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We have demonstrated that pulsed laser deposition (PLD) conditions, i.e. O2 partial pressure (pO2) and temperature (T), enable control over the polarity of resistance switching in PCMO (Pr0.7C0.3MnO3) i.e. unipolar resistive switching (URS) vs. bipolar resistive switching (BRS). We observe by detailed physical characterization that BRS occurs in poly-crystalline thin films while URS is seen in amorphous films – indicating the materials origin of URS vis-a-vis BRS. BRS shows attractive lower voltage operation, no forming and lower variability than URS.
We report the evidence of ferroelectricity from LN-type ZnSnO3 nanostructure arrayed thick films (10 - 20 µm) on Si with remanent polarization value as high as ≈ 30 µC/cm2 in nanowire arrays. A combined pulsed-laser deposition (PLD) technique and a solvothermal synthesis scheme was adopted to effectively synthesize the nanostructured samples assisted by conducting ZnO template-layers. The similar crystal symmetry and comparable lattice parameter between ZnO and LN-type ZnSnO3 facilitated the dense growth of high-quality ZnSnO3 nanostructure arrays in the form of one-dimensional vertical nanowires, nanorods and two-dimensional nanoflakes. The strategic synthesis method allowed controlled tunability of the morphology, crystallinity, and packing density of ZnSnO3 nanostructures, which in turn facilitated the measurement of ferroelectric (FE) properties using a simple sandwich-device geometry. Analyses of the FE properties in relation to the structures are presented and their potential for designing future Pb-free FE devices for non-volatile memory applications is discussed.
The compression and decompression behaviors of graphite oxide have been investigated using in situ Raman measurements in a diamond-anvil cell at room temperature. The so-called G band (in-plane E2g mode ∼1600 cm-1) was followed to 49 GPa during compression and back to ambient under decompression. The Raman frequency of the G band increases sublinearly with increasing hydrostatic pressure, eventually nearly flattening out at the highest pressure measured. This trend is reversed upon decompression, fully recovering to the ambient spectrum. The increased broadening suggests a reversible disordering of the structure without significant sp2-sp3 rehybridization under pressure.
Using our newly proposed interface conductance modal analysis (ICMA) formalism, we study the modal contributions to thermal interface conductance (G ) across the interface of crystalline silicon and crystalline germanium. We present the accumulation functions of G at different temperatures and predict G as a function of temperature after proper quantum-corrections have been applied. Different classes of vibration are identified across the interface, among which interfacial modes are determined to have the highest per mode contribution to G . The results demonstrate the ability of ICMA in not only calculating the spectral contributions to G but exactly pinpointing the shape of each vibrational eigen state.
The effects of alloying elements (Ni/Ta) on the temperature dependence of yield stress in Co3(Al,W) with the L12 structure have been investigated through compression tests of nearly single-phase polycrystalline alloys in the temperature range between room temperature to 1,473K. Compared with a ternary Co3(Al,W), a Ni/Ta-added Co3(Al,W) alloy exhibits a higher γ΄ solvus temperature and lower onset temperature of the yield stress anomaly (positive temperature dependence of yield stress), suggesting that the CSF energy is increased by Ni/Ta addition. As a consequence, the high-temperature strength in Co3(Al,W) is considerably enhanced.
CuxO thin films have been deposited on a quartz substrate by reactive radio frequency (rf) magnetron sputtering at different target powers Pt (140-190 W) while keeping other growth process parameters fixed. Room-temperature photoluminescence (PL) measurements indicate considerable improvement of crystallinity for the films deposited at Pt>170 W, with most pronounced excitonic features being observed in the film grown using Pt=190 W. These results corroborate well with the surface morphology of the films, which was found more flat, smooth and homogeneous for Pt >170 W films in comparison with those deposited at lower powers.
We report the measurements of ferroelectricity in LiNbO3 (LN)-type ZnSnO3 /ZnO nanocomposite thick films deposited on Pt-Si substrates using a novel combined chemical/physical technique. Phase-pure LN-type ZnSnO3 nanorods (NRs) were first synthesized using a low temperature solvothermal process and characterized in detail using X-ray diffraction, electron microscopy and Raman spectroscopy. The prototype device for polarization measurements was fabricated by depositing the as-prepared LN-type ZnSnO3 NRs onto conducting Pt-Si substrates (also served as bottom electrodes). A dielectric filler-layer of polycrystalline ZnO was deposited on top using pulsed laser deposition to fabricate LN-type ZnSnO3 /ZnO nanocomposite films. Polarization measurements of the Pt/ZnSnO3+ZnO/Pt nanocomposite capacitors at 300K showed indication of polarization switching in the hysteresis loops with a remanent polarization (Pr) of 13 μC/cm2 at a low applied voltage of 8 V. The work provides information on the coherent design of future FE memory devices based on the emerging non-toxic Pb-free material LN-ZnSnO3.
