scholarly journals Structural order enhances charge carrier transport in self-assembled Au-nanoclusters

2020 ◽  
Vol 11 (1) ◽  
Author(s):  
Florian Fetzer ◽  
Andre Maier ◽  
Martin Hodas ◽  
Olympia Geladari ◽  
Kai Braun ◽  
...  

AbstractThe collective properties of self-assembled nanoparticles with long-range order bear immense potential for customized electronic materials by design. However, to mitigate the shortcoming of the finite-size distribution of nanoparticles and thus, the inherent energetic disorder within assemblies, atomically precise nanoclusters are the most promising building blocks. We report an easy and broadly applicable method for the controlled self-assembly of atomically precise Au32(nBu3P)12Cl8 nanoclusters into micro-crystals. This enables the determination of emergent optoelectronic properties which resulted from long-range order in such assemblies. Compared to the same nanoclusters in glassy, polycrystalline ensembles, we find a 100-fold increase in the electric conductivity and charge carrier mobility as well as additional optical transitions. We show that these effects are due to a vanishing energetic disorder and a drastically reduced activation energy to charge transport in the highly ordered assemblies. This first correlation of structure and electronic properties by comparing glassy and crystalline self-assembled superstructures of atomically precise gold nanoclusters paves the way towards functional materials with novel collective optoelectronic properties.

Soft Matter ◽  
2020 ◽  
Vol 16 (40) ◽  
pp. 9183-9187
Author(s):  
Camille Blayo ◽  
Elaine A. Kelly ◽  
Judith E. Houston ◽  
Nikul Khunti ◽  
Nathan P. Cowieson ◽  
...  

A cationic azobenzene photosurfactant (AzoTAB) forms self-assembled structures with long-range order and optical anisotropy at high concentrations. These high-concentration mesophases are lost or disrupted with UV irradiation.


2020 ◽  
Author(s):  
Jordan M Cox ◽  
Bradley Mileson ◽  
Ananthan Sadagopan ◽  
Steven Lopez

Covalent organic frameworks (COFs) have emerged as versatile, functional materials comprised of low-cost molecular building blocks. The permanent porosity, long-range order, and high surface area of 3D-COFs permit co-crystallization with other materials driven by supramolecular interactions. We designed a new subphthalocyanine-based 3-D covalent organic framework (NEUCOF1) capable of forming co-crystals with fullerene (C60) via periodic ball-and-socket binding motifs. The high co-crystalline surface area and long-range order of NEUCOF1 eliminates the typical surface area vs. structural order trade-off in organic photovoltaics (OPVs). We used plane-wave density functional theory (PBE) to minimize NEUCOF1 and NEUCOF1–C60 co-crystals and determine their electronic band structures. Molecular dynamics (MD) simulations showed that NEUCOF1–C60 is likely to be stable up to 350 K. The band structures at 0 and 350 K suggest that charge transfer to the C60 acceptors is favorable and that directional charge transport is possible for these co-crystalline OPVs.


2019 ◽  
Author(s):  
Jordan M Cox ◽  
Ananthan Sadagopan ◽  
Steven Lopez

Covalent organic frameworks (COFs) have emerged as versatile, functional materials comprised of low-cost molecular building blocks. The permanent porosity, long-range order, and high surface area of 3D-COFs permit co-crystallization with other materials driven by supramolecular interactions. We designed a new subphthalocyanine-based 3-D covalent organic framework (NEUCOF1) capable of forming co-crystals with fullerene (C60) via periodic ball-and-socket binding motifs. The high co-crystalline surface area and long-range order of NEUCOF1 eliminates the typical surface area vs. structural order trade-off in organic photovoltaics (OPVs). We used plane-wave density functional theory (PBE) to minimize NEUCOF1 and NEUCOF1–C60 co-crystals and determine their electronic band structures. Molecular dynamics (MD) simulations showed that NEUCOF1–C60 is likely to be stable up to 350 K. The band structures at 0 and 350 K suggest that charge transfer to the C60 acceptors is favorable and that directional charge transport is possible for these co-crystalline OPVs.


2020 ◽  
Author(s):  
Jordan M Cox ◽  
Bradley Mileson ◽  
Ananthan Sadagopan ◽  
Steven Lopez

Covalent organic frameworks (COFs) have emerged as versatile, functional materials comprised of low-cost molecular building blocks. The permanent porosity, long-range order, and high surface area of 3D-COFs permit co-crystallization with other materials driven by supramolecular interactions. We designed a new subphthalocyanine-based 3-D covalent organic framework (NEUCOF1) capable of forming co-crystals with fullerene (C60) via periodic ball-and-socket binding motifs. The high co-crystalline surface area and long-range order of NEUCOF1 eliminates the typical surface area vs. structural order trade-off in organic photovoltaics (OPVs). We used plane-wave density functional theory (PBE) to minimize NEUCOF1 and NEUCOF1–C60 co-crystals and determine their electronic band structures. Molecular dynamics (MD) simulations showed that NEUCOF1–C60 is likely to be stable up to 350 K. The band structures at 0 and 350 K suggest that charge transfer to the C60 acceptors is favorable and that directional charge transport is possible for these co-crystalline OPVs.


