Endothelialization of sirolimus-eluting stents with slow and extended drug release in the porcine overstretch model

BACKGROUND: Vascular healing of intracoronary stents has been shown to be delayed in drug-eluting stents (DES) due to the cytotoxic compounds on the stent surface that prevent stent ingrowth and endothelialization. The lack of endothelialization explains the occurrence of late and very late stent thrombosis in DES. MATERIALS AND METHODS: In 11 house swines (body weight 38-45 kg), 3 stents were implanted randomly into the 3 large epicardial coronary arteries, namely a bare-metal stent (BMS), a sirolimus-eluting stent with slow-release (SES) and a SES with extended-release (SESXR). Stent length was 18 mm, and stent diameter 3 mm. All stents were of identical design. Animals were followed for 3 (n = 3), 7 (n = 4) and 14 (n = 4) days, respectively. One animal died before implantation due to hyperthermia. On the day of explantation, the animals were euthanized and endothelialization was tested by scanning electron microscopy after drying and sputtering the samples. Endothelial coverage was determined semiquantitatively by 2 observers. RESULTS: Endothelialization was more rapid with BMS and SESXR than SES at 3 and 14 days. At 7 days there were no significant differences between the 2 SES. CONCLUSIONS: Endothelialization of intracoronary stents is faster with BMS and SESXR at 3 days than with SES. These differences persist at 14 days, suggesting delayed vascular healing with the slow-release SES.

RF-sputter fabrication of magnetic garnet thin films and simulation modeling for 1-D magnetic photonic crystal waveguide devices

One dimensional magnetic photonic crystals (1D-MPC) are promising structures for integrated optical isolator applications. Rare earth substituted garnet thin films with proper Faraday rotation are required to fabricate planar 1D-MPCs. In this thesis, flat-top response 1D-MPC was proposed and spectral responses and Faraday rotation were modeled. Bismuth substituted iron garnet films were fabricated by RF magnetron sputtering and structures, compositions, birefringence and magnetooptical properties were studied. Double layer structures for single mode propagation were also fabricated by sputtering for the first time. Multilayer stacks with multiple defects (phase shift) composed of Ce-YIG and GGG quarter-wave plates were simulated by the transfer matrix method. The transmission and Faraday rotation characteristics were theoretically studied. It is found that flat-top response, with 100% transmission and near 45o rotation is achievable by adjusting the inter-defect spacing, for film structures as thin as 30 to 35 μm. This is better than 3-fold reduction in length compared to the best Ce-YIG films for comparable rotations, thus allows a considerable reduction in size in manufactured optical isolators. Transmission bands as wide as 7nm were predicted, which is considerable improvement over 2 defects structure. Effect of repetition number and ratio factor on transmission and Faraday rotation ripple factors for the case of 3 and 4 defects structure has been discussed. Diffraction across the structure corresponds to a longer optical path length. Thus the use of guided optics is required to minimize the insertion losses in integrated devices. This part is discussed in chapter 2 in this thesis. Bismuth substituted iron garnet thin films were prepared by RF magnetron sputtering. We investigated or measured the deposition parameters optimization, crystallinity, surface morphologies, composition, magnetic and magnetooptical properties. A very high crystalline quality garnet film with smooth surface has been heteroepitaxially grown on (111) GGG substrate for films less than 1μm. Dual layer structures with two distinct XRD peaks (within a single sputtered film) start to develop when films exceed this thickness. The development of dual layer structure was explained by compositional gradient across film thickness, rather than strain gradient proposed by other authors. Lower DC self bias or higher substrate temperature is found to help to delay the appearance of the 2nd layer. The deposited films show in-plane magnetization, which is advantageous for waveguide devices application. Propagation losses of fabricated waveguides can be decreased by annealing in an oxygen atmosphere from 25dB/cm to 10dB/cm. The Faraday rotation at λ=1.55μm were also measured for the waveguides. FR is small (10° for a 3mm long waveguide), due to the presence of linear birefringence. This part is covered in chapter 4. We also investigated the elimination of linear birefringence by thickness tuning method for our sputtered films. We examined the compressively and tensilely strained films and analyze the photoelastic response of the sputter deposited garnet films. It has been found that the net birefringence can be eliminated under planar compressive strain conditions by sputtering. Bi-layer GGG on garnet thin film yields a reduced birefringence. Temperature control during the sputter deposition of GGG cover layer is critical and strongly influences the magnetization and birefringence level in the waveguide. High temperature deposition lowers the magnetization and increases the linear birefringence in the garnet films. Double layer single mode structures fabricated by sputtering were also studied. The double layer, which shows an in-plane magnetization, has an increased RMS roughness upon upper layer deposition. The single mode characteristic was confirmed by prism coupler measurement. This part is discussed in chapter 5.

