Theoretical investigation of fluorination effect on the charge carrier transport properties of fused anthra-tetrathiophene and its derivatives

The crystal structures of known anthra-tetrathiophene (ATT) and its three fluorinated derivatives (ATT1, ATT2 and ATT3) were predicted by the Monte Carlo-simulated annealing method with the embedded electrostatic potential (ESP) charges. The most stable crystal structures were further optimized by the density functional theory with the dispersion energy (DFT-D) method. In addition, the effect of the electron-withdrawing fluorine atoms on the molecular geometry, molecular stacking, electronic and transport properties of title compounds were investigated by the density functional theory and the incoherent charge-hopping model. The calculated results show that the introduction of fluorine atoms does not affect the molecular planarity but decreases the HOMO-LUMO gap, which is beneficial to electron injection and provides more charge carrier stabilization. The improved electron mobility from ATT to ATT3 is attributed to the favorable molecular packing with strong π–π interaction and the short stacking distance. ATT2 and ATT3 exhibit remarkable angular dependence of mobilities and anisotropic behaviors. The band structures reveal that all the paths with larger transfer integrals are along the directions of large dispersions in the valence band (VB) and conduction band (CB). ATT3 has the largest electron mobility (0.48 cm² V⁻¹ s⁻¹) among the four compounds, indicating that fluorination is an effective approach to improve electron transport.     

Mining human mobility patterns from social geo-tagged data

Online social networks allow users to tag their posts with geographical coordinates collected through the GPS interface of smart phones. The time- and geo-coordinates associated with a sequence of posts/tweets manifest the spatial–temporal movements of people in real life. This paper aims to analyze such movements to discover people and community behavior. To this end, we defined and implemented a novel methodology to mine popular travel routes from geo-tagged posts. Our approach infers interesting locations and frequent travel sequences among these locations in a given geo-spatial region, as shown from the detailed analysis of the collected geo-tagged data.     

Molecular mobility in a homologous series of amorphous solid glucose oligomers

The molecular mobility of amorphous solid biomaterials influences the stability of dried foods and pharmaceuticals, the viability of seeds and spores, and the desiccation-tolerance of organisms during anhydrobiosis. Current understanding of how structure correlates with molecular mobility in the glassy state is inadequate. We used phosphorescence from vanillin dispersed in amorphous films to study the effect of temperature on molecular mobility in the homologous series of oligosaccharides glucose, maltose, maltotriose, maltotetraose, maltopentaose, maltohexaose, and maltoheptaose. Phosphorescence emission spectra and intensity decays were collected from −10 to as high as 130 °C. Emission peak energy, a measure of the extent of dipolar relaxation around the excited state prior to emission, decreased monotonically with temperature, decreasing more significantly in the glassy state in larger sugars (higher degree of polymerisation). The intensity decays were well fitted with sums of either four (glucose, maltose, maltotriose) or three exponentials (maltotetraose, maltopentaose, maltohexaose, maltoheptaose); fit lifetimes at each temperature varied over nearly two orders of magnitude, suggesting a comparable range in matrix dynamic heterogeneity. The lifetimes decreased monotonically with temperature, while the lifetime amplitudes favoured the long lifetime components at lower and short lifetime components at higher temperatures near T_g. Arrhenius analysis indicated that the rate of non-radiative decay, which reflects coupling of probe vibrations with matrix motions and thus provides an estimate of the matrix molecular mobility, increased with molecular size in the glassy state. Both apparent activation energy and activation entropy increased systematically with temperature in all sugars. These data provide additional evidence that the rate and extent of molecular mobility in glassy state carbohydrates is higher in sugars of greater molecular size (mass) and thus higher glass transition temperature and provides additional insight into the molecular dynamics of the glassy state in carbohydrates.     

Bulky rigid substitutions: A route to high electron mobility and high solid-state luminescence efficiency of perylene diimide

In this paper, we report that a kind of perylene diimide derivative with bulky rigid substituents, 1,7-bis(p-tert-butylphenoxy)-N,N′-dicyclohexyl-perylene-3,4,9,10-tetracarboxylic diimide (TBPCHPDI) possesses both high electron mobility (1.8 cm² V⁻¹s⁻¹) and high fluorescence quantum yield (0.32) in the solid state. Through X-ray diffraction (XRD), UV–Vis absorption and fluorescence spectra, and differential scanning calorimetry (DSC) measurements, it is demonstrated that the above phenomenon can be ascribed to the unique crystal structure of TBPCHPDI: due to steric hindrance of bulky rigid substituents, the intermolecular π–π actions are neglectable, providing high luminescence efficiency; in the mean time, the spacing between perylene chromophores is still very short (3.47 Å), which is favorable for the hopping transportation of charge carrier from one molecule to neighboring molecule. Therefore, our finding would help design and synthesize novel organic semiconductive materials with potential applications in electrically pumped lasers which require high emission efficiency when large current density is applied.     

