Piezoelectricity allows precise and robust conversion between electricity and mechanical force, and arises from the broken inversion symmetry in the atomic structure [1][2][3] . Reducing the dimensionality of bulk materials has been suggested to enhance piezoelectricity 4 . However, when the thickness of a material approaches a single molecular layer, the large surface energy can cause piezoelectric structures to be thermodynamically unstable 5 . Transition-metal dichalcogenides can retain their atomic structures down to the single-layer limit without lattice reconstruction, even under ambient conditions 6 . Recent calculations have predicted the existence of piezoelectricity in these two-dimensional crystals due to their broken inversion symmetry 7 . Here, we report experimental evidence of piezoelectricity in a free-standing single layer of molybdenum disulphide (MoS 2 ) and a measured piezoelectric coefficient of e 11 = 2.9 × 10 -10 C m −1 . The measurement of the intrinsic piezoelectricity in such free-standing crystals is free from substrate effects such as doping and parasitic charges. We observed a finite and zero piezoelectric response in MoS 2 in odd and even number of layers, respectively, in sharp contrast to bulk piezoelectric materials. This oscillation is due to the breaking and recovery of the inversion symmetry of the two-dimensional crystal. Through the angular dependence of electromechanical coupling, we determined the two-dimensional crystal orientation. The piezoelectricity discovered in this single molecular membrane promises new applications in low-power logic switches for computing and ultrasensitive biological sensors scaled down to a single atomic unit cell 8,9 .Since its discovery in 1880, piezoelectricity has found a wide range of applications in actuation, sensing and energy harvesting. The rapidly growing demand for high-performance and miniaturized devices in micro-electro-mechanical systems (MEMS) and electronics 10-12 calls for nanoscale piezoelectric materials, motivating theoretical investigations into novel low-dimensional systems such as nanotubes and single molecules 13,14 . Transition-metal dichalcogenides (TMDCs) are ideal candidates as low-dimensional piezoelectric materials because of their structural non-centrosymmetry 7 . Although there has been extensive research interest in the unique properties originating from such symmetry breaking, including circular dichroism and second harmonic generation (SHG) [15][16][17][18][19] , experimental quantitative determination of the intrinsic piezoelectric properties of these two-dimensional crystals has yet to be demonstrated. Here, we report the observation of piezoelectricity in freestanding monolayer MoS 2 membranes. Interestingly, we found that this molecular piezoelectricity only exists when there are an odd number of layers in the two-dimensional crystal where inversion symmetry breaking occurs. We observed an angular dependence of the piezoelectric response in agreement with the three-fold symmetry of the crystal, and based...

The mechanical reinforcement of polymer nanocomposites (PNCs) above the glass transition temperature, Tg, has been extensively studied. However, not much is known about the origin of this effect below Tg. In this Letter, we unravel the mechanism of PNC reinforcement within the glassy state by directly probing nanoscale mechanical properties with atomic force microscopy and macroscopic properties with Brillouin light scattering. Our results unambiguously show that the "glassy" Young's modulus in the interfacial polymer layer of PNCs is two-times higher than in the bulk polymer, which results in significant reinforcement below Tg. We ascribe this phenomenon to a high stretching of the chains within the interfacial layer. Since the interfacial chain packing is essentially temperature independent, these findings provide a new insight into the mechanical reinforcement of PNCs also above Tg.

In this article, we report the synthesis, structures, morphologies, and electrochromic properties of covalently bonded polyaniline (PANI)-TiO 2 hybrids. The hybrids were synthesized via a sol-gel process, followed by oxidative polymerization, using a bifunctional compound to bridge the two phases. In comparison with PANI, the hybrids show significant enhancement in optical contrast and coloration efficiency. Furthermore, when covalently bonded to PANI, the TiO 2 nanodomains can act as electron acceptors, reducing the oxidation potential and band gap of PANI, and improving the long-term electrochromic stability.

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Hybrid electrochromic materials were readily synthesized via copolymerization of aniline with p-phenylenediamine-functionalized single-walled carbon nanotubes (SWCNTs) in the presence of poly(styrene sulfonate) (PSS) dopant in an aqueous medium. Polyaniline (PANI)-grafted SWCNTs are formed, and they are uniformly dispersed in the PANI/PSS matrix. Impedance analysis shows that the charge-transfer resistances of the hybrids at all states are reduced drastically with increasing SWCNT loading. With 0.8 wt % SWCNTs, the charge-transfer resistances of the hybrid at +1.5 and -1.5 V are only about 20% and 12% of those of PANI/PSS, respectively, which is due to the greatly increased redox reactivity given by the enhanced electron transport in the hybrid and further doping function of the SWCNTs. The remarkable increase in redox reactivity leads to much enhanced electrochromic contrast from 0.34 for PANI to 0.47 for PANI-SWCNT-0.8%.

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