An official website of the United States government
Abstract 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.
more »
« less
Strain hardening and toughening in metal/molecular nanolayer/metal nanosandwiches
Introducing molecular nanolayers (MNLs) is attractive for enhancing the stability of, and inducing unusual properties at, inorganic thin film interfaces. Although organic molecules anchored to inorganic surfaces have been studied extensively, property enhancement mechanisms underpinned by molecular assemblies at inorganic thin film interfaces are yet to be revealed and understood. Here, ab initio molecular dynamics simulations of tensile strain of Au/MNL/Au thin film nanosandwich models provide insights into molecularly induced strain hardening and toughening. Au/MNL/Au nanosandwiches support up to ≈30% higher stresses and exhibit up to ≈140% higher toughness than pure Au slab models. Both hardening and toughening are governed by molecular length and terminal chemistry in the MNL. Strong Au/MNL interface bonding and greater molecular length promote defect creation in Au, which results in strain hardening. Accommodation of increasing post-hardening strains in the MNL mitigates the stress increase in the Au slabs, delays interface fracture, and contributes to toughening. Remarkably, toughening correlates with equilibrium interface strain, which could be used as a proxy for efficiently identifying promising inorganic/MNL combinations that provide toughening. Our findings are important for the discovery and design of inorganic–organic interfaces, nanomaterials, and composites.
more »
« less
- Award ID(s):
- 2135725
- PAR ID:
- 10595154
- Publisher / Repository:
- American Institute of Physics
- Date Published:
- Journal Name:
- Applied Physics Letters
- Volume:
- 124
- Issue:
- 26
- ISSN:
- 0003-6951
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
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.more » « less
-
A number of technological applications and scientific experiments require processes for preparing metal multilayers with electronically and thermally conductive interfaces. We investigate how in situ vs ex situ synthesis processes affect the thermal conductance of metal/metal interfaces. We use time-domain thermoreflectance experiments to study thermal transport in Au/Fe, Al/Cu, and Cu/Pt bilayer samples. We quantify the effect of exposing the bottom metal layer to an ambient environment prior to deposition of the top metal layer. We observe that for Au/Fe, exposure of the Fe layer to air before depositing the top Au layer significantly impedes interfacial electronic currents. Exposing Cu to air prior to depositing an Al layer effectively eliminates interfacial electronic heat currents between the two metal layers. Exposure to air appears to have no effect on interfacial transport in the Cu/Pt system. Finally, we show that a short RF sputter etch of the bottom layer surface is sufficient to ensure a thermally and electronically conductive metal/metal interface in all materials we study. We analyze our results with a two-temperature model and bound the electronic interface conductance for the nine samples we study. Our findings have applications for thin-film synthesis and advance fundamental understanding of electronic thermal conductance at different types of interfaces between metals.more » « less
-
Abstract Chirality is ubiquitous in nature and occurs at all length scales. The development of applications for chiral nanostructures is rising rapidly. With the recent achievements of atomically precise nanochemistry, total structures of ligand‐protected Au and other metal nanoclusters (NCs) are successfully obtained, and the origins of chirality are discovered to be associated with different parts of the cluster, including the surface ligands (e.g., swirl patterns), the organic–inorganic interface (e.g., helical stripes), and the kernel. Herein, a unified picture of metal–ligand surface bonding‐induced chirality for the nanoclusters is proposed. The different bonding modes of M–X (where M = metal and X = the binding atom of ligand) lead to different surface structures on nanoclusters, which in turn give rise to various characteristic features of chirality. A comparison of Au–thiolate NCs with Au–phosphine ones further reveals the important roles of surface bonding. Compared to the Au–thiolate NCs, the Ag/Cu/Cd–thiolate systems exhibit different coordination modes between the metal and the thiolate. Other than thiolate and phosphine ligands, alkynyls are also briefly discussed. Several methods of obtaining chiroptically active nanoclusters are introduced, such as enantioseparation by high‐performance liquid chromatography and enantioselective synthesis. Future perspectives on chiral NCs are also proposed.more » « less
-
Hybrid organic-inorganic materials are among the latest class of materials proposed for thermoelectric applications. The organic-inorganic interface is critical in determining the effective transport properties of the hybrid material. We study the thermoelectric properties of the tetrafluoro-tetracyanoquinodimethane (F4TCNQ)–silicon interface. Transfer of electrons from silicon to F4TCNQ results in holes trapped within the screening length of the interface that can move parallel to the interface. We measure the response of these trapped charges to applied temperature differential and compare the thermoelectric transport properties of the silicon with and without F4TCNQ. The results confirm the presence of interface charges and demonstrate an enhanced interface thermoelectric power factor. These outcomes of this study could be used in designing 3D hybrid structures with closely packed interfaces to replicate a bulk thermoelectric material.more » « less
