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The current demand in the automobile industry is in the control of air-fuel mixture in the combustion engine of automobiles. Oxygen partial pressure can be used as an input parameter for regulating or controlling systems in order to optimize the combustion process. Our goal is to identify and optimize the material system that would potentially function as the active sensing material for such a device that monitors oxygen partial pressure in these systems. We have used thin film samaria doped ceria (SDC) as the sensing material for the sensor operation, exploiting the fact that at high temperatures, oxygen vacancies generated due to samarium doping act as conducting medium for oxygen ions which hop through the vacancies from one side to the other contributing to an electrical signal. We have recently established that 6 atom % Sm doping in ceria films has optimum conductivity. Based on this observation, we have studied the variation in the overall conductivity of 6 atom % samaria doped ceria thin films as a function of thickness in the range of 50 nm to 300 nm at a fixed bias voltage of 2 volts. A direct proportionality in the increase in the overall conductivity is observed with the increase in sensing film thickness. For a range of oxygen pressure values from 0.001 Torr to 100 Torr, a tolerable hysteresis error, good dynamic response and a response time of less than 10 seconds was observed.
We have designed a field emission microscope (FEM) coupled to a chemical vapor deposition (CVD) reactor in order to observe directly the growths of individual carbon nanotubes (CNTs) from the nucleation stage. Catalyst metals are first deposited in situ on a sharp metallic tip during direct FEM imaging and formed into nanoparticles by dewetting. CNTs are then grown directly on these nanoparticles by CVD in acetylene or other hydrocarbon gases at appropriate temperatures (600-900°C). The FEM patterns are formed by electrons emitted from individual CNT caps. The videos are analyzed to extract the growth rates and models. In situ field emission I/V measurements are also performed. The most interesting new discovery is that the CNTs often rotate axially during growth, thus strongly supporting a recently proposed model of ‘screw-dislocation-like’ (SDL) mechanism. The event is not rare as four rotating CNT growths versus six non-rotating growths were observed. In one case the CNT rotated quite uniformly ∼180 times during its 11 min growth. This observation should aid researchers to better understand and control the growth of SWNTs.
Au/TiO2 thin films have been prepared from Titanium Tetrabuthoxide-acetylacetone solution and buthanol as solvent by sol-gel and dip-coating technique. Au nanoparticles were prepared from HAuCl4 solution. The deposition of Au nanoparticles was by spray pyrolysis method. The films from the sol gel solution were heat treated at 450°C for 1 hour. The surface structures, morphology, composition and optical properties on the films were investigated by atomic force microscopy (AFM), optical microscopy (OM), X-ray Diffraction (XRD) and UV-Vis spectrometer. It was found the film consisted of anatase phase (TiO2), Au nanoparticles in the range of 50 to 100 nm, and few cracks on the surface remaining attached to the glass substrate. In this study, we measured the photocatalytic degradation of a methylene blue (MB) aqueous solution by a film prepared by the sol-gel and dip-coating methods TiO2 and Au/TiO2films prepared by spray pyrolysis method. We found that Au nanoparticles deposited on the TiO2films improved the photocatalytic activity and minor degradation time that TiO2 films.
The thermal effect on the nanofluidic behaviors in a nanoporous silica gel is investigated experimentally. When a nanoporous silica gel is modified by silyl groups, its surface becomes hydrophobic. A sufficiently high external pressure must be applied to overcome the capillary effect; otherwise liquid infiltration could not occur. The formation and the disappearance of a solid–liquid interface are employed for energy storage or dissipation. When the hydrophobic surface of nanoporous silica gel is decomposed at various temperatures, the organic surface layers can be deactivated. As a result, the degree of hydrophobicity, which can be measured by the liquid infiltration pressure, is lowered. The infiltration and defiltration behaviors of liquid are dependent on the controlled by the decomposition-treatment temperature.
