlAs multiple-quantum-well vertical-cavity surface-emitting lasers (VCSELs) with lnGaAlAs/InP distributed Bragg reflectors are proposed for operation at the wavelength of 1.55 mum. The lasers have good heat diffusion characteristic, large index contrast in DBRs, and weak temperature sensitivity. They could be fabricated either by metal-organic chemical vapor deposition (MOCVD) or by molecular beam epitaxy (MBE) growth. The laser light-current characteristics indicate that a suitable reflectivity of the DBR on the light output side in a laser makes its output power increase greatly and its lasing threshold current reduce significantly, and that a small VCSEL could output the power around its maximum for the output mirror at the reflectivity varying in a broader range than a large VCSEL does. (C) 2004 Elsevier Ltd. All rights reserved.

Heteroepitaxy of Group IV and Group III-V semiconductor alloys for photovoltaic applications

Photovoltaic energy conversion represents a economically viable technology for realizing collection of the largest energy resource known to the Earth -- the sun. Energy conversion efficiency is the most leveraging factor in the price of energy derived from this process. This thesis focuses on two routes for high efficiency, low cost devices: first, to use Group IV semiconductor alloy wire array bottom cells and epitaxially grown Group III-V compound semiconductor alloy top cells in a tandem configuration, and second, GaP growth on planar Si for heterojunction and tandem cell applications.

Metal catalyzed vapor-liquid-solid grown microwire arrays are an intriguing alternative for wafer-free Si and SiGe materials which can be removed as flexible membranes. Selected area Cu-catalyzed vapor-liquid solid growth of SiGe microwires is achieved using chlorosilane and chlorogermane precursors. The composition can be tuned up to 12% Ge with a simultaneous decrease in the growth rate from 7 to 1 μm/min^-1. Significant changes to the morphology were observed, including tapering and faceting on the sidewalls and along the lengths of the wires. Characterization of axial and radial cross sections with transmission electron microscopy revealed no evidence of defects at facet corners and edges, and the tapering is shown to be due to in-situ removal of catalyst material during growth. X-ray diffraction and transmission electron microscopy reveal a Ge-rich crystal at the tip of the wires, strongly suggesting that the Ge incorporation is limited by the crystallization rate.

Tandem Ga_1-xIn_xP/Si microwire array solar cells are a route towards a high efficiency, low cost, flexible, wafer-free solar technology. Realizing tandem Group III-V compound semiconductor/Si wire array devices requires optimization of materials growth and device performance. GaP and Ga_1-xIn_xP layers were grown heteroepitaxially with metalorganic chemical vapor deposition on Si microwire array substrates. The layer morphology and crystalline quality have been studied with scanning electron microscopy and transmission electron microscopy, and they provide a baseline for the growth and characterization of a full device stack. Ultimately, the complexity of the substrates and the prevalence of defects resulted in material without detectable photoluminescence, unsuitable for optoelectronic applications.

Coupled full-field optical and device physics simulations of a Ga_0.51In_0.49P/Si wire array tandem are used to predict device performance. A 500 nm thick, highly doped "buffer" layer between the bottom cell and tunnel junction is assumed to harbor a high density of lattice mismatch and heteroepitaxial defects. Under simulated AM1.5G illumination, the device structure explored in this work has a simulated efficiency of 23.84% with realistic top cell SRH lifetimes and surface recombination velocities. The relative insensitivity to surface recombination is likely due to optical generation further away from the free surfaces and interfaces of the device structure.

Finally, GaP has been grown free of antiphase domains on Si (112) oriented substrates using metalorganic chemical vapor deposition. Low temperature pulsed nucleation is followed by high temperature continuous growth, yielding smooth, specular thin films. Atomic force microscopy topography mapping showed very smooth surfaces (4-6 Å RMS roughness) with small depressions in the surface. Thin films (~ 50 nm) were pseudomorphic, as confirmed by high resolution x-ray diffraction reciprocal space mapping, and 200 nm thick films showed full relaxation. Transmission electron microscopy showed no evidence of antiphase domain formation, but there is a population of microtwin and stacking fault defects.

