RESUMO
Theoretical and experimental studies suggest that energetic offsets between the charge transport energy levels in different morphological phases of polymer:fullerene bulk heterojunctions may improve charge separation and reduce recombination in polymer solar cells (PSCs). In this work, we use cyclic voltammetry, UV-vis absorption, and ultraviolet photoelectron spectroscopy to characterize hole energy levels in the polymer phases of polymer:fullerene bulk heterojunctions. We observe an energetic offset of up to 150 meV between amorphous and crystalline polymer due to bandgap widening associated primarily with changes in polymer conjugation length. We also observe an energetic offset of up to 350 meV associated with polymer:fullerene intermolecular interactions. The first effect has been widely observed, but the second effect is not always considered despite being larger in magnitude for some systems. These energy level shifts may play a major role in PSC performance and must be thoroughly characterized for a complete understanding of PSC function.
RESUMO
While varying the size and branching of solubilizing side chains in π-conjugated polymers impacts their self-assembling properties in thin-film devices, these structural changes remain difficult to anticipate. This report emphasizes the determining role that linear side-chain substituents play in poly(benzo[1,2-b:4,5-b']dithiophene-thieno[3,4-c]pyrrole-4,6-dione) (PBDTTPD) polymers for bulk heterojunction (BHJ) solar cell applications. We show that replacing branched side chains by linear ones in the BDT motifs induces a critical change in polymer self-assembly and backbone orientation in thin films that correlates with a dramatic drop in solar cell efficiency. In contrast, we show that for polymers with branched alkyl-substituted BDT motifs, controlling the number of aliphatic carbons in the linear N-alkyl-substituted TPD motifs is a major contributor to improved material performance. With this approach, PBDTTPD polymers were found to reach power conversion efficiencies of 8.5% and open-circuit voltages of 0.97 V in BHJ devices with PC71BM, making PBDTTPD one of the best polymer donors for use in the high-band-gap cell of tandem solar cells.
RESUMO
We compare the solar cell performance of several polymers with the conventional electron acceptor phenyl-C61-butyric acid methyl ester (PCBM) to fullerenes with one to three indene adducts. We find that the multiadduct fullerenes with lower electron affinity improve the efficiency of the solar cells only when they do not intercalate between the polymer side chains. When they intercalate between the side chains, the multiadduct fullerenes substantially reduce solar cell photocurrent. We use X-ray diffraction to determine how the fullerenes are arranged within crystals of poly-(2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT) and suggest that poor electron transport in the molecularly mixed domains may account for the reduced solar cell performance of blends with fullerene intercalation.
Assuntos
Fontes de Energia Elétrica , Fulerenos/química , Nanoestruturas/química , Nanoestruturas/ultraestrutura , Polímeros/química , Energia Solar , Transferência de Energia , Desenho de Equipamento , Análise de Falha de Equipamento , Tamanho da PartículaRESUMO
A generalized silica coating scheme is used to functionalize and protect sub-micron and micron size dicyclopentadiene monomer-filled capsules and polymer-protected Grubbs' catalyst particles. These capsules and particles are used for self-healing of microscale damage in an epoxy-based polymer. The silica layer both protects the capsules and particles, and limits their aggregation when added to an epoxy matrix, enabling the capsules and particles to be dispersed at high concentrations with little loss of reactivity.