Au-SnOx nanocomposite thin films composed of gold nanoparticles embedded in SnOx matrix were prepared by pulsed laser deposition technique and their crystal structure, morphology and chemical composition were evaluated by low angle X-ray diffraction, field-emission scanning electron microscopy and x-ray photoelectron spectroscopy, respectively. For the nanocomposite films with high Au percentage, the surfaces of nanocomposite films are very smooth, while for the films with low Au percentage, the films consist of many embedded Au nanoparticles with particle size of 5-20 nm. The XRD results revealed that in the nanocomposite films Au existed in a polycrystalline phase while SnOx in an amorphous phase. Surface plasmon resonance (SPR) responses of the Au-SnOx nanocomposite thin films were investigated as functions of Au percentage and film thickness in the Kretschmann geometry of attenuated total reflection using a polarized light beam at the wavelength of 640 nm. The reflectance minima (SPR dip) of SPR responses of the Au-SnOx nanocomposite films appeared at higher values of incident angle than that of a pure Au film and as the Au percentage decreases the SPR angles shift to higher values and the widths also become broader. The potential use of Au-SnOx nanocomposite films for SPR gas sensing was discussed.
Rice straw is among the most abundant herbaceous biomass, and regarded as the central feedstock for bioethanol production in Japan. We found that significant amounts of soft carbohydrates (SCs), defined as carbohydrates readily recoverable by mere extraction from the biomass or brief enzymatic saccharification, exist in rice straw in the form of free glucose, free fructose, sucrose, starch, and β-1,3-1,4-glucan. Based on the finding, we proposed a simple method for bioethanol production from rice straw samples with SCs, by a heat treatment for sterilization and starch gelatinization, followed by simultaneous saccharification/fermentation with Saccharomyces cerevisiae. This method would offer an efficient process for bioethanol production without the aid of harsh thermo/chemical pretreatment step.
The phase change materials (PCM) are known since years with high thermal storage capacity but with limited applications. The modified PCM mainly paraffin watery suspensions, so called PCM slurry, improve some PCM drawbacks (thermal conductivity) and as paraffin multifunctional fluids can work in both, heat transport and heat storage for cooling technology applications. The structural and thermophysical properties of two types PCM slurry were good basis for comparison of their efficiency: paraffin microcapsule slurry (A) and paraffin emulsion slurry (B), both working in temperature range of phase transition from 2-12 degreesC. The equipments as differential scanning calorimetry (DSC), model NETZSCH DSC 200 PC; scanning electron microscopy (SEM), JOEL model JSM-5510; hot stage optical microscopy, LINKAM model TMS 94 and hand made thermal cycling system operational with Danfoss cooling machine that ensured 2 kW cooling capacity at 40oC; gave accurate results, characterizing completely, from structural and thermal point of view both types of PCM multifunctional structured fluids. Structural stability of the advanced phase change multifunctional fluids was discussed on sample imaging in variable magnifications made by method of Hot Stage microscopy and precise SEM study. Systematization of the DSC results obtained, including temperature range of phase transition and thermal storage capacity, measured before and after repeatable thermal cycling of the PCM multifunctional fluids, allowed selection of the PCM slurry working samples with relatively high thermal capacity applicable to further development in prototypes. Heat absorbed/released, calculated by NETZSCH DSC software, was for PCM slurry A in the range of 80 to 82 kJ/kg, while PCM slurry B showed thermal storage capacity from 56 to 53 kJ/kg. Correlation between the structural properties and thermal storage capacity of the phase change multifunctional fluids led to practical conclusions concerning: homogeneity; crystal growth/conditions; structural compatibility between components; prediction of the heat flow behavior of multifunctional PCM slurries in cooling technology for storage and transport of heat.
