Hybrid organic-inorganic films consisted of molecular layers of a Keggin-structure polyoxometalate (POM: 12-tungstophosphoric acid, H(3)PW(12)O(40)) and 1,12-diaminododecane (DD) on 3-aminopropyl triethoxysilane (APTES)-modified silicon surface, fabricated via the layer-by-layer (LBL) self-assembly method are evaluated as molecular materials for electronic devices. The effect of the fabrication process parameters, including primarily compositions of deposition solutions, on the structural characteristics of the POM-based multilayers was studied extensively with a combination of spectroscopic methods (UV, FTIR, and XPS). Well-characterized POM-based films (both single-layers and multilayers) in a controlled and reproducible way were obtained. The conduction mechanisms in single-layered and multilayered structures were elucidated by the electrical characterization of the produced films supported by the appropriate theoretical analysis. Fowler-Nordheim (FN) tunneling and percolation mechanisms were encountered in good correlation with the structural characteristics of the films encouraging further investigation on the use of these materials in electronic and, in particular, in memory devices.
Transition-metal-oxide hybrids composed of high surface-to-volume ratio Ta2O5 matrices and a molecular analogue of transition metal oxides, tungsten polyoxometalates ([PW12O40](3-)), are introduced herein as a charge storage medium in molecular nonvolatile capacitive memory cells. The polyoxometalate molecules are electrostatically self-assembled on a low-dimensional Ta2O5 matrix, functionalized with an aminosilane molecule with primary amines as the anchoring moiety. The charge trapping sites are located onto the metal framework of the electron-accepting molecular entities as well as on the molecule/oxide interfaces which can immobilize negatively charged mobile oxygen vacancies. The memory characteristics of this novel nanocomposite were tested using no blocking oxide for extraction of structure-specific characteristics. The film was formed on top of the 3.1 nm-thick SiO2/n-Si(001) substrates and has been found to serve as both SiO2/Si interface states' reducer (i.e., quality enhancer) and electron storage medium. The device with the polyoxometalates sandwiched between two Ta2O5 films results in enhanced internal scattering of carriers. Thanks to this, it exhibits a significantly larger memory window than the one containing the plain hybrid and comparable retention time, resulting in a memory window of 4.0 V for the write state and a retention time around 10(4) s without blocking medium. Differential distance of molecular trapping centers from the cell's gate and electronic coupling to the space charge region of the underlying Si substrate were identified as critical parameters for enhanced electron trapping for the first time in such devices. Implementing a numerical electrostatic model incorporating structural and electronic characteristics of the molecular nodes derived from scanning probe and spectroscopic characterization, we are able to interpret the hybrid's electrical response and gain some insight into the electrostatics of the trapping medium.
Superhydrophobicity on transparent fluorinated ethylene propylene films with nano-protrusion morphology by Ar+ O2 plasma etching: Study of the degradation in hydrophobicity after exposure to the environment Photoresist modifications by plasma vacuum ultraviolet radiation: The role of polymer structure and plasma chemistry J. Vac. Sci. Technol. B 28, 993 (2010); 10.1116/1.3484249Ion beam deposition of tantalum pentoxide thin film at room temperature In this work we study the utilization of molecular transition metal oxides known as polyoxometalates (POMs), in particular the Keggin structure anions of the formula PW 12 O 40 3À , as active nodes for potential switching and/or fast writing memory applications. The active molecules are being integrated in hybrid Metal-Insulator/POM molecules-Semiconductor capacitors, which serve as prototypes allowing investigation of critical performance characteristics towards the design of more sophisticated devices. The charging ability as well as the electronic structure of the molecular layer is probed by means of electrical characterization, namely, capacitance-voltage and current-voltage measurements, as well as transient capacitance measurements, C (t), under step voltage polarization. It is argued that the transient current peaks observed are manifestations of dynamic carrier exchange between the gate electrode and specific molecular levels, while the transient C (t) curves under conditions of molecular charging can supply information for the rate of change of the charge that is being trapped and de-trapped within the molecular layer. Structural characterization via surface and cross sectional scanning electron microscopy as well as atomic force microscopy, spectroscopic ellipsometry, UV and Fourier-transform IR spectroscopies, UPS, and XPS contribute to the extraction of accurate electronic structure characteristics and open the path for the design of new devices with on-demand tuning of their interfacial properties via the controlled preparation of the POM layer. V C 2014 AIP Publishing LLC.
Non‐volatile information storage using a molecular element comprising a proton‐conducting polymeric layer (PCL) and a proton‐trapping layer (PTL) is presented (see figure). Application of a positive voltage (write operation) to the top ion‐blocking electrode (IBE) allows dissociation of neutral (n) molecules into anions (−) and protons (+), motion and trapping (storage) of protons in the PTL. A negative voltage (erase operation) moves back the trapped protons to the anions.
Molecular materials containing tungsten polyoxometalates as the active elements embedded into polymer matrices are investigated as candidates for electronic device applications. The transport properties of these materials are investigated varying the interelectrode spacing and the polyoxometalate concentration. The I–V characteristics of planar devices reveal a conductivity peak at room temperature conditions for intermolecular distances less than 3 nm and electrode distances less than 100 nm. The transport characteristics are discussed in terms of tunneling mechanisms.
We herein present the supramolecular construction of a completely fluorescent unquenched multichromophoric wheel consisting of boron dipyrromethene dyes arranged perpendicularly to the circular plane.
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