Ambient stability of colloidal nanocrystal quantum dots (QDs) is imperative for low-cost, high-efficiency QD photovoltaics. We synthesized air-stable, ultrasmall PbS QDs with diameter (D) down to 1.5 nm, and found an abrupt transition at D ≈ 4 nm in the air stability as the QD size was varied from 1.5 to 7.5 nm. X-ray photoemission spectroscopy measurements and density functional theory calculations reveal that the stability transition is closely associated with the shape transition of oleate-capped QDs from octahedron to cuboctahedron, driven by steric hindrance and thus size-dependent surface energy of oleate-passivated Pb-rich QD facets. This microscopic understanding of the surface chemistry on ultrasmall QDs, up to a few nanometers, should be very useful for precisely and accurately controlling physicochemical properties of colloidal QDs such as doping polarity, carrier mobility, air stability, and hot-carrier dynamics for solar cell applications.
Antiferroelectrics are essential ingredients for the widely applied piezoelectric and ferroelectric materials: the most common ferroelectric, lead zirconate titanate is an alloy of the ferroelectric lead titanate and the antiferroelectric lead zirconate. Antiferroelectrics themselves are useful in large digital displacement transducers and energy-storage capacitors. Despite their technological importance, the reason why materials become antiferroelectric has remained allusive since their first discovery. Here we report the results of a study on the lattice dynamics of the antiferroelectric lead zirconate using inelastic and diffuse X-ray scattering techniques and the Brillouin light scattering. The analysis of the results reveals that the antiferroelectric state is a 'missed' incommensurate phase, and that the paraelectric to antiferroelectric phase transition is driven by the softening of a single lattice mode via flexoelectric coupling. These findings resolve the mystery of the origin of antiferroelectricity in lead zirconate and suggest an approach to the treatment of complex phase transitions in ferroics.
The fast degradation of lead selenide (PbSe) nanocrystal quantum dots (NQDs) in ambient conditions impedes widespread deployment of the highly excitonic, thus versatile, colloidal NQDs. Here we report a simple in situ post-synthetic halide salt treatment that results in size-independent air stability of PbSe NQDs without significantly altering their optoelectronic characteristics. From TEM, NMR, and XPS results and DFT calculations, we propose that the unprecedented size-independent air stability of the PbSe NQDs can be attributed to the successful passivation of under-coordinated PbSe(100) facets with atomically thin PbX2 (X = Cl, Br, I) adlayers. Conductive films made of halide-treated ultrastable PbSe NQDs exhibit markedly improved air stability and behave as an n-type channel in a field-effect transistor. Our simple in situ wet-chemical passivation scheme will enable broader utilization of PbSe NQDs in ambient conditions in many optoelectronic applications.
Atomically thin graphene is an ideal model system for studying nanoscale friction due to its intrinsic two-dimensional (2D) anisotropy. Furthermore, modulating its tribological properties could be an important milestone for graphene-based micro- and nanomechanical devices. Here, we report unexpectedly enhanced nanoscale friction on chemically modified graphene and a relevant theoretical analysis associated with flexural phonons. Ultrahigh vacuum friction force microscopy measurements show that nanoscale friction on the graphene surface increases by a factor of 6 after fluorination of the surface, while the adhesion force is slightly reduced. Density functional theory calculations show that the out-of-plane bending stiffness of graphene increases up to 4-fold after fluorination. Thus, the less compliant F-graphene exhibits more friction. This indicates that the mechanics of tip-to-graphene nanoscale friction would be characteristically different from that of conventional solid-on-solid contact and would be dominated by the out-of-plane bending stiffness of the chemically modified graphene. We propose that damping via flexural phonons could be a main source for frictional energy dissipation in 2D systems such as graphene.
The acoustic anomalies and precursor dynamics of high-quality barium titanate single crystals were investigated by Brillouin light scattering and the birefringence measurements in the paraelectric phase above the cubic-totetragonal ferroelectric phase transition temperature (T c ). Two elastic stiffness coefficients C 11 and C 44 , the related sound velocities, and their absorption coefficients were determined from T c to 400 • C for the first time. The longitudinal acoustic (LA) mode showed a substantial softening over a wide temperature range above T c which was accompanied by a remarkable increase in the acoustic damping as well as growth of central peaks. The broad central peak (CP) exhibited a two-mode and one-mode behavior in the paraelectric and ferroelectric phase, respectively, which was consistent with recent far-infrared reflectivity measurements and first-principle-based calculations [Ponomareva et al., Phys. Rev. B 77, 012102 (2008)]. The acoustic anomalies and CP behavior were correlated with the anomalous birefringence, piezoelectric effect, and the deviation of the Curie-Weiss law observed from the same crystal. This strongly indicates similarity between the dynamics of polar clusters in typical ferroelectrics and the dynamics of polar nanoregions in relaxors, consistent with recent acoustic emission measurements [Dul'kin et al., Appl. Phys. Lett. 97, 032903 (2010)]. The relaxation times estimated from the central peak and the LA mode anomalies exhibited similar temperature dependences with comparable orders of magnitude, indicating that the polarization fluctuations due to the precursor polar clusters couples to the LA mode through density fluctuations. All these anomalies share common microscopic origin, correlated Ti off-centered motions forming polar clusters having local symmetry breaking in the paraelectric phase. The existence of the polar clusters were directly evidenced by the temperature evolution of the precise birefringence map. The narrow central peak within ±5 GHz proposed before was not confirmed to exist in the present study.
Common experience shows that friction converts mechanical energy into heat. The first part of this process is vibrational excitation of atoms at the interface between rubbing bodies. The second part is the removal of the vibration energy by transferring it from the interface to the substrate. However, it is difficult to disentangle the excitation and energy transfer processes. We solved this by using a system consisting of a SiO-terminated tip sliding over graphene deposited on mica with intercalated water between them. The intercalated water was found to increase friction by a factor of ∼3 relative to dry mica. Density functional theory calculations show that water broadens the spectral range of graphene vibrations-particularly the low-frequency flexural modes-thus providing new excitation channels and also by increasing the overlap with the atomic vibrations of the mica substrate, which facilitates coupling and energy transfer.
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