2010 ◽  
Vol 459 ◽  
pp. 124-128 ◽  
Author(s):  
Takashi Akahane ◽  
Miftakhul Huda ◽  
You Yin ◽  
Sumio Hosaka

In this paper, we report two kinds of guide patterns precisely created by electron beam drawing. These guide patterns are expected to precisely control the arrangement of nanodots self-assembled from block copolymer (BCP) in order to obtain long-range-order nanofabrication. The first guide pattern is comprised only of a post lattice. The second guide pattern adds guide lines to the post lattice. The added guide lines are expected to better control the location and orientation of the BCP nanodots. We succeeded in fabricating these two kinds of guide patterns for 22-nm- and 33-nm-pitch BCP nanodots.


MRS Bulletin ◽  
2008 ◽  
Vol 33 (9) ◽  
pp. 854-863 ◽  
Author(s):  
S.V. Sreenivasan

AbstractImprint lithography has a remarkable patterning resolution of less than 5 nm, and it is simultaneously capable of patterning over large areas with long-range order. This combination enables a broad range of potential applications including terabit-density magnetic storage, CMOS integrated circuits, and nanowire molecular memory. This article provides a review of the status of imprint lithography for nanoscale manufacturing. First, representative nanoscale devices and their manufacturing requirements are reviewed, along with key patterning challenges that have to be overcome to enable these nanoscale applications. Two classes of top–down nanopatterning techniques, namely, photon-based lithography and proximity mechanical nanopatterning (including imprint lithography), are described, followed by the three primary building blocks of imprint lithography: imprint masks, tools, and materials. Theresults of the lithography process are detailed in terms of process data such as long-range order in the placement and size of the nanostructures, process throughput, and overall cost considerations.


Author(s):  
Norman J. Morgenstern Horing

Chapter 13 addresses Bose condensation in superfluids (and superconductors), which involves the field operator ψ‎ having a c-number component (<ψ(x,t)>≠0), challenging number conservation. The nonlinear Gross-Pitaevskii equation is derived for this condensate wave function<ψ>=ψ−ψ˜, facilitating identification of the coherence length and the core region of vortex motion. The noncondensate Green’s function G˜1(1,1′)=−i<(ψ˜(1)ψ˜+(1′))+> and the nonvanishing anomalous correlation function F˜∗(2,1′)=−i<(ψ˜+(2)ψ˜+(1′))+> describe the dynamics and elementary excitations of the non-condensate states and are discussed in conjunction with Landau’s criterion for viscosity. Associated concepts of off-diagonal long-range order and the interpretation of <ψ> as a superfluid order parameter are also introduced. Anderson’s Bose-condensed state, as a phase-coherent wave packet superposition of number states, resolves issues of number conservation. Superconductivity involves bound Cooper pairs of electrons capable of Bose condensation and superfluid behavior. Correspondingly, the two-particle Green’s function has a term involving a product of anomalous bound-Cooper-pair condensate wave functions of the type F(1,2)=−i<(ψ(1)ψ(2))+>≠0, such that G2(1,2;1′,2′)=F(1,2)F+(1′,2′)+G˜2(1,2;1′,2′). Here, G˜2 describes the dynamics/excitations of the non-superfluid-condensate states, while nonvanishing F,F+ represent a phase-coherent wave packet superposition of Cooper-pair number states and off-diagonal long range order. Employing this form of G2 in the G1-equation couples the condensed state with the non-condensate excitations. Taken jointly with the dynamical equation for F(1,2), this leads to the Gorkov equations, encompassing the Bardeen–Cooper–Schrieffer (BCS) energy gap, critical temperature, and Bogoliubov-de Gennes eigenfunction Bogoliubons. Superconductor thermodynamics and critical magnetic field are discussed. For a weak magnetic field, the Gorkov-equations lead to Ginzburg–Landau theory and a nonlinear Schrödinger-like equation for the pair wave function and the associated supercurrent, along with identification of the Cooper pair density. Furthermore, Chapter 13 addresses the apparent lack of gauge invariance of London theory with an elegant variational analysis involving re-gauging the potentials, yielding a manifestly gauge invariant generalization of the London equation. Consistency with the equation of continuity implies the existence of Anderson’s acoustic normal mode, which is supplanted by the plasmon for Coulomb interaction. Type II superconductors and the penetration (and interaction) of quantized magnetic flux lines are also discussed. Finally, Chapter 13 addresses Josephson tunneling between superconductors.


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