The mutual influence of surface energy and substrate temperature on the saturation mobility in organic semiconductors

We report on a mutual correlation between the substrate temperature during semiconductor deposition and the surface energy of the gate dielectric on the charge carrier mobility in bottom gate top contact organic field effect transistors (OFETs) with N,N′-diphenyl-3,4,9,10-perylene tetracarboxylic diimide (DP-PDI) as organic semiconductor.     

Thermodynamic and diffusion kinetic studies of the Fe-Co system

The phase equilibria, thermodynamic properties and diffusion mobilities of the Fe-Co system were carefully assessed through the CALPHAD methods. As an indispensable tool, the first-principles calculations were carried out to study the magnetic moments and the enthalpies of mixing of the bcc_A2, bcc_B2, fcc_A1 and hcp_A3 phases as well as the point defect types of the bcc_B2 phase. In order to verify the heat capacities reported in the literature, new measurements were conducted in a high-temperature calorimetric apparatus using the three-dimensional calorimetric method. Because of the revision of the thermodynamic parameters in the present work, the diffusion mobilities for the fcc_A1 phase were reassessed. The diffusion mobilities for the bcc_A2 phase were established for the first time based on the experimental diffusion coefficients. For the low-temperature bcc_B2 phase, the diffusion couple experiments conducted in the present work show that the diffusion process is sluggish and the interdiffusion coefficients are difficult to determine. Therefore the tracer diffusivities of Co and Fe in the Fe-Co alloys were used to assess the diffusion mobilities for the bcc_B2 phase, while the composition-distance profile of one diffusion couple was served as a validation of its diffusion mobilities.     

Self‐Assembly of π‐Conjugated Amphiphiles: Free Standing,Ordered Sheets with Enhanced Mobility

Oligo(p‐phenylenevinylenes) (OPVs) with amphiphilic character are synthesized and their self‐assembly characteristics studied. Careful studies point at two morphologically different states of assemblies, with one being two dimensional sheets and the other as rolled tubes. This is also the first time that self‐assembled sheets are achieved for OPVs. Morphological and photo‐physical studies reveal a unique aggregate to aggregate transition between rolled tubes and two dimensional sheets, which is outlined as a more thermodynamic aggregate. The thermodynamic aggregate (2D sheet) is better ordered and consists of chromophores that are better excitonically coupled. The mobilities of these aggregates are also studied for a field effect transistor device and as expected sheets supersede rolled tubes by a couple of orders. More interestingly, the mobility values obtained for the well ordered chromophores in sheets is three orders higher than any other self‐assembled OPV previously reported. It is hypothesized that the better π interactions enforced by the amphiphilic design and the resultant supramolecular organization is a prime factor for such a remarkable rise in mobilities.     

Dielectric and microwave-absorbing behavior of hydrated wheat starch-gluten systems in relation to water mobility

Microwave heating has become popular in wheat-based food processing owing to its environmental friendliness, high-efficiency and low energy consumption. Water plays an important role in microwave food processing as it is a highly dielectric material that can react with many food components while being dynamic in complex food systems and affecting the overall dielectric response. In this study, hydrated systems of wheat starch, gluten (GLU) and starch-GLU mixtures (CBF) with different moisture contents were prepared and the variation patterns of their water mobility, dielectric properties and microwave absorption properties were measured. The results of low-field nuclear magnetic resonance (LF-NMR) analysis showed that water mobility was strongly influenced by moisture content and interactions between starch or GLU and water-restricted dynamic migration. In CBF, interactions between starch and water predominated under a reduced effect of GLU. As the water content increased, the complex permittivity showed an upward tendency, and the coupling capability of the hydrated systems with microwave was best at 35% moisture content. And the dielectric response and absorption characteristics of the hydrated systems fluctuated in a non-additive manner due to the interplay between moisture and the system components. Moreover, the correlation analysis was confirmed that the relationship between dielectric response behavior and water mobility, as higher water mobility more strongly influenced the augmentation of the dielectric characteristics and dominated changes in the locations of the microwave absorption peak and reflection loss value. These findings provide a possibility to manipulate the dielectric response changes of wheat-based materials under a microwave field through regulating the water mobility, thereby laying a theoretical basis to improve the utilization of microwave for wheat-based food production.     

Electronic structure,carrier mobility and device properties for mixed-edge phagraphene nanoribbon by hetero-atom doping

Phagraphene, a new carbon allotrope, was proposed recently. We here select a mixed-edge phagraphene ribbon to study B-, N-, and BN-doping effects respectively on the geometric stability, electronic structure, carrier mobility, and device property. Calculations show that the energetic and thermal stability for these ribbons are very high. With different doping types and doping sites, the bandgap size of a ribbon may be nearly unchanged, increased, or decreased as compared with the intrinsic ribbon, and even become a metal, thus presenting fully tunable electronic structures. For this, the charge transfer shifting edge bands and the new formed hybridized bands due to doping play a crucial role. More interestingly, doping at different positions can regulate the carrier mobility of ribbon, and the difference of two orders of magnitude for hole mobility can be generated by BN-doping. In addition, the study on device property shows that there is a prominent negative differential resistance characteristics occurring in a BN-doped ribbon device. These findings are meaningful for understanding the doping effects on electronic properties of phagraphene nanoribbons.