The titanium dioxide (TiO2) complexes are widely investigated for their striking and multipurpose capabilities. The TiO2 key feature lies in its photocatalytic activity for several reactions of social (bioengineering, environmental and artistic protection, pollution containment) and commercial (photovoltaic, alternative-energy, gas sensing) interests. The possibility to enhance specific reactions at the nanoscale by a fine tuning of the nano-sized single crystals properties boosted in the last decade the scientific research. Thus a theoretical understanding of the fundamental properties of TiO2 nanocrystals became necessary to predict and expedite the experimental effords.We present here a characterization of TiO2 0D nanoclusters and 1D nanowires in the framework of ab initio DFT calculations. Based on both theoretical and experimental evidences we defined a stoichiometric TiO2 NC by modifying a perfect bipyramidal morphology and then used this NC as a chain repetition unit in the NW. We analyzed the effect of the surface coverage by functionalizing dangling bonds with simple adsorbates (dissociated water and hydrogens) modeling two acidic environments. These terminations are important to model the basical interactions of TiO2 nanosystems with the hydration sphere, which is always found to surround the nanosamples and toaffect their photocatalytic activity. We thus address the electronic reorganization and the surface weight in determining the global features of the nanostructures. The structural reconstruction is found to depend on the surface coverage and the experimental evidences on the structural variations can be explained by a topological analysis of the Ti-O bonds. Quantum confinement effects in the electronic properties are observed through the bandgap widening and the discretization of the energy distribution, but the surface competes to determine the energy dispersion of the electronic levels. The hydrogenated nanocrystals do show occupied levels at the bottom of the coduction bands, thus leading to metallic nanowires in one dimension. Whereas in the hydrogenated cluster such levels present a localized charge distribution with respect to the whole structure and they are also similar for the atomic orbital character and energy position to the defect states obtained by oxygens desorption. From the analysis of the electronic density of states we found that Ti-H bonds induce in-gap states above the valence bands, whereas hydration leads to occupied states that shift the valence bands to lower binding energies. Formation energy calculations reveal that surface hydration leads to the most stable nanocrystals, in agreement with the experimental findings that water coverage stabilizes the surface.
The continuously growing and wide-spread utilization of blends of organic electron and hole conducting materials comprises ambipolar field-effect transistors as well as organic photovoltaic cells. Structural, optical and electrical properties are investigated in blends and neat films of the electron donor material Cu-phthalocyanine (CuPc) together with fullerene C60 and Cu-hexadecafluorophthalocyanine (F16CuPc) as electron acceptor materials, respectively. The difference in molecular structure of the spherical C60 and the planar molecule CuPc leads to nanophase separation in the blend, causing charge carrier transport which is limited by the successful formation of percolation paths. In contrast, blends of the similar shaped CuPc and F16CuPc molecules entail mixed crystals, as can be clearly seen by X-ray diffraction measurements. We discuss differences of both systems with respect to their microstructure as well as their electrical transport properties.
This study focused on the effect of UV irradiation on modification of polymethyl methacrylate-based photoresist, and then on wet photoresist (PR) removal of patterned structure (single damascene structure). Three single-wavelength UV sources were considered for PR treatment, with λ = 172, 222, and 283 nm. Modification of blanket PR was characterized using Fourier-transform infrared spectroscopy (FTIR; chemical change), spectroscopic ellipsometry (SE; thickness change), and dissolution in organic solvent (solubility change). While for patterned samples, scanning electron microscopy (SEM) was used for evaluation of cleaning efficiency. In comparison to 172 nm, the PR film irradiated by 222 nm and 283 nm photons resulted in formation of higher concentration in C=C bond. Immersion tests using pure N-methyl pyrrolidone (NMP) at 60 °C for 2 min showed that some improvement in PR removal was only observed for PR films treated by 283 nm UV for short irradiation times. Irradiation by photons at the other two wavelengths did not result in an enhancement of removal efficiency.
The PR film treated by 222 nm photons was chosen for further study with O3/H2O vapor at 90°C. Experimental results showed a complete PR and BARC removal for UV-treated PR, which can be explained by C=C bond cleavage by the oxidizer.
