In this paper, we have studied the energy transport properties of two porphyrincontaining metal organic frameworks (MOFs) for light-harvesting applications. The photoinduced singlet exciton migration is investigated using fluorescence quenching experiments, whereas details on exciton transport anisotropy and net displacements are obtained using a Förster theory analysis. The striking difference in the energy-transport properties for the two MOFs, albeit for similar molecular organization, is attributed to dissimilar spatial expanse and difference in the electronic structure of their porphyrin struts. The observed exciton displacements, of up to 60 nm, provides motivation to explore new MOF materials. Several new linkers are considered, leading to predictions of MOF structures, which provide both broadwavelength harvesting and unidirectional energy transporting MOFs with selected examples.

CIGS solar cells were fabricated on a hybrid back contact comprised of a TCO layer (ZnO:Ga (GZO)) and Mo layers. It was discovered that an additional Mo layer introduced underneath the TCO layer promotes sodium diffusion through the TCO back contact into the upper CIGS absorber layer. Improvement in V OC and J SC values relative to those of sodium-free solar cells was achieved with the Mo/GZO/Mo hybrid back contact as a result of the enhanced sodium diffusion.

Thermal scanning electron microscopy is a new temperature mapping technique based on thermal diffuse scattering in electron backscatter diffraction in a scanning electron microscope. It provides both nano-scale resolution and far-field non-contact temperature mapping capabilities no other methods can adequately combine. While a calculated spatial resolution of less than 100 nm has already been realized using 20 keV electrons, lower energy incident electrons should enable still higher spatial resolution (even down to 10 nm). In this paper, the feasibility of this approach is examined.

Clozapine remains the most effective antipsychotic for management of schizophrenia, one of the most challenging mental disorders. Yet, this medication is underutilized due to the frequent blood draws associated with monitoring adverse side effects and maintaining effective drug levels in the body. Lab-on-a-chip (LOC)-based diagnostics at the point-of-care could decrease the burden on patients and doctors, enable personalized medicine, and improve treatment outcomes. Towards that goal, we present the development of an electrochemically active biomaterial probe to facilitate monitoring of clozapine as part of patient’s treatment regimen. The probe consists of the naturally derived polymer chitosan modified with catechol to provide a redox capacitor system, allowing for significant amplification. We demonstrate a 3- fold increase of the electrochemical signal generated by clozapine with the catechol-modified chitosan system over bare gold electrodes. The improved signal-to-noise ratio and overall performance of the bio-amplifier yield a detection limit below 1 μM, thus sufficient for the clinically relevant range of 1–3 μM. We further characterize the robustness of the biomaterial system with respect to re-use and storage, and demonstrate retention of its amplification characteristics when implemented on an electrochemical microchip. Our results align well with the clinical requirements and represent a critical first step in developing a point-of-care device for improved and personalized schizophrenia treatment.

Photoluminescence (PL), scanning electronic microscopy (SEM) and Raman scattering have been studied in crystalline ZnO nanosheets with different sizes after the thermal annealing at 400 °C for 2 hours in ambient air. ZnO nanosheets were created by the electrochemical (anodization) method using the variation of the etching durations with obtained ZnO nanosheet sizes from the range 40-360 nm. Earlier it was shown using the X ray diffraction (XRD) method that thermal annealing performed the ZnO oxidation and crystallization with the creation of the wurtzite crystal lattice. Four PL bands are revealed in PL spectra with the PL peaks at 1.60, 2.08, 2.50 and 3.10 eV. Size decreasing of ZnO nanosheets stimulates tremendous changes of ZnO optical parameters. It is shown that decreasing the ZnO nanosheet sizes is accompanied by the intensity increase of a set of Raman peaks and the surface defect related PL bands. The reasons of emission transformation and the nature of optical transitions have been discussed as well.

