Search for: All records

Incorporating molecular nanolayers (MNLs) at inorganic interfaces offers promise for reaping unusual enhancements in fracture energy, thermal and electrical transport. Here, we reveal that multilayering MNL-bonded inorganic interfaces can result in viscoelastic damping bandgaps. Molecular dynamics simulations of Au/octanedithiol MNL/Au multilayers reveal high-damping-loss frequency bands at 33 ≤ ν ≤ 77 GHz and 278 ≤ ν ≤ 833 GHz separated by a low-loss bandgap 77 ≤ ν ≤ 278 GHz region. The viscoelastic bandgap scales with the Au/MNL interface bonding strength and density, and MNL coverage. These results and the analyses of interfacial vibrations indicate that the viscoelastic bandgap is an interface effect that cannot be explained by weighted averages of bulk responses. These findings prognosticate a variety of possibilities for accessing and tuning novel dynamic mechanical responses in materials systems and devices with significant inorganic–organic interface fractions for many applications, e.g., smart composites and sensors with self-healing/-destructing mechanical responses.

 

Advances in interface science over the last 20 years have demonstrated the use of molecular nanolayers (MNLs) at inorganic interfaces to access emergent phenomena and enhance a variety of interfacial properties. Here, we capture important aspects of how a MNL can induce multifold enhancements and tune multiple interfacial properties, including chemical stability, fracture energy, thermal and electrical transport, and electronic structure. Key challenges that need to be addressed for the maturation of this emerging field are described and discussed. MNL-induced interfacial engineering has opened up attractive opportunities for designing organic–inorganic hybrid nanomaterials with high interface fractions, where properties are determined predominantly by MNL-induced interfacial effects for applications. 

Controlling nanoporosity to favorably alter multiple properties in layered crystalline inorganic thin films is a challenge. Here, we demonstrate that the thermoelectric and mechanical properties of Ca 3 Co 4 O 9 films can be engineered through nanoporosity control by annealing multiple Ca(OH) 2 /Co 3 O 4 reactant bilayers with characteristic bilayer thicknesses (b t ). Our results show that doubling b t , e.g. , from 12 to 26 nm, more than triples the average pore size from ∼120 nm to ∼400 nm and increases the pore fraction from 3% to 17.1%. The higher porosity film exhibits not only a 50% higher electrical conductivity of σ ∼ 90 S cm −1 and a high Seebeck coefficient of α ∼ 135 μV K −1 , but also a thermal conductivity as low as κ ∼ 0.87 W m −1 K −1 . The nanoporous Ca 3 Co 4 O 9 films exhibit greater mechanical compliance and resilience to bending than the bulk. These results indicate that annealing reactant multilayers with controlled thicknesses is an attractive way to engineer nanoporosity and realize mechanically flexible oxide-based thermoelectric materials.