Immobilizing bacteriorhodopsin on a single electron transistor

As awareness of potential human and environmental impacts from toxins has increased, so has the development of innovative sensors. Bacteriorhodopsin (bR) is a light activated proton pump contained in the purple membrane (PM) of the bacteria Halobacterium salinarum. Bacteriorhodopsin is a robust protein which can function in both wet and dry states and can withstand extreme environmental conditions. A single electron transistor(SET) is a nano-scale device that exploits the quantum mechanical properties of electrons to switch on and off. SETs have tremendous potential in practical applications due to their size, ultra low power requirements, and electrometer-like sensitivity. The main goal of this research was to create a bionanohybrid device by integrating bR with a SET device. This was achieved by a multidisciplinary approach. The SET devices were created by a combination of sputtering, photolithography, and focused ion beam machining. The bionanomaterial bacteriorhodopsin was created through oxidative fermentation and a series of transmembrane purification processes. The bR was then integrated with the SET by electrophoretic deposition, creating a bionanohybrid device. The bionanohybrid device was then characterized using a semiconductor parametric analyzer. Characterization demonstrated that the bR modulated the operational characteristics of the SET when bR was activated with light within its absorbance spectrum. To effectively integrate bacteriorhodopsin with microelectromechanical systems (MEMS) and nanoelectromechanical systems (NEMS), it is critical to know the electrical properties of the material and to understand how it will affect the functionality of the device. Tests were performed on dried films of bR to determine if there is a relationship between inductance, capacitance, and resistance (LCR) measurements and orientation, light-on/off, frequency, and time. The results indicated that the LCR measurements of the bR depended on the thickness and area of the film, but not on the orientation, as with other biological materials such as muscle. However, there was a transient LCR response for both oriented and unoriented bR which depended on light intensity. From the impedance measurements an empirical model was suggested for the bionanohybrid device. The empirical model is based on the dominant electrical characteristics of the bR which were the parallel capacitance and resistance. The empirical model suggests that it is possible to integrate bR with a SET without influencing its functional characteristics.

Investigation into the impact of grain boundaries, film interface, and crystallographic orientation on the ionic conductivity of thin film gadolinium-doped ceria

The research reported in this dissertation investigates the impact of grain boundaries, film interface, and crystallographic orientation on the ionic conductivity of thin film Gd-doped CeO2 (GDC). Chapter 2 of this work addresses claims in the literature that submicron grain boundaries have the potential to dramatically increase the ionic conductivity of GDC films. Unambiguous testing of this claim requires directly comparing the ionic conductivity of single-crystal GDC films to films that are identical except for the presence of submicron grain boundaries. In this work techniques have been developed to grow GDC films by RF magnetron sputtering from a GDC target on single crystal r plane sapphire substrates. These techniques allow the growth of films that are single crystals or polycrystalline with 80 nm diameter grains. The ionic conductivities of these films have been measured and the data shows that the ionic conductivity of single crystal GDC is greater than that of the polycrystalline films by more than a factor of 4 over the 400-700°C temperature range. Chapter 3 of this work investigates the ionic conductivity of surface and interface regions of thin film Gd-doped CeO2. In this study, single crystal GDC films have been grown to thicknesses varying from 20 to 500 nm and their conductivities have been measured in the 500-700°C temperature range. Decreasing conductivity with decreasing film thickness was observed. Analysis of the conductivity data is consistent with the presence of an approximately 50 nm layer of less conductive material in every film. This study concludes that the surface and interface regions of thin film GDC are less conductive than the bulk single crystal regions, rather than being highly conductive paths. Chapter 4 of this work investigates the ionic conductivity of thin film Gd-doped CeO2 (GDC) as a function of crystallographic orientation. A theoretical expression has been developed for the ionic conductivity of the [100] and [110] directions in single crystal GDC. This relationship is compared to experimental data collected from a single crystal GDC film. The film was grown to a thickness of _300 nm and its conductivity measured along the [100] and [110] orientations in the 500-700°C temperature range. The experimental data shows no statistically significant difference in the conductivities of the [100] and [110] directions in single crystal GDC. This result agrees with the theoretical model which predicts no difference between the conductivities of the two directions.

