Hugo Santos Silva

Increased thermal stabilization of polymer photovoltaic cells with oligomeric PCBM

The first oligomerisation of phenyl-C61-butyric acid methyl ester (PCBM) using a facile atom transfer radical addition polymerization (ATRAP) and its exploitation for organic photovoltaic devices is described. Oligo{(phenyl-C61-butyric acid methyl ester)-alt-[1,4-bis(bromomethyl)-2,5-bis(octyloxy)benzene]} (OPCBMMB) shows opto-electronic properties equivalent to those of PCBM but has a higher glass transition temperature. When mixed with various band gap semiconducting polymers, OPCBMMB delivers performances similar to PCBM but with an enhanced stabilization of the bulk heterojunction in photovoltaic devices on plastic substrates under thermal stress, regardless of the degree of crystallinity of the polymer and without changing opto-electronic properties.

Designing intrinsically photostable low band gap polymers: a smart tool combining EPR spectroscopy and DFT calculations

A rapid and efficient method to identify the weak points of the complex chemical structure of low band gap (LBG) polymers, designed for efficient solar cells, when submitted to light exposure is reported. This tool combines Electron Paramagnetic Resonance (EPR) using the ‘spin trapping method’ coupled with density functional theory modelling (DFT). First, the nature of the short life-time radicals formed during the early-stages of photo-degradation processes are determined by a spin-trapping technique. Two kinds of short life-time radical (R˙ and R′O˙) are formed after ‘short-duration’ illumination in an inert atmosphere and in ambient air, respectively. Second, simulation allows the identification of the chemical structures of these radicals revealing the most probable photochemical process, namely homolytical scission between the Si atom of the conjugated skeleton and its pendent side-chains. Finally, DFT calculations confirm the homolytical cleavage observed by EPR, as well as the presence of a group that is highly susceptible to photooxidative attack. Therefore, the synergetic coupling of a spin trapping method with DFT calculations is shown to be a rapid and efficient method for providing unprecedented information on photochemical mechanisms. This approach will allow the design of LBG polymers without the need to trial the material within actual solar cell devices, an often long and costly screening procedure.

Triplet States of Tetrazoles, Nitrenes and Carbenes from Matrix Photolysis of Tetrazoles, and Phenylcyanamide as a Source of Phenylnitrene

Photolysis of 1- and 5-aryltetrazoles at 5-10 K using a 266 nm laser immediately generates their triplet excited states, which are characterized by their electron spin resonance (ESR) spectra with zero-field splitting parameters D = 0.12-0.13 cm-1 and E = 0.002-0.008 cm-1. Further photolysis of all of the aryltetrazoles affords arylnitrenes ( D ≅ 1 cm-1), and in the case of 5-aryltetrazoles also arylcarbenes ( D ≅ 0.5 cm-1). The formation of arylnitrenes from 5-aryltetrazoles, where no aryl-N bond is present, is explained by the photochemical rearrangement of initially formed nitrile imines ArCN+N-R to carbodiimides. The monosubstituted carbodiimide PhN═C═NH isomerizes to phenylcyanamide, PhNH-CN, and photolysis of the latter causes rapid elimination of HCN and formation of phenylnitrene. When N-methyl groups are present in the tetrazoles, methylnitrene, CH3-N, is formed too. In the case of 5-phenyltetrazole, additional hydrogen shift and fragmentation afford cyano- and isocyanonitrenes, NCN and CNN.