Heterojunction with intrinsic thin layer (HIT) solar cells have achieved conversion efficiencies higher than 22%. Yet, many questions concerning the device physics governing these cells remain unanswered. We use numerical modeling to analyze the role of a-Si:H layers and tunneling on cell performance. For cells with n-type c-Si (n-HIT cells), incorporating the indium-tin-oxide (ITO) as an n-type semiconductor creates an n+/p/n structure. Most device simulations do not work with this structure. Our modeling indicates that the n+/p/n device often produces irregular S-shaped current density–voltage (J-V) curves, which have been observed experimentally but were not previously understood. However, if tunneling is included, there are specific conditions where the n+/p/n structure performs as a robust solar cell with efficiencies exceeding 20%. Additional analysis examines voltage-dependent carrier collection in n-HIT cells, as well as material and interface properties that limit fill factor.In p-HIT cells, modeling the ITO layer as a semiconductor, rather than as a metallic contact, significantly reduces the impact of a-Si:H layer parameters on device performance. In p-HIT cells, the a-Si:H layers adjacent to the ITO layer play the role of a buffer that reduces interface recombination at the a-Si:H/c-Si interface and prevents tunneling of electrons from the ITO layer to the c-Si absorber. Tunneling through the a-Si:H layers adjacent to the back contact is important to attain regular J-V curves.
Two aluminosilicate oxyfluoride glass systems, a lead-cadmium-aluminosilicate oxyfluoride and a lithium-lanthanum-aluminosilicate oxyfluoride, doped with different TbF3 concentrations, have been fabricated and investigated. By appropriate heat treatment of the as-prepared glasses above, transparent glass-ceramics (TGC) were obtained. The glass-ceramics contain Tb:Pb(Cd)F2 or Tb:LaF3 nano-crystals in the glass-matrix. Differential scanning calorimetry, Raman scattering, and luminescence under both UV and β-particle excitation have been investigated on as-prepared glasses and glass-ceramics. It has been found that the terbium-doped lithium-lanthanum-aluminosilicate oxyfluoride glass exhibits good UV excited luminescence and β-induced luminescence. The luminescence yield increases for glass-ceramic compared to that of the as-prepared glass. The including of LaF3 in the glass-matrix is beneficial for a higher Tb-doping concentration and a high light yield. The light yield of lithium-lanthanum-aluminosilicate oxyfluoride glass and glass-ceramic is comparable to that of Schott IQI-301 product. However, the terbium-doped lead-cadmium-aluminosilicate oxyfluoride glass and glass-ceramic have a detrimental luminescence performance. The lead cations in the glass-matrix may create non-bridging oxygen defects, which are a strong source of charge traps, and correlated to a strong Raman “Boson” peak.
The future expansion of nuclear power provides materials challenges that are not easily overcome, for example the safe immobilisation of nuclear waste is an important component in any future expansion of nuclear power. The use of ceramic-based materials, as opposed to borosilicate glasses, is now being investigated widely. The ability of ceramics to be tailored to a specific waste stream is now understood and obtainable quickly and with minimal cost. A second component that limits the expansion of fission-based technologies is the development of materials that are not only tolerant of radiation damage, but are also capable of retaining mechanical strength at high temperatures. One concern for any material however, is the effect of radiation damage, primarily from alpha-decay damage, which in many systems can transform the material from crystalline to amorphous. The effects of such radiation damage on both the structural and chemical properties can range from trivial to critical, for example volume expansion and are the primary focus of much research. As part of a long-term research programme the effects on radiation tolerance of a range of ordered and disordered materials are discused.
To update the status of knowledge on the recombination-enhanced dislocation glides (REDG) in semiconductors, which is one of the causes of serious degradation in bipolar devices, research progress achieved for the last decade has been surveyed. Rather than presenting a complete review over a wide range of material systems, a particular attention has been paid to the REDG effect in 4H-SiC for which a lot of information has been accumulated owing to extensive studies. Although the REDG effect exhibits features that could be interpreted in terms of the phonon-kick mechanism, conclusive proof is still lacking.
Bone grafts need to comply with some criteria of biocompatibility, including favoring neovascularization, new bone formation, and discourage inflammatory response and graft rejection. It is also expected that these materials should have mechanical properties similar to those of natural bone, that is, having enough pores to permit osteoprogenitor cells and vascular endothelium penetration but maintaining strength and flexibility.
Here, a new resistant and flexible tridimensional multilayered bioceramic composite was obtained by using chitosan and hydroxyapatite in combination with cells and their associated growth factors from the bone marrow tissue, allowing the development of a biocompatible bone graft.