The kesterite semiconductor Cu2ZnSnS(e)4 is seen as a suitable absorber layer to replace Cu(In,Ga)Se2 in thin film solar cells, if thin film photovoltaics are to be deployed on the terawatt scale. Currently the best devices, and hence the best kesterite absorber layers are grown away from stoichiometry and are zinc rich and copper poor, presumably leading to the formation of ZnS(e). However, it has been shown that secondary phases present in an absorber layer reduce device performance. If growth in Zn rich conditions seems to be mandatory, then any secondary phases formed should be grown on the surface of the absorber layer so that they may be easily removed by etching. Therefore, it is important to know how and why secondary phases form, and if possible, how to segregate them to the surface of the absorber layer.

Here we show that ZnSe is formed at the initial stages of absorber formation from annealing metal stacks in selenium vapor. Further we demonstrate that the way the precursor metals are distributed on the substrate leads to different absorber layer performances in full devices. The importance of selenium vapor pressure is highlighted in respect to the order of selenisation of the metals, Zn before Cu. Additionally, the importance of selenium and tin selenide vapor pressure during annealing is reviewed with regard to avoiding a decomposition of the Cu2ZnSnSe4 to ZnSe and Cu2Se phases. Regardless of the atmosphere above the absorber, the reaction of the absorber with molybdenum appears unavoidable without the use of a passivation strategy. Counter-intuitively, it is demonstrated that for our absorber layers grown under Zn-rich conditions, removal of the ZnSe is harmful for device performance.

This study reveals that an “old” mechanism for shape memory in oriented polymers is in fact just one separate contribution for “supercontraction” in Nephila spider major ampulate silks. When Nephila spider silks are in contact with liquid water, they “super”-contract up to 28% of the original stretched length. However, we discovered that under glass transition conditions these silks only relax with a maximum shrinkage of 13%, and this phenomenon is defined as T g -contraction. Structural components permanent order (PO), permanent disorder (PD), meta order (MO) and meta disorder (MD) were proposed from the primary amino-acid sequence of the silk protein to explain morphological changes in the two contraction phenomena: MD contributes 13% of the full supercontraction and contributes to T g -contraction; whereas MO (the proline-containing motifs) contributes the rest for the full super-contraction and does not contribute to T g -contraction. The morphology in Nephila spider silk structure suggests two separate mechanisms to generate the shape memory effect in synthetic polymers.

Zn(S,O,OH) Chemical Bath Deposited (CBD) remains one of the most studied Cd-free buffer layer for replacing the CBD-CdS buffer layer in a Cu(In,Ga)Se2-based (CIGSe) solar cells and has already demonstrated its potential to lead to high-efficiencies. However, in order to further increase the deposition rate of the Zn(S,O,OH) layer during the CBD, the inclusion of additives can be a reasonable strategy, as long as the efficiencies of solar cells are maintained. The aim of this work is to understand the effect of the introduction of additives such as hydrogen peroxide (H2O2), H2O2+ethanolamine (C2H7NO) and H2O2+tri-sodium citrate (Na3C6H5O7) during CBD on the deposition mechanism, the growth rate and the quality of the buffer layer. It has been shown that the combined use of H2O2 and citrate in the bath formulation allows the deposition of Zn(S,O,OH) via a mix of “ion-by-ion” and “cluster-by-cluster” mechanisms that have good properties as buffer layers leading to high efficiency solar cells.

Recent exploratory syntheses of polar intermetallic compounds containing gold have established gold’s tremendous ability to stabilize new phases with diverse and fascinating structural motifs. In particular, Au-rich polar intermetallics contain Au atoms condensed into tetrahedra and diamond-like three-dimensional frameworks. In Au-poor intermetallics, on the other hand, Au atoms tend to segregate, which maximizes the number of Au-heteroatom contacts. Lastly, among polar intermetallics with intermediate Au content, complex networks of icosahedra have emerged, including discovery of the first sodium-containing, Bergman-type, icosahedral quasicrystal. Gold’s behavior in this metal-rich chemistry arises from its various atomic properties, which influence the chemical bonding features of gold with its environment in intermetallic compounds. Thus, the structural versatility of gold and the accessibility of various Au fragments within intermetallics are opening new insights toward elucidating relationships among metal-rich clusters and bulk solids.

