An official website of the United States government
We measure and model monolayers of concentrated diffusing colloidal probes interacting with polymerized liquid crystal (PLC) planar surfaces. At topological defects in local nematic director profiles at PLC surfaces, we observe time-averaged two-dimensional particle density profiles of diffusing colloidal probes that closely correlate with spatial variations in PLC optical properties. An inverse Monte Carlo analysis of particle concentration profiles yields two-dimensional PLC interfacial energy landscapes on the kT -scale, which is the inherent scale of many interfacial phenomena ( e.g. , self-assembly, adsorption, diffusion). Energy landscapes are modelled as the superposition of macromolecular repulsion and van der Waals attraction based on an anisotropic dielectric function obtained from the liquid crystal birefringence. Modelled van der Waals landscapes capture most net energy landscape variations and correlate well with experimental PLC director profiles around defects. Some energy landscape variations near PLC defects indicate either additional local repulsive interactions or possibly the need for more rigorous van der Waals models with complete spectral data. These findings demonstrate direct, sensitive measurements of kT -scale van der Waals energy landscapes at PLC interfacial defects and suggest the ability to design interfacial anisotropic materials and van der Waals energy landscapes for colloidal assembly.
more »
« less
1D nanowires of non-centrosymmetric molecular semiconductors grown by physical vapor deposition
Understanding how dipolar, non-centrosymmetric organic semiconductors self-assemble, nucleate, and crystallize is integral for designing new molecular solids with unique physical properties and light-matter interactions. However, dipole–dipole and van der Waals interactions compete to direct the assembly of these compounds, making it difficult to predict how solids are formed from individual molecules. Here, we investigate four small molecules ( TpCPD , TpDCF , AcCPD , and AcDCF ) possessing anisotropic, non-planar structures and large dipole moments, and establish robust algorithms to control their molecular self-assembly via simple physical vapor deposition. Each molecule contains a central polar moiety, consisting of either a cyclopentadienone (CPD, ca. 3.5 D dipole moment) or dicyanofulvene (DCF, ca. 7.0 D dipole moment) core, that is surrounded by either four twisted phenyl (Tp) groups or a fused aromatic (acenaphthene, Ac) ring system. We find that only molecules containing the fused ring system form 1D nanowires due to the stronger van der Waals associations of the long, planar acenaphthene moieties. We examine the kinetics of self-assembly for AcDCF and create diverse 1D morphologies, including both curved and linear nanostructures. Finally, using conductive AFM (c-AFM) measurements, we show that 1D AcDCF wires support higher current densities relative to randomly-oriented clusters lacking long-range order.
more »
« less
- Award ID(s):
- 1706633
- PAR ID:
- 10175593
- Date Published:
- Journal Name:
- Molecular Systems Design & Engineering
- Volume:
- 5
- Issue:
- 1
- ISSN:
- 2058-9689
- Page Range / eLocation ID:
- 110 to 116
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Dipole-dipole interactions ( V dd ) between closely spaced atoms and molecules are related to real photon and virtual photon exchange between them and decrease in the near field connected with the characteristic Coulombic dipole field law. The control and modification of this marked scaling with distance have become a long-standing theme in quantum engineering since dipole-dipole interactions govern Van der Waals forces, collective Lamb shifts, atom blockade effects, and Förster resonance energy transfer. We show that metamaterials can fundamentally modify these interactions despite large physical separation between interacting quantum emitters. We demonstrate a two orders of magnitude increase in the near-field resonant dipole-dipole interactions at intermediate field distances (10 times the near field) and observe the distance scaling law consistent with a super-Coulombic interaction theory curtailed only by absorption and finite size effects of the metamaterial constituents. We develop a first-principles numerical approach of many-body dipole-dipole interactions in metamaterials to confirm our theoretical predictions and experimental observations. In marked distinction to existing approaches of engineering radiative interactions, our work paves the way for controlling long-range dipole-dipole interactions using hyperbolic metamaterials and natural hyperbolic two-dimensional materials.more » « less
-