Fabrication of nanoparticles by short-distance sputter deposition

During the past decades, tremendous research interests have been attracted to investigate nanoparticles due to their promising catalytic, magnetic, and optical properties. In this thesis, two novel methods of nanoparticle fabrication were introduced and the basic formation mechanisms were studied. Metal nanoparticles and polyurethane nanoparticles were separately fabricated by a short-distance sputter deposition technique and a reactive ion etching process. First, a sputter deposition method with a very short target-substrate distance is found to be able to generate metal nanoparticles on the glass substrate inside a RIE chamber. The distribution and morphology of nanoparticles are affected by the distance, the ion concentration and the process time. Densely-distributed nanoparticles of various compositions are deposited on the substrate surface when the target-substrate distance is smaller than 130mm. It is much less than the atoms’ mean free path, which is the threshold in previous research for nanoparticles’ formation. Island structures are formed when the distance is increased to 510mm, indicating the tendency to form continuous thin film. The trend is different from previously-reported sputtering method for nanoparticle fabrication, where longer distance between the target and the substrate facilitates the formation of nanoparticle. A mechanism based on the seeding effect of the substrate is proposed to interpret the experimental results. Secondly, in polyurethane nanoparticles’ fabrication, a mechanism is put forward based on the microphase separation phenomenon in block copolymer thin film. The synthesized polymers have formed dispersed and continuous phases because of the different properties between segments. With harder mechanical property, the dispersed phase is remained after RIE process while the continuous phase is etched away, leading to the formation of nanoparticles on the substrate. The nanoparticles distribution is found to be affected by the heating effect, the process time and the plasma power. Superhydrophilic property is found on samples with these two types of nanoparticles. The relationship between the nanostructure and the hydrophilicity is studied for further potential applications.

Assessment of detectability of neutral interstellar deuterium by IBEX observations

Context. The abundance of deuterium in the interstellar gas in front of the Sun gives insight into the processes of filtration of neutral interstellar species through the heliospheric interface and potentially into the chemical evolution of the Galactic gas. Aims: We investigate the possibility of detection of neutral interstellar deuterium at 1 AU from the Sun by direct sampling by the Interstellar Boundary Explorer (IBEX). Methods: Using both previous and the most recent determinations of the flow parameters of neutral gas in the local interstellar cloud (LIC) and an observation-based model of solar radiation pressure and ionization in the heliosphere, we simulated the flux of neutral interstellar D at IBEX for the actual measurement conditions. We assessed the number of interstellar D atom counts expected during the first three years of IBEX operation. We also simulated the observations expected during an epoch of high solar activity. In addition, we calculated the expected counts of D atoms from the thin terrestrial water layer covering the IBEX-Lo conversion surface, sputtered by neutral interstellar He atoms. Results: Most D counts registered by IBEX-Lo are expected to come from the water layer, exceeding the interstellar signal by 2 orders of magnitude. However, the sputtering should stop once the Earth leaves the portion of orbit traversed by interstellar He atoms. We identify seasons during the year when mostly the genuine interstellar D atoms are expected in the signal. During the first 3 years of IBEX operations about 2 detectable interstellar D atoms are expected. This number is comparable to the expected number of sputtered D atoms registered during the same time intervals. Conclusions: The most favorable conditions for the detection occur during low solar activity, in an interval including March and April each year. The detection chances could be improved by extending the instrument duty cycle, say, by making observations in the special deuterium mode of IBEX-Lo.

First direct observation of sputtered lunar oxygen

We present the first direct measurement of neutral oxygen in the lunar exosphere, detected by the Chandrayaan-1 Energetic Neutral Analyzer (CENA). With the lunar surface consisting of about 60% of oxygen in number, the neutral oxygen detected in CENA's energy range (11 eV−3.3 keV) is attributed to have originated from the lunar surface, where it was released through solar wind ion sputtering. Fitting of CENA's mass spectra with calibration spectra from ground and in-flight data resulted in the detection of a robust oxygen signal, with a flux of 0.2 to 0.4 times the flux of backscattered hydrogen, depending on the solar wind helium content and particle velocity. For the two solar wind types observed, we derive subsolar surface oxygen atom densities of N0= (1.1 ± 0.3) · 107m−3 and (1.4 ± 0.4) · 107m−3, respectively, which agree well with earlier model predictions and measured upper limits. From these surface densities, we derive column densities of NC= (1.5 ± 0.5) · 1013 m−2and (1.6 ± 0.5) · 1013 m−2. In addition, we identified for the first time a helium component. This helium is attributed to backscattering of solar wind helium (alpha particles) from the lunar surface as neutral energetic helium atoms, which has also been observed for the first time. This identification is supported by the characteristic energy of the measured helium atoms, which is roughly 4 times the energy of reflected solar wind hydrogen, and the correlation with solar wind helium content.

