Biradicaloid compounds with an open-shell ground state have been the subject of intense research in the past decade. Although diindenoacenes are one of the most developed families, only a few examples have been reported as active layers in organic field-effect transistors (OFETs) with a charge mobility of around 10−3 cm2 V−1 s−1 due to a steric disadvantage of the mesityl group to kinetically stabilize compounds. Herein, we disclose our efforts to improve the charge transport of the diindenoacene family based on hexahydro-diindenopyrene (HDIP) derivatives with different annelation modes for which the most reactive position has been functionalized with (triisopropylsilyl)ethynyl (TIPS) groups. All the HDIP derivatives show remarkably higher stability than that of TIPS-pentacene, enduring for 2 days to more than 30 days, which depends on the oxidation potential, the contribution of the singlet biradical form in the ground state and the annelation mode. The annelation mode affects not only the band gap and the biradical character (y0) but also the value of the singlet–triplet energy gap (ΔES–T) that does not follow the reverse trend of y0. A method based on comparison between experimental and theoretical bond lengths has been disclosed to estimate y0 and shows that y0 computed at the projected unrestricted Hartree–Fock (PUHF) level is the most relevant among those reported by all other methods. Thanks to their high stability, thin-film OFETs were successfully fabricated. Well balanced ambipolar transport was obtained in the order of 10−3 cm2 V−1 s−1 in the bottom-gate/top-contact configuration, and unipolar transport in the top-gate/bottom-contact configuration was obtained in the order of 10−1 cm2 V−1 s−1 which is the highest value obtained for biradical compounds with a diindenoacene skeleton.Biradicaloid HDIP derivatives show that the ΔES–T gap does not follow the reverse trend of the biradical character but depends more on the delocalization of the radical centres at the outer rings.相似文献
We present analytical and numerical models of magnetohydrodynamic(MHD) buoyancy-driven flow within the liquid pool of a horizontal Bridgman crystal growth furnace, under the influence of a uniform vertical magnetic field B0. A horizontal differentially heated cylinder, whose aspect ratio (radius to length) is small enough for a fully developed regime to be established in the central core, is considered. With Hartmann layers remaining electrically inactive, a modified Rayleigh number RaG, which is the ration of the ordinary Rayleigh number to the square of the Hartmann number, is found to control the MHD reorganisation of the flow. This modified Rayleigh number is a measure of the importance of thermal convection relative to diffusion if velocity is estimated from the balance between the torques of buoyancy and the Laplace force. When RaG is much smaller than unity (quasi-diffusive regime), an analytical modelling of the flow, based on a power series of RaG, demonstrates that this balance requires secondary vortices within vertical mid-planes of the cylinder, both within the core flow and near the end walls. A 3-D numerical calculation of the flow provides evidence of the transition from a convective MHD flow (when RaG is still of the order of unity) to the quasi-diffusive flow, analytically studied. Indeed, this transition takes the form of a rather complex 3-D MHD organisation of the flow which is due to the nonuniformity of the axial temperature gradient along the cylinder. 相似文献
The depinning transition of a front moving in a time-independent random potential is studied. The temporal development of
the overall roughness w(L,t) of an initially flat front, , is the classical means to have access to the dynamic exponent. However, in the case of front propagation in quenched disorder
via extremal dynamics, we show that the initial increase in front roughness implies an extra dependence over the system size
which comes from the fact that the activity is essentially localized in a narrow region of space. We propose an analytic expression
for the exponent and confirm this for different models (crack front propagation, Edwards-Wilkinson model in a quenched noise etc.).
Received 27 August 1999 相似文献
The properties of poly(D ,L ‐lactide)‐block‐poly(2‐hydroxyethyl acrylate) (PLA‐b‐PHEA) block copolymers by means of in vitro / in vivo (rat) degradation are investigated and compared to those of PLA homopolymer. Over 12 weeks, we observe mass loss and molecular weight decrease. In vitro and in vivo findings are very similar for each polymer tested. When a short PHEA block is used (PLA‐b‐PHEA 15 000–3 000 g · mol?1, 85/15 wt%), the degradation process is found to be very similar to that of homo‐PLA, and to be typical of a bulk erosion mechanism, with no mass loss observed until week 7 and continuous decrease of molar mass within this timeframe. For a longer PHEA block length within the block copolymer (PLA‐b‐PHEA 15 000–7 500 g · mol?1, 65/35 wt%), the degradation mechanism is modified, with a significant mass loss observed at early times and only a slight decrease in molar mass. The latter finding is related to the pronounced hydrophilicity and softness of the material induced by the PHEA block, which allow easy diffusion and rapid leakage of the degradation residues from the material towards the aqueous medium. Schwann cells are found to better adhere on spin‐coated films of PLA‐b‐PHEA (85/15 wt%) than on PLA ones. These results show the potential of such hydrophilized PLA‐based copolymers for use in peripheral nerve repair.
High electron and hole (e-h) densities of about 1022 cm-3 have been produced in silicon, using 620 nm wavelength laser pulses of 100 fs duration. These density values are determined by measuring the dependence of the pulse self-reflectivity on its energy. By comparison with a fully non-linear model of light propagation, we show that dissipation processes inside the plasma are dominated by e-h collisions, with a characteristic time of 3 × 10-16s. The onset of melting within 100 fs and its nature, considering the high plasma density, are also discussed in view of scattered light measurements. 相似文献
The reaction of rare-earth nitrides with fluorides or the pyrolysis of these fluorides in gaseous ammonia atmosphere leads, in the case of lanthanum, cerium, and gadolinium, to nitride fluorides of general formula LnNxF3?3x. They crystallize with a fluorite-type structure which can be described in a consistent manner in terms of a Willis model. The magnetic properties of Gd3NF6 have been studied. 相似文献
Residual stress measurement using neutron diffraction is becoming an increasingly important tool in engineering stress analysis.
To this effect, a new generation of dedicated engineering strain instruments are being built at neutron sources, offering
considerable improvements in both counting time and spatial resolution. Alongside these improvements, measurements in complex
geometry prototype components are increasingly in demand. As a result, there is a strong drive towards integrated sample positioning
systems that allow for simplified setup and operating of experiments on components with complex geometries. 相似文献
The fabrication of water-in-oil emulsions is a process with widespread applications in formulation engineering. The most common process approach is to use a stirred vessel provided with a high speed dispersing impeller or a rotor-stator head and operated in batch or semi-batch mode. The mean drop size and the drop size distribution are usually correlated by the properties of the surfactants and the specific mechanical energy dissipated by the mixer among others. The present paper addresses an application in the oil industry: the large-scale manufacturing of a fine water-in-oil emulsion. Instead of using a tank-based operation, the idea is to create the emulsion in line and operate the process in a continuous mode. Several commercial in-line dispersing technologies are available and the purpose is here to determine the process and dispersing technology parameters that make possible the fabrication of a stable emulsion. Likewise in stirred tank, it is shown that apart from the energy dissipation rate, the kinetics properties of the surfactants and the process configuration also play a major role in obtaining a stable emulsion. 相似文献