Synthesis and characterization of naphthalimide-functionalized polynorbornenes

ABSTRACT: Highly fluorescent and photostable (2-alkyl)-1H-benzo[de]isoquinoline-1,3(2H)-diones with a polymerizable norbornene scaffold have been synthesized and polymerized using ring-opening metathesis polymerization. The monomers presented herein could be polymerized in a living fashion, using different comonomers and different monomer ratios. All obtained materials showed good film-forming properties and bright fluorescence caused by the incorporated push–pull chromophores. Additionally, one of the monomers containing a methylpiperazine functionality showed protonation-dependent photoinduced electron transfer which opens up interesting applications for logic gates and sensing. GRAPHICAL ABSTRACT: [Image: see text

Highly Norbornylated Cellulose and Its “Click” Modification by an Inverse-Electron Demand Diels–Alder (iEDDA) Reaction

A facile, catalyst-free synthesis of a norbornylated cellulosic material (NC) with a high degree of substitution (2.9) is presented by direct reaction of trimethylsilyl cellulose with norbornene acid chloride. The resulting NC is highly soluble in organic solvents and its reactive double bonds were exploited for the copper-free inverse-electron demand Diels–Alder (iEDDA) “click” reaction with 3,6-di(pyridin-2-yl)-1,2,4,5-tetrazine. Reaction kinetics are comparable to the well-known Huisgen type 1,3-dipolar cycloaddition of azide with alkynes, while avoiding toxic catalysts

Ligand-free preparation of polymer/CuInS2 nanocrystal films and the influence of 1,3-benzenedithiol on their photovoltaic performance and charge recombination properties

Bulk heterojunction solar cells based on conjugated polymer donors and fullerene-derivative acceptors received much attention in the last decade. Alternative acceptors like organic non-fullerene acceptors or inorganic nanocrystals have been investigated to a lesser extent, however, they also show great potential. In this study, one focus is set on the investigation of the in situ growth of copper indium sulfide nanocrystals in a conjugated polymer matrix. This preparation method allows fabricating a hybrid active layer without long-chained ligands, which could hinder charge separation and transport. On the contrary, surfactants for the passivation of the nanocrystal surface are missing. To tackle this problem, we modified the absorber layer with 1,3-benzenedithiol and investigated the influence on charge transfer and solar cell performance. Using ToF-SIMS measurements, we could show that 1,3-benzenedithiol is successfully incorporated and homogeneously distributed in the absorber layer, which significantly increases the power conversion efficiency of the corresponding solar cells. This can be correlated with an improved charge transfer between the nanocrystals and the conjugated polymer as revealed by transient absorption spectroscopy as well as prolonged carrier lifetimes as disclosed from transient photovoltage measurements

A pyrrolopyridazinedione-based copolymer for fullerene-free organic solar cells

The recent success of non-fullerene acceptors in organic photovoltaics also entails a change in the requirements to the polymer donor in terms of optical and morphological properties leading to a demand for novel conjugated polymers. Herein, we report on the synthesis of a 1,4-bis-(thiophene-2-yl)-pyrrolopyridazinedione based copolymer with 2-ethylhexyl substituents on the pyrrolopyridazinedione moiety. A 2D conjugated benzodithiophene (BDT) was chosen as comonomer. The resulting copolymer T-EHPPD-T-EHBDT showed a molecular weight of 10.2 kDa, an optical band gap of 1.79 eV, a hole mobility of 1.8 × 10−4 cm2 V−1 s−1 and a preferred face-on orientation with regard to the substrate. The comparably wide band gap as well as the determined energy levels (HOMO: −5.47 eV, LUMO: −3.68 eV) match well with the narrow band gap non-fullerene acceptor ITIC-F, which was used as the acceptor phase in the bulk heterojunction absorber layers in the investigated solar cells. The solar cells, prepared in inverted architecture, revealed power conversion efficiencies up to 7.4% using a donor:acceptor ratio of 1 : 1 in the absorber layer

Nanoimprinted Comb Structures in a Low Bandgap Polymer: Thermal Processing and Their Application in Hybrid Solar Cells

In this paper, we investigate conjugated polymer layers structured by nanoimprint lithography toward their suitability for the fabrication of nanostructured polymer/metal sulfide hybrid solar cells. Consequently, we first study the thermal stability of the nanoimprinted conjugated polymer layers by means of scanning electron microscopy and grazing incidence small-angle X-ray scattering, which reveals a reasonable thermal stability up to 145 °C and sufficient robustness against the solvent mixture used in the subsequent fabrication process. In the second part, we demonstrate the preparation of nanostructured polymer/copper indium sulfide hybrid solar cells via the infiltration and thermal decomposition of a mixture of copper and indium xanthates. Although this step needs temperatures of more than 160 °C, the nanostructures are retained in the final polymer/copper indium sulfide layers. The nanostructured solar cells show significantly improved power conversion efficiencies compared to similarly prepared flat bilayer devices, which is based on a distinct improvement of the short circuit current in the nanostructured solar cells