Rare earth (e.g., Eu, Er, Yb, Tm) doped Y2O3 nanocrystals are promising fluorescent bioimaging agents which can overcome well known problems of currently used organic dyes like photobleaching, phototoxicity, and light scattering. Furthermore, the alternative quantum dots (QDs) composed of heavy metals (e.g., CdSe) possess inherently low biocompatibility due to the heavy metal content. In the present work, monodisperse spherical Y2O3:Eu3+ nanocrystals were successfully synthesized by microwave assisted urea precipitation method followed by thermochemical treatment. This is a green, fast and reproducible synthesis method, which is surfactant and hazardous precursors free. The as prepared particles were non-aggregated, spherical particles with a narrow size distribution. The calcined particles have a polycrystalline structure preserving the monodispersity and the spherical morphology of the as prepared particles. After calcination of Y(OH)CO3:Eu3+ precursors at 900°C for 2 hours, a highly crystalline cubic Y2O3 structure was obtained. The Y2O3:Eu3+ spherical particles showed a strong red emission peak at 613nm due to the 5D0–7F2 forced electric dipole transition of Eu3+ ions under UV excitation (235 nm) as revealed by the photoluminescence analysis (PL). The effect of reaction time on size and photoluminescence properties of calcined particles and also the effect of reaction temperature and pressure on the size and the yield of the precipitation process have been studied. The intense red fluorescent emission, excellent stability and potential low toxicity make these QDs promising for applications in bio-related areas such as fluorescence cell imaging or fluorescence bio labels.
Cellulose is one of the most abundant substances in the world, and the major constituent in the wood structure. Phenolic adhesive is largely used in the wood manufacture for gluing the wood panels together. The cellulose/phenolic adhesive interface is a representative of the interface between the wood panels and adhesives in the wood products. As the wood panels and adhesive are sensitive to environmental humidity, the interfacial adhesion of such interface when subjected to a humid environment can be a major factor in the durability of final products. Here, the role of water molecules on the adhesion property of cellulose/phenolic adhesive interface is investigated by molecular dynamics simulations. The simulation results reveal that the adhesion energy between cellulose and phenolic adhesive can be reduced by 86.5% with saturated moisture ingress. Meanwhile, it is demonstrated that the adhesion energy can be recovered after the interface experiences further dry conditioning. The hydrogen bonds between the cellulose and phenolic adhesive are found to account for the strong interfacial adhesion, which can be interrupted in the presence of water molecules and recovered after further dry conditioning. The adhesion property between the wood panels and adhesives is mainly determined by water molecules absorbed at the bilayer interface, which should be considered in a wet condition.
The interest in adopting hydrogen peroxide (H2O2) rocket propulsion systems has rekindled because H2O2 is more environmentally friendly than alternative propellants, has a high density to maximize the oxidizer-to-fuel ratio, and is able to be stored non-cryogenically. Simulations utilizing ab initio molecular dynamics have been generated to analyze the decomposition of H2O2 on the surface of a silver (Ag) metal cluster. The electronic structure for an atomic model of gaseous H2O2 molecules in the vicinity of an Ag13 cluster – one central Ag atom coordinated by the remaining twelve Ag atoms – was analyzed through density functional theory (DFT). After undergoing thermalization, the system was equilibrated at a high temperature of approximately 2000 K. The molecular dynamics did confirm that the Ag catalyst functions in facilitating the H2O2 decomposition to the final products of water and oxygen, while that the overall mechanism contains several intermediates.
Diamond-like carbon (DLC) has widespread attention as a new material for its application to thin film solar cells and other semiconducting devices. DLC can be produced at a lower cost than amorphous silicon, which is utilized for solar cells today. However, the electrical properties of DLC are insufficient for this purpose because of many dangling bonds in DLC. To solve this problem, we investigated the effects of the fluorine incorporation on the structural and electrical properties of DLC.
We prepared five kinds of fluorinated DLC (F-DLC) thin film with different amounts of fluorine. Films were deposited by the radio-frequency plasma enhanced chemical vapor deposition (RF-PECVD) method. C6H6 and C6HF5 were used as source gases. The total gas flow rate was constant and the gas flow rate ratio R (=C6H6 / (C6H6 + C6HF5)) was changed from 0 to 1 in 0.25 ratio steps. We also prepared nitrogen doped DLC (F-DLC) on p-Si using N2 gas as a doping gas to form nitrogen doped DLC (F-DLC) / p-Si heterojunction diodes.