This multilayered graft made out of chitosan functionalized with phosphate groups and mineralized with calcium phosphate (hydroxyapatite) was analyzed with scanning electron microscopy (SEM), X ray diffraction (XRD), energy dispersive X-ray analysis (EDX) and Fourier transform infrared spectroscopy (FTIR) to assess the degree of phosphorylation and the amount of hydroxyapatite present in the graft. The composite was further characterized by mechanical testing (Vicker's microhardness test), in vitro osteoblasts culture citotoxicity tests.
The results showed that this multilayered graft has mechanical properties comparable to that of trabecular bone and it was capable to keed osteogenic cells alive.
Wafer level bonding is an important technology for the manufacturing of numerous Microelectromechanical Systems. In this work the aluminum thermo-compression wafer bonding is characterized. The effects and significance of various bond process parameters and surface treatment methods are reported on the final bond interfaces integrity and strength. Experimental variables include the bonding temperature, bonding time, and bonding atmosphere (forming gas and inert gas). Bonded wafer samples were investigated with scanning acoustic microscopy, scanning electron microscopy, and four point bending test. Interfacial adhesion energy and bond quality were found to be positively correlated with bonding temperature. A bonding temperature of 500 °C or greater is necessary to obtain bond strengths of 8-10 J/m2.
We report that the nonlinear optical response of polarity controlled ZnO films grown by selective growth technique of Zn-polar and O-polar ZnO layers on sapphire substrate using Cr-compound buffer layers. ZnO layers grown on CrN/sapphire show Zn polar, while those grown on Cr2O3/sapphire result in O-polar ZnO films. In order to verify the origin of nonlinear optical response of ZnO, the polarity-controlled ZnO thin films grown on different buffer layers were investigated as nonlinear optical materials for second harmonic generation (SHG). The effective nonlinear optical coefficient (deff) of ZnO grown on Cr-compound buffer layers showed a higher value than that of ZnO grown on MgO buffer layers. Finally, by combining suggested in-situ polarity control technique with photolithography technique, we have fabricated 1D and 2D periodically-polarity-inverted (PPI) hetro-structures with periodicity ranging from 60 μm to 2 μm. The lateral polarity inversion is confirmed by piezo response microscopy. Such PPI ZnO heterostructures show the enhancement of SHG intensity comparing with the ZnO films.
The Center for Research on Interface Structures and Phenomena (CRISP) is a National Science Foundation (NSF) Materials Research Science and Engineering Center (MRSEC). CRISP is a partnership between Yale University, Southern Connecticut State University (SCSU) and Brookhaven National Laboratory. A main focus of CRISP research is complex oxide interfaces that are prepared using epitaxial techniques, including molecular beam epitaxy (MBE). Complex oxides exhibit a wealth of electronic, magnetic and chemical behaviors, and the surfaces and interfaces of complex oxides can have properties that differ substantially from those of the corresponding bulk materials. CRISP employs this research program in a concerted way to educate students at all levels. CRISP has constructed a robust MBE apparatus specifically designed for safe and productive use by undergraduates. Students can grow their own samples and then characterize them with facilities at both Yale and SCSU, providing a complete research and educational experience. This paper will focus on the implementation of the CRISP Teaching MBE facility and its use in the study of the synthesis and properties of the crystalline oxide-silicon interface.
Excitons in semiconductor alloys feel a random disorder potential leading to inhomogeneous line broadening and a lack of knowledge about the dominating recombination processes. Nevertheless, we demonstrate competing localization effects due to disorder (random potential fluctuations) and shallow point defects. We were able to spectrally separate donor-bound and quasi-free excitons within the whole wurtzite-type composition range of MgxZn1-xO (0 ≤ x ≤ 0.33) using spectrally resolved (x ≤ 0.06) and time-resolved photoluminescence (x ≥ 0.08). We found out that donor-bound excitons dominate photoluminescence spectra even for Mg-contents up to x = 0.18 and still appear for x = 0.33.