Paul Bazylewski

Efficient energy transfer from ZnO to Nd3+ ions in Nd-doped ZnO films deposited by magnetron reactive sputtering

In this paper, a detailed study of the luminescent properties of Nd3+ ions in sputtered ZnO thin films is reported for the first time. Experimental evidence is provided showing that Nd is inserted and optically active in the ZnO matrix. Despite the small amount (<2%) of rare earth in these thin ZnO films, intense luminescence signals have been collected, indicating efficient infrared emission of Nd3+ in ZnO. Direct excitation of Nd3+ ions in the ZnO matrix was possible, suggesting that most of the Nd atoms are in the 3+ form at all deposition temperatures. Moreover, intense Nd3+ emission has been recorded also when the host was excited, indicating that an efficient energy transfer occurs from ZnO to Nd ions. Both the transfer efficiency and the Nd3+ concentration seem to depend on the deposition temperature. In particular, indirect excitation of the sample deposited at 400 °C generates a richer emission pattern compared to lower temperatures. The careful analysis of the luminescence data indicated that the new pattern comes from Nd sites that cannot be efficiently directly excited, but that are characterized by intense emission under indirect excitation of the host. The possible transfer mechanisms leading to this behavior will be outlined.

Self-Ordering Properties of Functionalized Acenes for Annealing-Free Organic Thin Film Transistors

Presented here is a study of the molecular self-ordering properties of four bis(phenylethynyl) anthracene based organic semiconductors related to their electronic structure employing X-ray spectroscopy techniques and density functional theory (DFT) calculations. The local molecular order through polarization dependence of C 1s → π* transitions revealed ordered π-stacking nearly perpendicular to the substrate due to van der Waals interactions between alkyl groups. DFT calculations were used to deconvolute the measured electronic structure and examine effects of small changes in molecular geometry in relation to measured charge carrier mobility in top contact field effect transistors. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) are found to be conjugated from the anthracene core across the bridging ethynyl groups to the thiophene and phenyl end groups. The inclusion of ethynyl bridges connecting the thiophenes has a twofold effect of both reducing the rotational freedom of this functional group and increasing HOMO/LUMO conjugation across the molecules. These features help create a more rigid upright structure for HB-ant-THT with better molecular orbital conjugation and subsequent higher mobility. With this understanding of how different functional groups interact with an acene core, future synthesis of new materials may be directed toward annealing-free organic semiconducting materials.

The characterization of Co-nanoparticles supported on graphene

The results of density functional theory (DFT) calculations and measurements of X-ray photoelectron (XPS) and X-ray emission (XES) spectra of Co-nanoparticles dispersed on graphene/Cu composites are presented. It is found that for 0.02nm and 0.06nm Co coverage the Co atoms form islands which are strongly oxidized under exposure at the air. For Co (2nm) coverage the upper Co-layers is oxidized whereas the lower layers contacting with graphene is in metallic state. Therefore Co (2 nm) coverage induces the formation of protective oxide layer providing the ferromagnetic properties of Co nanoparticles which can be used as spin filters in spintronics devices.

Insight into photon conversion of Nd3+ doped low temperature grown p and n type tin oxide thin films

The synthesis of multifunctional high-quality oxide thin films is a major current research challenge given their potential applications. Herein, we report on p and n type tin oxides thin films as functional TCOs with photon management properties through doping with Nd3+ rare earth ions. We show that the structure, composition, carrier transport and optical properties of the sputtered Nd:SnOx films can be easily tuned by simply varying the Ar/O2 gas flow ratio (R) during the deposition step. The increase of the oxygen content leads to drastic changes of the material properties from p-type SnO to n-type SnO2. Furthermore, all Nd:SnOx films are found to be highly conductive with resistivities as low as 1 × 10−3 Ω cm−1 and carrier mobilities up to 129 cm2 V−1 s−1. Thanks to deep XPS and NEXAFS spectroscopies, we gained insight into the coordination and oxidation degrees of the elements within the matrices. The insertion and optical activation of the incorporated Nd3+ ions have been successfully achieved in both matrices. As a consequence, strong NIR luminescence lines, typical of Nd3+ ions, were recorded under UV laser excitation. We experimentally show that the efficient Nd3+ photoluminescence in the near infrared region originates from efficient sensitization from the host matrix, through energy transfer. We found that the SnO2 host matrix provides more efficient sensitization of Nd3+ as compared to the SnO matrix. An energy transfer mechanism is proposed to explain the observed behaviour.

Selective Area Band Engineering of Graphene using Cobalt-Mediated Oxidation.

This study reports a scalable and economical method to open a band gap in single layer graphene by deposition of cobalt metal on its surface using physical vapor deposition in high vacuum. At low cobalt thickness, clusters form at impurity sites on the graphene without etching or damaging the graphene. When exposed to oxygen at room temperature, oxygen functional groups form in proportion to the cobalt thickness that modify the graphene band structure. Cobalt/Graphene resulting from this treatment can support a band gap of 0.30 eV, while remaining largely undamaged to preserve its structural and electrical properties. A mechanism of cobalt-mediated band opening is proposed as a two-step process starting with charge transfer from metal to graphene, followed by formation of oxides where cobalt has been deposited. Contributions from the formation of both CoO and oxygen functional groups on graphene affect the electronic structure to open a band gap. This study demonstrates that cobalt-mediated oxidation is a viable method to introduce a band gap into graphene at room temperature that could be applicable in electronics applications.

Characterization of metal-functionalized flax orbitide as a new candidate for light-emitting semiconductor

Organic materials display promise in numerous electronic applications, complimentary to traditional semi-conducting materials. Cyclolinopeptides show promise in light-emitting applications as an organic semiconductor. Photoluminescence measurements indicate charge transfer between the peptide and the metal, resulting in an increase in intensity of the emission from around the metal in the Cyclolinopeptide complex. Complementary X-ray absorption near-edge spectroscopy (XANES) shows a change in occupation of energy states in the peptide when complexed with the metal, indicating charge transfer, but peak positions show the peptide is not chemically changed by the metal. Combining X-ray emission and XANES provides element specific partial density of states, to estimate the element specific energy gap which is the proposed emission range for the peptide material. Organic light emitting diode devices have been fabricated, although no measurable emission has been seen as of yet. The devices have diode like current-voltage characteristics showing the peptide is semi-conducting with a threshold voltage of approximately 2.5 V.