The influence of the red and green LED light exposure on the memory function of the nanocrystalline MoOx embedded ZrHfO high-k gate dielectric has been investigated. Since the performance of the device is mainly dependent on the hole trapping and detrapping mechanisms, the light exposure affects the hole generation, transfer, and storage to and in the dielectric structure. Both the charge storage capacity and the leakage current were increased from the light exposure. The Coulomb blockade phenomenon in the leakage current density vs. gate voltage curve disappears under the light exposure condition. The light exposure effect is potentially important for practical application of the device.

A novel flat, wood-based carbon material with heterogeneous pores, referred to as flat lignocellulosic carbon material (FLCM), was successfully fabricated by carbonizing samples of the softwood Picea jezoensis (Ezomatsu or Jezo spruce, a Japanese conifer). Simultaneous improvements of the specific surface area of the FLCM and the affinity of electric double-layer capacitor (EDLC) for electrolyte solvents were achieved by vacuum ultraviolet/ozone (VUV/O3) treatment. The specific surface area of the VUV/O3-treated FLCM showed a 50% increase over that of the original FLCM. The spectra measured by X-ray photoelectron spectroscopy (XPS) indicated that the number of O-C=O (carboxyl or ester) bonds increased, whereas the number of C-C bonds decreased. Additionally, the feasibility of using the FLCM as a self-supporting electrode in EDLCs was examined by measuring the electrochemical properties in a three-electrode system. The FLCM was confirmed as an appropriate self-supporting EDLC electrode material without warps and cracks. In addition, the FLCM can be used without any binder. Realization of FLCM-based EDLC electrodes with bendability, an area of several tens of square centimeters, and no risk of warp or crack formation, were indicated. Thus, FLCMs present a fascinating class of self-supporting carbon electrode materials for EDLCs.

Deformation behavior of an 18R-type long period stacking ordered (LPSO) phase in the Mg-Zn-Y system was studied by micro-pillar compressions of single crystalline specimens prepared by focused ion beam (FIB) technique as a function of loading axis orientation and specimen dimensions. When the loading axis is inclined to the basal plane of the LPSO phase by 42°, basal slip of (0001)<11 $\bar 2$ 0>-type is activated irrespective of the specimen dimensions. When the loading axis is parallel to the basal plane, the formation of thick deformation bands are observed for all specimens tested. Strong size-dependence of yield stress values is observed for both types of micro-pillar specimens with different loading axis orientations.

Papers in the Appendix were published in electronic format as Volume 1534

Thermal effects on the crystal structure, electrical and optical characteristics of the Al and F co-doped ZnO films (ZnO:AlF3) are discussed in the paper. The ZnO:AlF3 thin films are prepared by RF sputtering with a constant power (ZnO/AlF3=100W/75W) toward the ZnO and AlF3 targets. The substrate temperature varied from room temperature to 250 °C with a step of 50 °C during thin film deposition. The crystalline quality of the ZnO:AlF3 film improved as the substrate temperature increased, with a corresponding increase in grain size. The improvement of the film quality leads to a higher electron mobility, with electron mobility of 0.85 cm2/V-s for the film deposited at the substrate temperature of 250 °C. The doping effect of fluorine in ZnO, and hence carrier concentration, was reduced at high temperature due to the vaporization of fluorine. This led to a reduction of carrier concentration with increase of temperature from 25 to 200°C. The corresponding resistivity increased from 3.60×10−2 to 6.0×10−2 Ω-cm. While for a further increase in substrate temperature, the doping of Al to the ZnO film was increased and resulted in an increase in carrier concentration.

