Precise engineering of quantum dot array coupling through their barrier widths

Quantum dots are known to confine electrons within their structure. Whenever they periodically aggregate into arrays and cooperative interactions arise, novel quantum properties suitable for technological applications show up. Control over the potential barriers existing between neighboring quantum dots is therefore essential to alter their mutual crosstalk. Here we show that precise engineering of the barrier width can be experimentally achieved on surfaces by a single atom substitution in a haloaromatic compound, which in turn tunes the confinement properties through the degree of quantum dot intercoupling. We achieved this by generating self-assembled molecular nanoporous networks that confine the twodimensional electron gas present at the surface. Indeed, these extended arrays form up on bulk surface and thin silver films alike, maintaining their overall interdot coupling. These findings pave the way to reach full control over two-dimensional electron gases by means of self-assembled molecular networks

Zigzag-Elongated Fused π-Electronic Core: A Molecular Design Strategy to Maximize Charge-Carrier Mobility

Printed and flexible electronics requires solution‐processable organic semiconductors with a carrier mobility (μ) of ≈10 cm2 V−1 s−1 as well as high chemical and thermal durability. In this study, chryseno[2,1‐b:8,7‐b′]dithiophene (ChDT) and its derivatives, which have a zigzag‐elongated fused π‐electronic core (π‐core) and a peculiar highest occupied molecular orbital (HOMO) configuration, are reported as materials with conceptually new semiconducting π‐cores. ChDT and its derivatives are prepared by a versatile synthetic procedure. A comprehensive investigation reveals that the ChDT π‐core exhibits increasing structural stability in the bulk crystal phase, and that it is unaffected by a variation of the transfer integral, induced by the perpetual molecular motion of organic materials owing to the combination of its molecular shape and its particular HOMO configuration. Notably, ChDT derivatives exhibit excellent chemical and thermal stability, high charge‐carrier mobility under ambient conditions (μ ≤ 10 cm2 V−1 s−1), and a crystal phase that is highly stable, even at temperatures above 250 °C

High Performance Oxygen-bridged N-shaped Semiconductors with Stabilized Crystal Phase and Blue Luminescence

Here, we describe an oxygen-bridged N-shaped π-electron core, dinaphtho[2,3-d:2\u27,3\u27-d"]benzo[1,2-b:4,5-b\u27]difuran (DNBDF), as a new entity of organic semiconducting materials. Interestingly, by introduction of flexible alkyl chains at appropriate positions, DNBDF π-cores exhibit solution processability, a highly stabilized crystal phase, high mobility, and blue luminescence as a solid.平成26年度関西大学若手研究者育成経費JSPS科学研究費補助金　若手研究(B)(No.25810118)JSPS科学研究費補助金　基盤研究(C)(No.26410254)JSPS科学研究費補助金　基盤研究(B)(No.25288091

Mixed-Orbital Charge Transport in N-Shaped Benzene- and Pyrazine-Fused Organic Semiconductors.

The hole-carrier transport of organic semiconductors is widely known to occur via intermolecular orbital overlaps of the highest occupied molecular orbitals (HOMO), though the effect of other occupied molecular orbitals on charge transport is rarely investigated. In this work, we first demonstrate evidence of a mixed-orbital charge transport concept in the high-performance N-shaped decyl-dinaphtho[2,3-d:2',3'-d']benzo[1,2-b:4,5-b']dithiophene (C10-DNBDT-NW), where electronic couplings of the second HOMO (SHOMO) and third HOMO (THOMO) also contribute to the charge transport. We then present the molecular design of an N-shaped bis(naphtho[2',3':4,5]thieno)[2,3-b:2',3'-e]pyrazine (BNTP) π-electron system to induce more pronounced mixed-orbital charge transport by incorporating the pyrazine moiety. An effective synthetic strategy for the pyrazine-fused extended π-electron system is developed. With substituent engineering, the favorable two-dimensional herringbone assembly can be obtained with BNTP, and the decylphenyl-substituted BNTP (C10Ph-BNTP) demonstrates large electronic couplings involving the HOMO, SHOMO, and THOMO in the herringbone assembly. C10Ph-BNTP further shows enhanced mixed-orbital charge transport when the electronic couplings of all three occupied molecular orbitals are taken into consideration, which results in a high hole mobility up to 9.6 cm2 V-1 s-1 in single-crystal thin-film organic field-effect transistors. The present study provides insights into the contribution of HOMO, SHOMO, and THOMO to the mixed-orbital charge transport of organic semiconductors

Organometallic Bonding in an Ullmann-Type On-Surface Chemical Reaction Studied by High-Resolution Atomic Force Microscopy

The on-surface Ullmann-type chemical reaction synthesizes polymers by linking carbons of adjacent molecules on solid surfaces. Although an organometallic compound is recently identified as the reaction intermediate, little is known about the detailed structure of the bonded organometallic species and its influence on the molecule and the reaction. Herein atomic force microscopy at low temperature is used to study the reaction with 3,9-diiododinaphtho[2,3-b:2′,3′-d]thiophene (I-DNT-VW), which is polymerized on Ag(111) in vacuum. Thermally sublimated I-DNT-VW picks up a Ag surface atom, forming a C[BOND]Ag bond at one end after removing an iodine. The C[BOND]Ag bond is usually short-lived, and a C[BOND]Ag[BOND]C organometallic bond immediately forms with an adjacent molecule. The existence of the bonded Ag atoms strongly affects the bending angle and adsorption height of the molecular unit. Density functional theory calculations reveal the bending mechanism, which reveals that charge from the terminus of the molecule is transferred via the Ag atom into the organometallic bond and strengths the local adsorption to the substrate. Such deformations vanish when the Ag atoms are removed by annealing and C[BOND]C bonds are established

Naphtho[2,1-<i>b</i>:6,5-<i>b</i>′]difuran: A Versatile Motif Available for Solution-Processed Single-Crystal Organic Field-Effect Transistors with High Hole Mobility

We here report naphtho­[2,1-<i>b</i>:6,5-<i>b</i>′]­difuran derivatives as new p-type semiconductors that achieve hole mobilities of up to 3.6 cm² V^–1 s^–1 along with high <i>I</i>_on/<i>I</i>_off ratios in solution-processed single-crystal organic field-effect transistors. These features originate from the dense crystal packing and the resulting large intermolecular π-orbital overlap as well as from the small reorganization energy, all of which originate from the small radius of an oxygen atom

Naphtho[2,1-<i>b</i>:6,5-<i>b</i>′]difuran: A Versatile Motif Available for Solution-Processed Single-Crystal Organic Field-Effect Transistors with High Hole Mobility

We here report naphtho­[2,1-<i>b</i>:6,5-<i>b</i>′]­difuran derivatives as new p-type semiconductors that achieve hole mobilities of up to 3.6 cm² V^–1 s^–1 along with high <i>I</i>_on/<i>I</i>_off ratios in solution-processed single-crystal organic field-effect transistors. These features originate from the dense crystal packing and the resulting large intermolecular π-orbital overlap as well as from the small reorganization energy, all of which originate from the small radius of an oxygen atom