Joseph Cameron

Oligothiophene Cruciform with a Germanium Spiro Center: A Promising Material for Organic Photovoltaics†

A fascinating packing motif is observed in a novel cruciform oligothiophene containing a Ge (violet; see picture) spiro center. Long-range interchain interactions between molecules and strong electronic coherence between orthogonal chains within the molecules are present. Such ordering is advantageous for bulk charge transport, as demonstrated by high short-circuit currents in bulk heterojunction organic solar cells.

Solution processable diketopyrrolopyrrole (DPP) cored small molecules with BODIPY end groups as novel donors for organic solar cells

Summary Two novel triads based on a diketopyrrolopyrrole (DPP) central core and two 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) units attached by thiophene rings have been synthesised having high molar extinction coefficients. These triads were characterised and used as donor materials in small molecule, solution processable organic solar cells. Both triads were blended with PC71BM as an acceptor in different ratios by wt % and their photovoltaic properties were studied. For both the triads a modest photovoltaic performance was observed, having an efficiency of 0.65%. Moreover, in order to understand the ground and excited state properties and vertical absorption profile of DPP and BODIPY units within the triads, theoretical DFT and TDDFT calculations were performed.

Thiazole-induced rigidification in substituted dithieno-tetrathiafulvalene: the effect of planarisation on charge transport properties.

Summary Two novel tetrathiafulvalene (TTF) containing compounds 1 and 2 have been synthesised via a four-fold Stille coupling between a tetrabromo-dithienoTTF 5 and stannylated thiophene 6 or thiazole 4. The optical and electrochemical properties of compounds 1 and 2 have been measured by UV–vis spectroscopy and cyclic voltammetry and the results compared with density functional theory (DFT) calculations to confirm the observed properties. Organic field effect transistor (OFET) devices fabricated from 1 and 2 demonstrated that the substitution of thiophene units for thiazoles was found to increase the observed charge transport, which is attributed to induced planarity through S–N interactions of adjacent thiazole nitrogen atoms and TTF sulfur atoms and better packing in the bulk.

Synthesis and properties of novel star-shaped oligofluorene conjugated systems with BODIPY cores

Summary Star-shaped conjugated systems with varying oligofluorene arm length and substitution patterns of the central BODIPY core have been synthesised, leading to two families of compounds, T-B1–T-B4 and Y-B1–Y-B4, with T- and Y-shaped motifs, respectively. Thermal stability, cyclic voltammetry, absorption and photoluminescence spectroscopy of each member of these two families were studied in order to determine their suitability as emissive materials in photonic applications.

Nanoparticles of Cu2ZnSnS4 as performance enhancing additives for organic field-effect transistors

The addition of oleylamine coated Cu2ZnSnS4 (CZTS) nanoparticles to solutions of an organic semiconductor used to fabricate organic field-effect transistors (OFETs) has been investigated. The oligothiophene-based small molecule 5T-TTF and the polymer poly(3-hexylthiophene) (P3HT) were each applied in the transistors with various concentrations of CZTS (5–20%). Atomic force microscopy (AFM) was applied to characterise the surface morphology of the OFETs. The use of 5 and 10 wt% of the CZTS nanoparticles in 5T-TTF and P3HT solutions, respectively, appears to be a simple and effective way of improving OFET performance.

Incorporation of perfluorohexyl-functionalised thiophenes into oligofluorene-truxenes: synthesis and physical properties.

Summary Oligofluorene-functionalised truxenes containing perfluorohexylthiophene units at the terminal positions on the arms were synthesised, and their optical and electrochemical properties were investigated to determine the effect that the perfluorohexylthiophene unit has on the HOMO and LUMO properties of the oligomers. By synthesising a molecule with longer oligofluorene arms the effects of the perfluorohexylthiophene unit on larger oligomers was explored. The effect of steric hindrance from the perfluorohexyl chain was also evaluated by altering the position of the chain on the thiophene moiety.

Acceptor–donor–acceptor small molecules based on derivatives of 3,4-ethylenedioxythiophene for solution processed organic solar cells

Three simple semiconducting acceptor–donor–acceptor (A–D–A) small molecules based on an electron-rich (3,4-ethylenedioxythiophene) EDOT central core have been synthesised (DIN-2TE, DRH-2TE, DECA-2TE) and characterised. Organic photovoltaic (OPV) devices incorporating these materials have been prepared and evaluated. The physical properties of the molecules were characterised by TGA, DSC, UV/vis spectroscopy and cyclic voltammetry. The optical HOMO–LUMO energy gaps of the molecules in the solid state were in the range 1.57–1.82 eV, and in solution 1.88–2.04 eV. Electrochemical HOMO–LUMO energy gaps determined by cyclic voltammetry were found to be in the range 1.97–2.31 eV. The addition of 1% 1,8-diiodooctane (DIO) to photoactive blends of the A–D–A molecules and PC71BM more than doubled the power conversion efficiency (PCE) in the case of DRH-2TE:PC71BM devices to 1.36%.

Investigating the effect of heteroatom substitution in 2,1,3-benzoxadiazole and 2,1,3-benzothiadiazole compounds for organic photovoltaics

Two new donor–acceptor−donor molecules, featuring either 2,1,3-benzothiadiazole (BT) or 2,1,3-benzoxadiazole (BO) and capped by benzofuranyl-thienyl groups, are presented. The structures of these novel compounds differ only in the identity of one heteroatom in the acceptor unit. Replacement of the sulfur atom in BT with oxygen results in a marked improvement in the performance of PC61BM blends in bulk heterojunction organic photovoltaic (BHJ OPV) devices: a 10-fold increase in PCE is observed when switching to the BO analogue. This is partly due to a preferable morphology in the donor-fullerene blends formed upon spin-coating from chlorinated solvents.