Electrical resistivity change in amorphous Ta42Si13N45 films by stress relaxation

In a first experiment, a reactively sputtered amorphous Ta₄₂Si₁₃N₄₅ film about 260 nm thick deposited on a flat and smooth alumina substrate was thermally annealed in air for 30 min and let cooled again repeatedly at successively higher temperatures from 200 to 500 °C. This treatment successively and irreversibly increases the room temperature resistivity of the film monotonically from its initial value of 670 μΩ cm to a maximum of 705 μΩ cm (+5.2 %). Subsequent heat treatments at temperatures below 500 °C and up to 6 h have no further effect on the room temperature resistivity. The new value remains unchanged after 3.8 years of storage at room temperature. In a second experiment, the evolution of the initially compressive stress of a film similarly deposited by reactive sputtering on a 2-inch silicon wafer was measured by tracking the wafer curvature during similar thermal annealing cycles. A similar pattern of irreversible and reversible changes of stress was observed as for the film resistivity. Transmission electron micrographs and secondary ion mass profiles of the film taken before and after thermal annealing in air establish that both the structure and the composition of the film scarcely change during the annealing cycles. We reason that the film stress is implicated in the resistivity change. In particular, to interpret the observations, a model is proposed where the interface between the film and the substrate is mechanically unyielding.

Can IBEX detect interstellar neutral helium or oxygen from anti-ram directions?

To better constrain the parameters of the interstellar neutral flow, we searched the Interstellar Boundary EXplorer (IBEX)-Lo database for helium and oxygen from the interstellar medium in the anti-ram direction in the three years (2009-2011) with the lowest background rates. We found that IBEX-Lo cannot observe interstellar helium from the anti-ram direction because the helium energy is too low for indirect detection by sputtering off the IBEX-Lo conversion surface. Our results show that this sputtering process has a low energy threshold between 25 and 30 eV, whereas the energy of the incident helium is only 10 eV for these observations. Interstellar oxygen, on the other hand, could in principle be detected in the anti-ram hemisphere, but the expected magnitude of the signal is close to the detection limit imposed by counting statistics and by the magnetospheric foreground.

Monte-Carlo simulation of Callisto's exosphere

We model Callisto's exosphere based on its ice as well as non-ice surface via the use of a Monte-Carlo exosphere model. For the ice component we implement two putative compositions that have been computed from two possible extreme formation scenarios of the satellite. One composition represents the oxidizing state and is based on the assumption that the building blocks of Callisto were formed in the protosolar nebula and the other represents the reducing state of the gas, based on the assumption that the satellite accreted from solids condensed in the jovian sub-nebula. For the non-ice component we implemented the compositions of typical CI as well as L type chondrites. Both chondrite types have been suggested to represent Callisto's non-ice composition best. As release processes we consider surface sublimation, ion sputtering and photon-stimulated desorption. Particles are followed on their individual trajectories until they either escape Callisto's gravitational attraction, return to the surface, are ionized, or are fragmented. Our density profiles show that whereas the sublimated species dominate close to the surface on the sun-lit side, their density profiles (with the exception of H and H-2) decrease much more rapidly than the sputtered particles. The Neutral gas and Ion Mass (NIM) spectrometer, which is part of the Particle Environment Package (PEP), will investigate Callisto's exosphere during the JUICE mission. Our simulations show that NIM will be able to detect sublimated and sputtered particles from both the ice and non-ice surface. NIM's measured chemical composition will allow us to distinguish between different formation scenarios. (C) 2015 Elsevier Inc. All rights reserved.

Characterization of HFO2 Capacitors

Hafnium oxide (HfOn) is a promising dielectric for future microelectronic applications. Hf02 thin films (10-75nm) were deposited on Pt/Si02/Si substrates by pulsed DC magnetron reactive sputtering. Top electrodes of Pt were formed by e-beam evapo- ration through an aperture mask on the samples to create MIM (Metal-Insulator-Metal) capacitors. Various processing conditions (Arloz ratio, DC power and deposition rate) and post-deposition annealing conditions (time and temperature) were investigated. The structure of the Hf02 films was characterized by X-ray diffraction (XRD) and the roughness was measured by a profilometer. The electrical properties were characterized in terms of their relative permittivity (E,(T) and ~,.(f)) and leakage behavior (I-V, I-T and I- time). The electrical measurements were performed over a temperature range from -5 to 200°C. For the samples with best experimental results, the relative permittivity of HfOa was found to be -- 27 after anneal and increased by 0.027%/"C with increasing temperature over the measured temperature range. At 25"C, leakage current density was below lop8 ~ l c m ' at 1 volt. The leakage current increased with temperature above a specific threshold temperature below which the leakage current didn't change much. The leakage current increased with voltage. At voltages below lvolt, it's ohmic; at higher voltages, it follows Schottky model. The breakdown field is - 1 . 8 2 ~ lo6 Vlcm. The optical bandgap was measured with samples deposited on quartz substrates to be 5.4eV after anneal.