Two-dimensional (2-D) atomically thin graphene has exhibited overwhelming excellent properties over its bulk counterpart graphite, yet the broad applications and explorations of its unprecedented properties require a diversity of its geometric morphologies, beyond its inherently planar structures. In this study, we present a self-folding approach for converting 2-D planar free-standing graphene to 2-D and 3-D folded structures through the evaporation of its liquid solutions. This approach involves competition between the surface energy of the liquid, and the deformation energy and van der Waals energy of graphene. An energy-based theoretical model is developed to describe the self-folding process during liquid evaporation by incorporating both graphene dimensions and surface wettability. The critical elastocapillary length by liquid evaporation is extracted and exemplified by investigating three typical graphene geometries with rectangular, circular and triangular shapes. After the complete evaporation of the liquid, the critical self-folding length of graphene that can enable a stable folded pattern by van der Waals energy is also obtained. In parallel, full-scale molecular dynamics (MD) simulations are performed to monitor the evolution of deformation energies and folded patterns with liquid evaporation. The simulation results demonstrate the formation of 2-D folded racket-like and 3-D folded cone-like patterns and show remarkable agreement with theoretical predictions in both energy variations and folded patterns. This work offers quantitative guidance for controlling the self-folding of graphene and other 2-D materials into complex structures by liquid evaporation.more » « less
-
Abstract Anisotropic planar polaritons - hybrid electromagnetic modes mediated by phonons, plasmons, or excitons - in biaxial two-dimensional (2D) van der Waals crystals have attracted significant attention due to their fundamental physics and potential nanophotonic applications. In this Perspective, we review the properties of planar hyperbolic polaritons and the variety of methods that can be used to experimentally tune them. We argue that such natural, planar hyperbolic media should be fairly common in biaxial and uniaxial 2D and 1D van der Waals crystals, and identify the untapped opportunities they could enable for functional (i.e. ferromagnetic, ferroelectric, and piezoelectric) polaritons. Lastly, we provide our perspectives on the technological applications of such planar hyperbolic polaritons.more » « less
-
Recently a new research field of quasi-one-dimensional (1D) van der Waals quantummaterials has emerged from earlier work on low-dimensional systems [1-2]. The quasi-1D van der Waalsmaterials have 1D motifs in their crystal structure [1]. Many of these materials reveal strongly correlatedphenomena such as charge density waves (CDW) [1-2]. The CDW phase is a periodic modulation of theelectronic charge density, accompanied by distortions in the underlying crystal lattice. Potential uses for CDWmaterials include memory storage and oscillators [3]. Raman spectroscopy can identify the CDW transitions todifferent phases via the appearance of phonon peaks due to emerging superstructure or the disappearance ofcertain peaks due to the loss of translation symmetry in the crystal lattice [3]. In this presentation, we report theresults of the angle and temperature-dependent Raman scattering spectroscopy investigation of themechanically exfoliated nanowires of the quasi-1D Nb van der Waals material. It is known that Nb forms in atetragonal crystal structure with space group 124 (P4/mcc). Recently, this material attracted attention as aCDW material with multiple phase transitions, some of them, possibly, near room temperature. Littleinformation is known on the Raman characteristics of this material. Our Raman data for different polarizationangles show strong anisotropy in the response depending on the crystal direction. The most pronouncedRaman peaks reveal strong temperature dependence. The results of the measurements will be compared withthe theoretical predictions. Our data is important for further investigation of this quasi-1D CDW material forpossible applications in phase-change memory and reconfigurable devices. A.A.B. acknowledges the support of the Vannevar Bush Faculty Fellowship (VBFF) from the Office of NavalResearch (ONR) contract N00014-21-1-2947 “One-Dimensional Quantum Materials” and the National ScienceFoundation (NSF) program Designing Materials to Revolutionize and Engineer our Future (DMREF) via aproject DMR-1921958 “Data-Driven Discovery of Synthesis Pathways and Distinguishing ElectronicPhenomena of 1D van der Waals Bonded Solids”. A. D. and S. K. acknowledge support through the MaterialGenome Initiative funding allocated to the National Institute of Standards and Technology. [1] A. A. Balandin, F. Kargar, T. T. Salguero, and R. Lake, “One-dimensional van der Waals quantummaterials", Mater. Today, 55, 74 (2022). [2] A. A. Balandin, R. K. Lake, and T. T. Salguero, "One-dimensional van der Waals materials - Advent of a newresearch field" Appl. Phys. Lett., 121, 040401 (2022). [3] A. A. Balandin, S. V. Zaitzev-Zotov, and G. Grüner, "Charge-density-wave quantum materials and devices—New developments and future prospects", Appl. Phys. Lett., 119, 170401 (2021). [4] R. Samnakay, et al., “Zone-folded phonons and the charge-density-wave transition in 1T-TaSe2 thin films, Nano Lett., 15, 2965 (2015).more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/C9ME00100J