国产掺镱双包层光纤的激光特性

采用MCVD方法研发了掺镱双包层光纤，并对其结构特性、荧光特性和激光特性进行了测试和研究。其D形内包层尺寸为400／450μm，数值孔径为0．36，纤芯直径约为16μm，数值孔径约为0．18。荧光谱线的范围为1000-1140nm，1030nm处的峰宽大于50nm。采用大功率激光二极管单端泵浦6m长的双包层光纤，在泵浦人纤功率为61W时，获得了32W的激光输出，斜率效率为64％。该光纤在高功率处未发现饱和现象，通过优化光纤参数与泵浦方式还可以提高转化效率和输出功率。实验表明该光纤可以取代进口光纤用作高功率

Electronic properties of graphene grain boundaries

Grain boundaries and defect lines in graphene are intensively studied for their novel electronic and magnetic properties. However, there is not a complete comprehension of the appearance of localized states along these defects. Graphene grain boundaries are herein seen as the outcome of matching two semi-infinite graphene sheets with different edges. We classify the energy spectra of grain boundaries into three different types, directly related to the combination of the four basic classes of spectra of graphene edges. From the specific geometry of the grains, we are able to obtain the band structure and the number of localized states close to the Fermi energy. This provides a new understanding of states localized at grain boundaries, showing that they are derived from the edge states of graphene. Such knowledge is crucial for the ultimate tailoring of electronic and optoelectronic applications.

Effects of sapphire substrate annealing on ZnO epitaxial films grown by MOCVD

The annealing effects of sapphire substrate on the quality of epitaxial ZnO films grown by metalorganic chemical vapor deposition (MOCVD) were studied. The atomic steps formed on (0 0 0 1) sapphire (alpha-Al2O3) substrate surface by annealing at high temperature was analyzed by atomic force microscopy (AFM). The annealing effects of sapphire substrate on the ZnO films were examined by X-ray diffraction (XRD), AFM and photoluminescence (PL) measurements. Experimental results indicate that the film quality is strongly affected by annealing treatment of the sapphire substrate surface., The optimum annealing temperature of sapphire substrates is given. (c) 2006 Elsevier B.V. All rights reserved.

MOCVD growth and properties of ZnO thin films on LiNbO3 substrates

ZnO thin films were grown on (0001)LiNbO3 substrates by the MOCVD technique. The substrate temperatures during growth were changed from 400 to 600 degrees C. The X-ray diffraction (XRD) pattern of the ZnO film showed a strong [002] reflection peak, and the peak intensity was dependent on substrate temperature. The ZnO columnar grains were highly oriented along the (002) direction when the film processing temperature was 600 degrees C. The optical transmission and PL results also indicated that highest crystalline quality of the ZnO films could be obtained at elevated temperatures. (c) 2005 Elsevier B.V. All rights reserved.

Annealing effect on properties of ZnO thin films grown on LiNbO3 substrates by MOCVD

ZnO films were grown on (0 0 0 1) LiNbO3 substrates by metal organic chemical vapor deposition (MOCVD). Annealing of ZnO films was performed in air for I h at 800 degrees C. The effects of annealing on the structural and optical properties of ZnO thin films on LiNbO3 substrates were investigated using X-ray diffraction (XRD), atomic force microscopy (AFM) and photoluminescence (PL) measurements. XRD patterns and AFM showed that the as-grown and the annealed ZnO films grown on LiNbO3 substrates had c-axis preferential orientation, the crystallinity of the ZnO films grown on LiNbO3 Substrates was improved, and the grain size increased by annealing. The PL spectra showed that the intensity of the UV near-band-edge peak was increased after annealing, while the intensity of visible peak (deep-level emission) decreased. (c) 2005 Elsevier B.V. All rights reserved.

Study on the hydrolytic property and thermal stability of LiAlO2 substrate

The hydrolytic property and thermal stability of LiAlO2 (LAO), important factors for its application, were examined by AFM and X-ray rocking curve. We found that H2O may be deleterious for LAO surface polishing when the root mean square (RMS) value is less than 1 nm. However, when the RMS value is more than 1 nm it may be useful for LAO polishing. (100)-plane LAO substrates are annealed in the range of 850-900 degrees C in flux N-2, Slick AlN layer probably is produced on the substrate surface. M-plane GaN layer has grown on the substrate by metal-organic chemical vapor deposition (MOCVD) method. Theses results show that LiAlO2 crystal is a promising substrate of fabricating high-efficiency LEDs by MOCVD. (c) 2006 Elsevier B.V. All rights reserved.

Nonpolar m-plane thin film GaN and InGaN/GaN light-emitting diodes on LiAlO2(100) substrates

The nonpolar m-plane (1 (1) over bar 00) thin film GaN and InGaN/GaN light-emitting diodes (LEDs) grown by metal-organic chemical vapor deposition on LiAlO2 (100) substrates are reported. The LEDs emit green light with output power of 80 mu W under a direct current of 20 mA for a 400x400 mu m(2) device. The current versus voltage (I-V) characteristic of the diode shows soft rectifying properties caused by defects and impurities in the p-n junction. The electroluminescence peak wavelength dependence on injection current, for currents in excess of 20 mA, saturates at 515-516 nm. This proves the absence of polarization fields in the active region present in c-plane structures. The light output intensity versus current (L-I) characteristic of the diode exhibits a superlinear relation at low injection current caused by nonradiative centers providing a shunt path and a linear light emission zone at high current level when these centers are saturated. (c) 2007 American Institute of Physics.