X-ray photoelectron spectroscopy (XPS) showed that fluorine concentration in the DLC films was controlled. Moreover, the XPS analysis of the C1s spectrum at R=2/4 showed the presence of CF bonding. At R=1, CF2 bonding was observed in addition to CF bonding. The sheet resistivity of the films changed from 3.07×1012 to 4.86×109 Ω. The minimum value was obtained at R=2/4. The current-voltage characteristics indicated that nitrogen doped F-DLC of 2/4 and p-Si heterojunction diode exhibited the best rectification characteristics and its energy conversion efficiency had been maximized. This is because of a decrease of dangling bonds density by ESR analysis and an increase of sp2 structures by Raman analysis. When the fluorine is over certain content, the sheet resistivity increases because chain structures become larger, which is due to the CF2 bonding in F-DLC prevents ring structures. Many C2F4 species were observed and it may become precursors of the chain structure domains, such as (CF2)n.
In this study, we revealed effects of fluorine incorporation on DLC and succeeded in increasing its conductivity and improving rectification characteristics of DLC/ p-Si hetero-junction diodes. Our results indicate that DLC fluorination is effective for the semiconducting material, such as solar cell applications.
Stable, electrically conductive, thin film materials are key components for high temperature sensors operating in harsh environments. In this work, nanocomposite Pt-Zr-B and Pt-Si thin film materials were grown to a nominal thickness of 200 nm on both r-cut sapphire (α-Al2O3) substrates using e-beam evaporation, and their structure, morphology, and chemical composition was characterized following thermal treatments in an air laboratory furnace up to 1300°C. In the Pt-Zr-B system, oxidation of a nanolaminate architecture consisting of ZrB2 and pure Pt layers leads to boron oxide evaporation and the formation of Pt grains decorated by tetragonal-ZrO2 nanocrystallites at high temperature. Electrical conductivity measurements with a 4-point probe show that this nanocomposite film structure can maintain a film conductivity > 1x106 S/m up to 1300°C, depending on the Pt/ZrB2 layer thickness ratio. In the Pt-Si system, film compositions were varied to yield either nanocrystalline Pt3Si, Pt2Si, or PtSi phases depending on the Pt-Si ratio, or an amorphous phase at high Si content. Above 1000°C in air, Pt-oxide and Si-oxide phases form and coexist with the Pt-Si phases, and some Pt-Si film conductivities remain as high as 1x106 S/m after annealing at 1000°C for 6 hours. It was found that a 100 nm thick amorphous alumina capping layer grown by atomic layer deposition (ALD) aids in limiting film oxidation, but film stress leads to regions of delamination.
The unique properties of silicon oxide materials, no matter intrinsic or doped, utilized in thin film solar cells (TFSCs) in the area of photovoltaic (PV) are making TFSCs one of the most attractive photovoltaic technologies for the development of high-performing electricity production units to be integrated in everyday life. In comparison to other silicon materials, the particular diphasic structure of silicon oxide materials, in which hydrogenated microcrystalline silicon (μc-Si:H) crystallites are surrounded by an oxygen-rich hydrogenated amorphous silicon (a-Si:H) phase, causes them present excellent photoelectrical material properties, such as a low-parasitic absorption in the broadband spectral range, independent controllability of longitudinal and lateral conductivity, refractive indices (3.5-2.0), band gap (2.0-2.6 eV) and conductivity tenability (with orders of 1-10-9 S/cm) with oxygen doping, and so on. Various types of silicon oxide materials, including intrinsic, p- or n- type, further applied in TFSCs have also played significant roles in improving the efficiency of various types of single-, dual-, and triple-junction thin-film solar cells from both the optical and electrical points of view. In this paper, we present our latest progress in studying the performance improvement role of intrinsic or doped silicon oxide materials in pin-type a-Si:H, a-SiGe:H, and μc-Si:H single-junction solar cells. By effectively tuning the band gap values of intrinsic a-SiOx:H materials with oxygen doping and adopting the layers with a suitable band gap (1.86 eV) as the P/I buffer layers of a-Si:H solar cells fabricated on metal organic chemical vapor deposition (MOCVD) boron-doped zinc oxide (ZnO:B) substrates, a significant Voc increases up to 909 mV and an excellent external quantum efficiency (EQE) response of 75% at the 400 nm typical wavelength can be achieved by matching the band gap discontinuity between the p-type nc-SiOx:H window and a-Si:H intrinsic layers. The serious leakage current characteristics of pin-type