The Influence of Alkoxy Substitutions on the Properties of Diketopyrrolopyrrole-Phenyl Copolymers for Solar Cells.

A previously reported diketopyrrolopyrrole (DPP)-phenyl copolymer is modified by adding methoxy or octyloxy side chains on the phenyl spacer. The influence of these alkoxy substitutions on the physical, opto-electronic properties, and photovoltaic performance were investigated. It was found that the altered physical properties correlated with an increase in chain flexibility. Well-defined oligomers were synthesized to verify the observed structure-property relationship. Surprisingly, methoxy substitution on the benzene spacer resulted in higher melting and crystallization temperatures in the synthesized oligomers. This trend is not observed in the polymers, where the improved interactions are most likely counteracted by the larger conformational possibilities in the polymer chain upon alkoxy substitution. The best photovoltaic performance was obtained for the parent polymer: fullerene blends whereas the modifications on the other two polymers result in reduced open-circuit voltage and varying current densities under similar processing conditions. The current densities could be related to different polymer: fullerene blend morphologies. These results show that supposed small structural alterations such as methoxy substitution already significantly altered the physical properties of the parent polymer and also that oligomers and polymers respond divergent to structural alterations made on a parent structure.

Small band gap polymers synthesized via a modified nitration of 4,7-dibromo-2,1,3-benzothiadiazole.

The nitration of 4,7-dibromo-2,1,3-benzothiadiazole was modified by using CF(3)SO(3)H and HNO(3) as the nitrating agent, and the related yield was improved greatly. On the basis of this improvement, two new small band gap polymers, P1TPQ and P3TPQ, were developed. Bulk heterojunction solar cells based on P3TPQ and [6,6]-phenyl-C(71)-butyric acid methyl ester exhibit interesting results with a power conversion efficiency of 2.1% and photoresponse up to 1.1 µm.

Geminate charge recombination in polymer/fullerene bulk heterojunction films and implications for solar cell function.

We have studied the influence of three different fullerene derivatives on the charge generation and recombination dynamics of polymer/fullerene bulk heterojunction (BHJ) solar cell blends. Charge generation in APFO3/[70]PCBM and APFO3/[60]PCBM is very similar and somewhat slower than charge generation in APFO3/[70]BTPF. This difference qualitatively matches the trend in free energy change of electron transfer estimated from the LUMO energies of the polymer and fullerene derivatives. The first order (geminate) charge recombination rate is significantly different for the three fullerene derivatives studied and increases in the order APFO3/[70]PCBM < APFO3/[60]PCBM < APFO3/[70]BTPF. The variation in electron transfer rate cannot be explained from the LUMO energies of the fullerene derivatives and single-step electron transfer in the Marcus inverted region and simple considerations of expected trends for the reorganization energy and free energy change. Instead we suggest that geminate charge recombination occurs from a state where electrons and holes have separated to different distances in the various materials because of an initially high charge mobility, different for different materials. In a BHJ thin film this charge separation distance is not sufficient to overcome the electrostatic attraction between electrons and holes and geminate recombination occurs on the nanosecond to hundreds of nanoseconds time scale. In a BHJ solar cell, we suggest that the internal electric field in combination with polarization effects and the dynamic nature of polarons are key features to overcome electron-hole interactions to form free extractable charges.

Polymer photovoltaics with alternating copolymer/fullerene blends and novel device architectures.

The synthesis of novel conjugated polymers, designed for the purpose of photovoltaic energy conversion, and their properties in polymer/fullerene materials and photovoltaic devices are reviewed. Two families of main-chain polymer donors, based on fluorene or phenylene and donor-acceptor-donor comonomers in alternating copolymers, are used to absorb the high-energy parts of the solar spectrum and to give high photovoltages in combinations with fullerene acceptors in devices. These materials are used in alternative photovoltaic device geometries with enhanced light incoupling to collect larger photocurrents or to enable tandem devices and enhance photovoltage.

Structure-property relationships of small bandgap conjugated polymers for solar cells.

Conjugated polymers as electron donors in solar cells based on donor/acceptor combinations are of great interest, partly due to the possibility of converting solar light with a low materials budget. Six small bandgap polymers with optical bandgap ranging from 1.0-1.9 eV are presented in this paper. All polymers utilize an electron donor-acceptor-donor (DAD) segment in the polymer backbone, creating a partial charge-transfer, to decrease the bandgap. The design, synthesis and the optical characteristics as well as the solar cell characteristics of the polymers are discussed. The positions of the energy levels of the conjugated polymer relative to the electron acceptor are of significant importance and determine not only the driving force for exciton dissociation but also the maximum open-circuit voltage. This work also focuses on investigating the redox behavior of the described conjugated polymers and electron acceptors using square wave voltammetry. Comparing the electrochemical data gives important information of the structure-property relationships of the polymers.