Sputter optimization of AlN on diamond substrates for high frequency SAW resonators

The AlN/diamond structure is an attractive combination for SAW devices and its application at high frequencies. In this work, the synthesis of AlN thin films by reactive sputtering has been optimized on diamond substrates in order to process high frequency devices. Polished microcrystalline and as-grown nanocrystalline diamond substrates have been used to deposit AlN of different thickness under equal sputtering conditions. For the smoother substrates, the FWHM of the rocking curve of the (002) AlN peak varies from 3.8° to 2.7° with increasing power. SAW one port resonators have been fabricated on these films, whose electrical characterization (in terms of S11 parameters) is reported.

'Enhancement of the crystallization process of TbxFe1-x thin films upon the formation of alpha-Tb phase'

TbxFe1−x thin films deposited by sputtering on Mo were investigated structurally and magnetically. The microstructure consists of TbFe2 nanoparticles embedded in an amorphous matrix, and the Tb content can be correlated with an increase in the volume of these nanoparticles. Similar microstructure and behavior were found when TbFe2 was deposited on glass and on a Pt buffer layer. Nevertheless, thermal treatments promote a different effect, depending on the mechanical stiffness of the buffer layer. The layers deposited on Mo, a rigid material, show crystalline TbFe2 together with α-Tb phase upon thermal treatment. In contrast, TbFe2 does not crystallize properly on Pt, a material with a lower stiffness than Mo. Intermediate results were observed on the film deposited on glass. Experimental results show the impact of the buffer stiffness on the crystallization process. Moreover, the formation of α-Tb appears to be fundamental to crystallized TbFe2 on layers deposited on rigid buffers

Investigation on the structural and magnetic properties of sputtered TbFe2/Fe3Ga heterostructures

We have analyzed the structural and magnetic properties of as-grown and annealed [TbFe2/Fe3Ga]n heterostructures grown by sputtering. Evidence of the bcc structure in the Fe3Ga layers has been found. The diffraction peak related to this structure shifts to high angles with the annealing temperature. Also, we have observed a change in the microstructure of the Tb-Fe layers when the thickness layer is reduced in the as-grown heterostructures. Moreover, the Tb content is lower than 33% of the TbFe2 Laves phase and it depends on the layer thickness. The thermal treatments promote the increase of the Tb content, but only in the heterostructures with thick layers. The strong lattice mismatch between the Tb-Fe and Fe-Ga layers seems to prevent a complete Tb diffusion upon the annealing process. Thus, the crystallization of the TbFe2 Laves phase is inhibited in the heterostructures with thin layers, although our experimental results indicate the presence of potential magnetostrictive TbFeGa alloys

Optimización de las condiciones de electrodeposición para la obtención de núcleos sensores

Mostraremos los resultados obtenidos en la búsqueda de las condiciones de crecimiento óptimas para que las propiedades magnéticas de aleaciones de CoP sean las adecuadas para utilizarlas como núcleos de sensores. Demostraremos que utilizando una densidad de corriente adecuada en el proceso de electrodeposición, es posible obtener aleaciones formadas por capas ferromagnéticas de distinta composición que presentan anisotropía en el plano y un campo coercitivo comparable al de las aleaciones producidas por enfriamiento ultrarrápido. Como ánodos empleamos láminas de cobalto de 1 mm de espesor y una pureza del 99.95%. Como sustratos utilizamos tanto láminas de Cu como sustratos fabricados por sputtering. Durante la electrodeposición se ha utilizado la agitación del electrolito y la vibración del cátodo para facilitar el desprendimiento de las burbujas de H2 que se generan durante el proceso. De esta forma se han obtenido las monocapas controlando los dos parámetros siguientes: la densidad de corriente y el tiempo de aplicación de la misma. Por otro lado, para las multicapas se han aplicado pulsos de corriente donde se han tenido que controlar la duración de los pulsos y la intensidad de los mismos.