We report mechanoluminescence (ML) in Sm3+-doped Sr3Sn2O7 phosphors with perovskite-related structure. The ML from Sr3Sn2O7:Sm3+, emitted strong reddish-orange light upon compression, is clearly observable by naked eyes. Based on the comparison between ML spectrum and photoluminescence spectrum, the ML emission was identified to be due to electron transition from an excited state 4G5/2 to the ground state 6HJ (J = 5/2, 7/2, 9/2) in Sm3+ ions. Although the ML emission was gradually decayed as compressive load was applied repeatedly, it recovered completely upon irradiation with UV light (254 nm). This behavior indicating that ML of Sr3Sn2O7:Sm3+ is intimately related to the charge traps. The charge transfer state (CTS) band in the PL excitation spectra was observed for Sr3Sn2O7:Sm3+, indicating that the efficient energy transfer from the host to the Sm3+ ions. The formation of CTS and the charge traps may be responsible for this ML performance.

We report the effects of electron irradiation on graphene Field Effect Transistor (FET) devices. We irradiated the graphene devices with 30keV electrons and measured the electrical transport properties in high vacuum in-situ. Upon electron irradiation, a Raman ‘D’ band appears. In addition, we observed that the doping behavior of the graphene devices changed from P to N type as a result of the irradiation. We also observed a shift of the Dirac point while the graphene FET device stays in vacuum and after it interacted with environmental molecules under ambient conditions.

The temperature induced structural transformations in physical mixtures of 1nm palladium and ultrafine (∼0.5nm) copper nanoparticles supported on carbon were studied using in-situ real time synchrotron based x-ray diffraction. These nanoparticles were subjected to two-step thermal annealing from 25°C to 700°C. The Pd and Cu nanoparticles were found to coalesce forming alloy nanoparticles that subsequently undergo a structural phase transformation from ordered B2 to disordered fcc. The random alloy formed at the end of the thermal treatments was found to be copper-rich.

Natural light harvesting organisms have evolved to harvest sunlight efficiently. Green sulfur bacteria, which contain chlorosomes, can survive in extremely low light conditions mainly because of efficient light absorption and transfer of energy, facilitated by the assembled dye molecules. Due to these reasons, chlorosomes have been used in dye sensitized solar cells to improve the light absorption and performance. The chlorosome absorption spectrum is fixed and their size is dependent on the organism. Various solution-based techniques have been developed for synthesizing mimics by supramolecular self-assembly. However, controlling the size of agglomerates and their subsequent deposition on surfaces to fabricate a device is difficult. In this work, a one-step aerosol-based self-assembly technique has been developed for the first time, to assemble and deposit chlorin (Bacteria chlorophyll mimics) agglomerates. A shift in absorption spectra of 79 nm which is comparable to the natural system was obtained. The analysis shows that kinetics of nucleation play an important role in assembly.

Heteroepitaxy of SiGe alloys on Si (001) under certain growth conditions has previously been shown to cause self-assembly of nanostructures called Quantum Dot Molecules, QDMs, where pyramidal pits and 3D islands cooperatively form. QDMs have potential applications to nanologic device architectures such as Quantum Cellular Automata that relies on localization of charges inside islands to create bi-stable logic states. In order to determine the applicability of QDMs to such structures it is necessary to understand the nano-scale chemistry of QDMs because the chemistry affects local bandgap which in turn affects a QDM’s charge confinement property. We investigate the nanoscale chemistry of QDMs in the Si0.7Ge0.3/Si (100) system using Auger Electron Spectroscopy (AES). Our AES analysis indicates that compressively strained QDM pit bases are the most Ge rich regions in a QDM. The segregation of Ge to these locations cannot be explained by strain energy minimization.

Ionic liquid (IL) ion sources with different emitter tip materials and tip numbers were developed and examined on ion beam characteristics with respect to its ILs wettability. As a result of ion current measurements, the most stable emission current was obtained for the graphite emitter tip and the ion current increased with increase of the tip number. The results indicate that the emitter wettability corresponding to the supplying flow rate and the number of emission site play an important role to stabilize and increase the beam current.