Fullerene van der waals Oligomers as electron traps

Density functional theory calculations indicate that van der Waals fullerene dimers and larger oligomers can form interstitial electron traps in which the electrons are even more strongly bound than in isolated fullerene radical anions. The fullerenes behave like super atoms , and the interstitial electron traps represent one-electron intermolecular σ-bonds. Spectroelectrochemical measurements on a bis-fullerene-substituted peptide provide experimental support. The proposed deep electron traps are relevant for all organic electronics applications in which non-covalently linked fullerenes in van der Waals contact with one another serve as n-type semiconductors

2D van der waals heterojunction of organic and inorganic monolayers for high responsivity phototransistors

Van der Waals (vdW) heterostructures composing of organic molecules with inorganic 2D crystals open the door to fabricate various promising hybrid devices. Here, a fully ordered organic self‐assembled monolayer (SAM) to construct hybrid organic–inorganic vdW heterojunction phototransistors for highly sensitive light detection is used. The heterojunctions, formed by layering MoS 2 monolayer crystals onto organic [12‐(benzo[b]benzo[4,5]thieno[2,3‐d]thiophen‐2‐yl)dodecyl)]phosphonic acid SAM, are characterized by Raman and photoluminescence spectroscopy as well as Kelvin probe force microscopy. Remarkably, this vdW heterojunction transistor exhibits a superior photoresponsivity of 475 A W −1 and enhanced external quantum efficiency of 1.45 × 10 5 %, as well as an extremely low dark photocurrent in the pA range. This work demonstrates that hybridizing SAM with 2D materials can be a promising strategy for fabricating diversified optoelectronic devices with unique properties

Driving forces for the self-assembly of graphene oxide on organic monolayers

Graphene oxide (GO) flakes were self-assembled from solution on surfaces of self-assembled monolayers (SAMs), varying in the chemical structure of their head groups. The coverage density of GO relates to strength of attractive interaction, which is largest for Coulomb interaction provided by positively charged SAM head groups and negatively charged GO. A rough surface enhances the coverage density but with the same trend in driving force dependency. The self-assembly approach was used to fabricate field-effect transistors with reduced GO (rGO) as active layer. The SAMs as attractive layer for self-assembly remain almost unaffected by the reduction from GO to rGO and serve as ultra-thin gate dielectrics in devices, which operate at low voltages of maximum 3 V and exhibit a shift of the Dirac voltage related to the dipole moment of the SAMs

Scalable self-assembled reduced graphene oxide transistors on flexible substrate

To enable graphene oxide (GO) flakes for application based on solution processable technology, we show that they can be self-assembled from solution on flexible substrate driven by a Coulomb interaction with the self-assembled monolayer (SAM). Field-effect transistors exhibit a high hole mobility around 14 cm2/V·s after a reduction process from GO to reduced GO (rGO), and meanwhile the device resistance shows a linear scaling behavior with the channel length. Due to the flexibility of the SAM, the device parameters maintain stable, while different strains are applied to the substrate. This approach makes the combination of rGO and SAM suitable for low-cost flexible applications

Solvent effects on the vibronic one-photon absorption profiles of dioxaborine heterocycles

© 2005 American Institute of Physics. The electronic version of this article is the complete one and can be found at: http://dx.doi.org/10.1063/1.2121590DOI: 10.1063/1.2121590The vibronic profiles of one-photon absorption spectra of dioxaborine heterocycles in gas phase and solution have been calculated at the Hartree-Fock and density-functional-theory levels. The polarizable continuum model has been applied to simulate the solvent effect, while the linear coupling model is used to compute the Franck-Condon and Herzberg-Teller contributions. It is found that a good agreement between theory and experiment can be achieved when the solvent effect and electron correlation are taken into account simultaneously. For the first excited charge-transfer state, the maximum of its Herzberg-Teller profile is blueshifted from that of the Franck-Condon profile. The shifted energy is found to be around 0.2 eV, which agrees well with the measured energy difference between two- and one-photon absorptions of the first excited state

Influence of self-assembled monolayer dielectrics on the morphology and performance of α,ω-dihexylquaterthiophene in thin film transistors

Three different ultrathin hybrid dielectrics based on self-assembled monolayers (SAMs) from phosphonic acid molecules were investigated on aluminum oxide. The impact of the underlying SAMs on the semiconductor morphology and transistor device performance was studied by reducing the film thickness of the subsequently deposited α,ω-dihexylquaterthiophene semiconductor to one monolayer and less. The nature of the SAM relates to the molecular orientation of submonolayer films, which is investigated by photoluminescence microscopy and atomic force microscopy. SAMs with high surface energy tend to induce a face-on growing of the semiconductor, whereas for SAMs with low surface energy an edge-on growth is favorable

Spatially Resolved Bottom‐Side Fluorination of Graphene by Two‐Dimensional Substrate Patterning

Patterned functionalization can, on the one hand, open the band gap of graphene and, on the other hand, program demanding designs on graphene. The functionalization technique is essential for graphene‐based nanoarchitectures. A new and highly efficient method was applied to obtain patterned functionalization on graphene by mild fluorination with spatially arranged AgF arrays on the structured substrate. Scanning Raman spectroscopy (SRS) and scanning electron microscopy coupled with energy‐dispersive X‐ray spectroscopy (SEM‐EDS) were used to characterize the functionalized materials. For the first time, chemical patterning on the bottom side of graphene was realized. The chemical nature of the patterned functionalization was determined to be the ditopic scenario with fluorine atoms occupying the bottom side and moieties, such as oxygen‐containing groups or hydrogen atoms, binding on the top side, which provides information about the mechanism of the fluorination process. Our strategy can be conceptually extended to pattern other functionalities by using other reactants. Bottom‐side patterned functionalization enables utilization of the top side of a material, thereby opening up the possibilities for applications in graphene‐based devices

Manufacturing Nanoparticles with Orthogonally Adjustable Dispersibility in Hydrocarbons, Fluorocarbons, and Water

We describe a universal wet‐chemical shell‐by‐shell coating procedure resulting in colloidal titanium dioxide (TiO2) and iron oxide (Fe3O4) nanoparticles with dynamically and reversibly tunable surface energies. A strong covalent surface functionalization is accomplished by using long‐chained alkyl‐, triethylenglycol‐, and perfluoroalkylphosphonic acids, yielding highly stabilized core–shell nanoparticles with hydrophobic, hydrophilic, or superhydrophobic/fluorophilic surface characteristics. This covalent functionalization sequence is extended towards a second noncovalent attachment of tailor‐made nonionic amphiphilic molecules to the pristine coated core–shell nanoparticles via solvophobic (i.e. either hydrophobic, lipophobic, or fluorophobic) interactions. Thereby, orthogonal tuning of the surface energies of nanoparticles via noncovalent interactions is accomplished. As a result, this versatile bilayer coating process enables reversible control over the colloidal stability of the metal oxide nanoparticles in fluorocarbons, hydrocarbons, and water