Anisotropic crystallographic properties, strain, and their effects on band structure of m -plane GaN on LiAlO2 (100)

The m-plane GaN films grown on LiAlO2(100) by metal-organic chemical vapor deposition exhibit anisotropic crystallographic properties. The Williamson-Hall plots point out they are due to the different tilts and lateral correlation lengths of mosaic blocks parallel and perpendicular to GaN[0001] in the growth plane. The symmetric and asymmetric reciprocal space maps reveal the strain of m-plane GaN to be biaxial in-plane compress epsilon(xx)=-0.79% and epsilon(zz)=-0.14% with an out-of-plane dilatation epsilon(yy)=0.38%. This anisotropic strain further separates the energy levels of top valence band at Gamma point. The energy splitting as 37 meV as well as in-plane polarization anisotropy for transitions are found by the polarized photoluminescence spectra at room temperature. (c) 2008 American Institute of Physics.

In situ characterization of alloy catalysts for low-temperature graphene growth.

Low-temperature (∼450 °C), scalable chemical vapor deposition of predominantly monolayer (74%) graphene films with an average D/G peak ratio of 0.24 and domain sizes in excess of 220 μm(2) is demonstrated via the design of alloy catalysts. The admixture of Au to polycrystalline Ni allows a controlled decrease in graphene nucleation density, highlighting the role of step edges. In situ, time-, and depth-resolved X-ray photoelectron spectroscopy and X-ray diffraction reveal the role of subsurface C species and allow a coherent model for graphene formation to be devised.

Efficient carbon nanotube field emitter using electrospun carbon nanofibers as a flexible electrode

Thermal-stable, conductive, and flexible carbon fabric (CF), which is composed of thin carbon fibers prepared by electrospinning, was used for the substrate of carbon nanotube (CNT) field emitter arrays. The field emitter arrays were prepared by chemical vapor deposition (CVD). The current density-electric field characteristics revealed that the CNT field emitter arrays on CF produced a higher current density at a lower turn-on voltage compared to ones on a Si substrate. This emitter integrated with a gate electrode based on hierarchy-structured carbon materials, CNTs on CF, can be used for light sources, displays, and other electronic devices. © 2009 Materials Research Society.

Field emission properties of single-walled carbon nanotubes with a variety of emitter morphologies

Field emission properties of single-walled carbon nanotubes (SWCNTs), which were prepared through alcohol catalytic chemical vapor deposition for 10-60s, were characterized in a diode configuration. Protrusive bundles at the top surface of samples act selectively as emission sites. The number of emission sites was controlled by emitter morphologies combined with texturing of Si substrates. SWCNTs grown on a textured Si substrate exhibited a turn-on field as low as 2.4 V/μm at a field emission current density of 1 μA/cm 2. Uniform spatial luminescence (0.5 cm2) from the rear surface of the anode was revealed for SWCNTs prepared on the textured Si substrate. Deterioration of field emission properties through repetitive measurements was reduced for the textured samples in comparison with vertically aligned SWCNTs and a random network of SWCNTs prepared on flat Si substrates. Emitter morphology resulting in improved field emission properties is a crucial factor for the fabrication of SWCNT-electron sources. Morphologically controlled SWCNTs with promising emitter performance are expected to be practical electron sources. © 2008 The Japan Society of Applied Physics.

A simple combinatorial method aiding research on single-walled carbon nanotube growth on substrates

Establishing fabrication methods of carbon nanotubes (CNTs) is essential to realize many applications expected for CNTs. Catalytic growth of CNTs on substrates by chemical vapor deposition (CVD) is promising for direct fabrication of CNT devices, and catalyst nanoparticles play a crucial role in such growth. We have developed a simple method called "combinatorial masked deposition (CMD)", in which catalyst particles of a given series of sizes and compositions are formed on a single substrate by annealing gradient catalyst layers formed by sputtering through a mask. CMD enables preparation of hundreds of catalysts on a wafer, growth of single-walled CNTs (SWCNTs), and evaluation of SWCNT diameter distributions by automated Raman mapping in a single day. CMD helps determinations of the CVD and catalyst windows realizing millimeter-tall SWCNT forest growth in 10 min, and of growth curves for a series of catalysts in a single measurement when combined with realtime monitoring. A catalyst library prepared using CMD yields various CNTs, ranging from individuals, networks, spikes, and to forests of both SWCNTs and multi-walled CNTs, and thus can be used to efficiently evaluate self-organized CNT field emitters, for example. The CMD method is simple yet effective for research of CNT growth methods. © 2010 The Japan Society of Applied Physics.