The manipulation of single magnetic molecules may enable new strategies for high-density information storage and quantum-state control. However, progress in these areas depends on developing techniques for addressing individual molecules and controlling their spin. Here, we report success in making electrical contact to individual magnetic N@C(60) molecules and measuring spin excitations in their electron tunnelling spectra. We verify that the molecules remain magnetic by observing a transition as a function of magnetic field that changes the spin quantum number and also the existence of non-equilibrium tunnelling originating from low-energy excited states. From the tunnelling spectra, we identify the charge and spin states of the molecule. The measured spectra can be reproduced theoretically by accounting for the exchange interaction between the nitrogen spin and electron(s) on the C(60) cage.

Anatase TiO 2 is typically a central component in high performance dye-sensitised solar cells (DSCs). This study demonstrates the benefits of high temperature synthesised mesoporous titania for the performance of solid-state DSCs. In contrast to earlier methods, the high temperature stability of mesoporous titania is enabled by the self-assembly of the amphiphilic block copolymer polyisoprene-block-polyethylene oxide (PI-b-PEO) which compartmentalises TiO 2 crystallisation, preventing the collapse of porosity at temperatures up to 700 • C. The systematic study of the temperature dependence on DSC performance reveals a parameter trade-off: while high temperature annealed anatase consisted of larger crystallites and had a higher conductivity, this came at the expense of a reduced specific surface area.While the reduction in specific surface areas was found to be detrimental for liquid-electrolyte DSC performance, solid-state DSCs benefitted from the increased anatase conductivity and exhibited a performance increase by a factor of three.

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We have explored the opto-electronic properties of a new series of hole-transport materials based on main-chain triphenylamine-based poly(azomethine)s. 4,4 0 -Diaminotriphenylamine (TPA) was polymerized under benign conditions with either terephthalaldehyde (TPA-14Ta), 2,5-thiophenedicarboxaldehyde (TPA-25Th) or 1,3-isophthalaldehyde (TPA-13Iso) to yield polymers with an M n of 5700-16 000 g mol À1 . Despite the non-linear, or 'kinked', backbone geometry, all polymers form lyotropic solutions in chloroform and this liquid crystal (nematic) ordering could be maintained in the solid film after spin casting. All polymers exhibit high glass-transition temperatures (T g > 250 C) and display outstanding thermal stabilities, i.e. 5% wt loss in excess of 400 C under nitrogen. The HOMO and LUMO energy levels of these polymers were in the range of 5.0-5.3 and 2.4-3.3 eV below the vacuum level, respectively. Introduction of a thiophene heterocycle (TPA-25Th) resulted in a material with a low optical band-gap of approximately 2.0 eV, whereas TPA-14Ta and TPA-13Iso showed optical band gaps of 2.3 and 2.6 eV, respectively. A photovoltaic device based on a TPA-25Th/PCBM blend (1 : 3) showed an EQE of 20% at 500 nm. Under simulated sunlight, the device gives an open-circuit voltage of 0.41 V, a short-circuit current of 1.23 mA cm À2 and a fill factor of 0.24, leading to a power conversion efficiency of 0.12%.

Thermally grown SiO 2 layers on Si (100) substrate have been subjected to different external voltage bias during XPS analysis to induce changes in the measured binding energy difference between Si 4+ and Si 0 in Si2p and Si KLL regions. The Si2p binding energy difference increases from 3.2 to 4.8 for samples containing 1-7 nm oxide thickness, and furthermore, this difference can be influenced by application of an external bias to the sample. Application of negative d.c. bias increases the binding energy difference, whereas positive bias decreases it. The voltage dependence of the binding energy difference exhibits a sigmoid character with an abrupt change near 0 V. Both the binding energy difference and differential change between the positive and negative bias have similar functional dependence on the thickness. This is attributed to differential charging between the silicon oxide layer and silicon substrate, which is decreased when a positive bias is applied to the sample (and therefore attracting a larger proportion of the stray electrons from the vacuum chamber to partially neutralize the oxide). Similarly, when negative bias is applied, the stray electrons are repelled from the sample resulting in less neutralization and an increased differential charging. Through external biasing, it is determined that charging in the SiO 2 /Si system persists all of the way down to 1 nm. Application of a.c. (square-wave) bias is equivalent to simultaneous application of negative and positive bias together. However, the differential change in the binding energy difference in the positive and negative cycle is frequency dependent and approaches to the d.c. results at lower frequencies.

We present an X-ray photoelectron spectroscopic (XPS) investigation of potential screening across two gold electrodes fabricated on a porous polymer surface which is impregnated with the ionic liquid (IL) N-N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide [DEME-TFSI]. The IL provides a sheet of conducting layers to the insulating polymer film, and allows monitoring charging and screening dynamics at the polymer + IL/vacuum interface in a laterally resolved fashion across the electrodes. Time-resolved measurements are also implemented by recording F1s peaks of the IL, while imposing 10 mHz square-wave (SQW) pulses across the two electrodes in a source-drain geometry. Variations in the F1s binding energy reflect directly the transient local electrical potential, and allow us to visualize screening of the otherwise built-in local voltage drop on and across the metal electrodes in the range of millimeters. Accordingly, the device is partitioned into two oppositely polarized regions, each following polarization of one electrode through the IL medium. On the other extreme, upon imposing relatively fast 1 kHz SQW pulses the charge screening is prevented and the device is brought to assume a simple resistor role. A simple equivalent circuit model also reproduces the observed voltage transients qualitatively. The presented structure and variants of XPS measurements, enabling us to record voltage transients in unexpectedly large lateral distances away from the electrodes, can impact the understanding of various electrochemical concepts.

The molten-salt assisted self-assembly (MASA) process is applicable to fabricate high quality mesoporous metal lithiate thin films that exhibit excellent performance as electrocatalysts for water oxidation.

Lithium ion batteries (LIBs) currently deliver the highest energy density of any known secondary electrochemical energy storage system. However, new cathode materials, which can deliver both high energy and power densities, are needed to improve LIBs. Herein, we report on the synthesis of a new organic-based redox-active material centered about phenothiazine and phenylenediamine units. Improved Coulombic efficiencies and greater capacity retention during cycling are observed through the copolymerization of a phenothiazine-based monomer that yields cross-linked materials. With this as the positive electrode in Li-coin cells, high specific capacities (150 mAh/g) are delivered at very positive operating voltages (2.8−4.3 V vs Li + /Li), yielding high energy densities. The material has low charge transfer resistance as verified by electrochemical impedance spectroscopy, which contributes in delivering previously unseen power densities in coin cells for organic-based cathodes. Excellent retention of capacity (82%) is observed at ultrafast discharge rates (120 C).