narrow-gap (Eg<1.5 eV) a-SiGe:H single-junction solar cells can also be finely tuned by integrating an n-type μc-SiOx:H layer with a small oxygen content in addition to improving the long-wavelength response, an effective approach gives rise to the highest FF of 70.62% for pin-type a-SiGe:H single-junction solar cells with an average band gap of 1.48 eV. In addition, our studies proved that the application of p-type μc-SiOx:H window layers in μc-Si:H single-junction solar cells can effectively improve the short-wavelength light coupling by suppressing the parasitic absorption and promoting the anti-reflectivity with a graded refractive index profile. On the basis of the optimum single-junction solar cells with omnipotent silicon oxide materials, an initial efficiency of 16.07% has been achieved for pin-type a-Si:H/a-SiGe:H/μc-Si:H triple-junction solar cells with an active area of 0.25 cm2. The omnipotent properties of silicon oxide layers in TFSCs, including effective optical coupling and trapping, suitability in compensating for the band gap discontinuity, the shunt-quenching capacity, and so on, make them likely to be extended to other types of solar cells such as polycrystalline chalcopyrite Cu(In,Ga)Se2 (CIGS) and perovskite-sensitized solar cells, opening up new opportunities for acquiring solar cells with higher performance.
Thermodynamic modeling of the MOCVD process, using the standard free energy minimization algorithm, cannot always explain the deposition of hybrid films that occurs. The present investigation explores a modification of the procedure to account for the observed simultaneous deposition of metallic iron, Fe3O4, and carbon nanotubes from a single precursor. Such composite films have potential application in various device architectures and sensors, and are being studied as electrode material in energy storage devices such as lithium ion batteries and supercapacitors.
With ferric acetylacetonate [Fe(acac)3] as the precursor, MOCVD in argon ambient results in a nanocomposite of CNT, Fe, and Fe3O4 (characterized by XRD and Raman spectroscopy) when growth temperature T and total reactor pressure P are in the range from 600°C-800°C and 5-30 torr, respectively. No previous report could be found on the single-step formation of a CNT-metal-metal oxide composite. Equilibrium thermodynamic modeling using available software predicts the deposition of only Fe3C and carbon, without any co-deposition of Fe and Fe3O4, in contrast with experimental observations. To reconcile this contradiction, the modeling of the process was approached by taking the molecular structure of the precursor into account, whereas “standard” thermodynamic simulations are restricted to the total number of atoms of each element in the reactant(s) as the input. When Ocon (statistical average of the oxygen atom(s) taken up by each metal atom during CVD) is restricted to lie between 0 and 1, thermodynamic computations predict simultaneous deposition of FeO1-x, Fe3C, Fe3O4 and C in the inert ambient. At high temperature and in a carbon-rich atmosphere, iron carbide decomposes to iron and carbon. Furthermore, FeO1-x yields Fe and Fe3O4 when cooled below 567°C. Therefore, the resulting film would be composed of Fe3O4, Fe and C, in agreement with experiment. The weight percentage of carbon (∼40%) calculated from thermodynamic analysis matches well with experimental data from TG-DTA.
Polymeric nanoparticles having redox-active catechol moieties, a common structural motif found in naturally-occurring antioxidants, were developed. We synthesized an amphiphilic catechol-bearing polymer that self-assembled to form nanoparticles with a diameter of 126 nm. The nanoparticles showed enhanced ROS-scavenging activity compared to the small catecholic compound dopamine. Furthermore, the nanoparticles inhibited ROS-mediated angiogenesis as shown by the endothelial cell tube formation assay and the chicken chorioallantoic membrane (CAM) assay.
A new measurement technique using a cantilever probe with an integrated thermal sensor is investigated for measuring thermal conductivity at the nanometer scale. The probe is used in a configuration wherein the laser from an atomic force microscope (AFM) heats the tip of the probe above ambient temperature. Heat is transferred from the probe to a sample based on the thermal conductivity of the sample. The heat flow creates a temperature change, as small as 0.01 °C, which is detected by the thermal sensor. The measurement technique presented offers a simple and effective method for mapping the thermal conductivity of a number of materials. We explore the ability of the technique to map silicon oxide on silicon, carbon fibers and gold nanoparticles. Analysis shows that the technique can be used to produce images with a thermal resolution surpassing 25 nm.