TY  - JOUR
A1  - Wade, Jessica
A1  - Wood, Sebastian
A1  - Collado-Fregoso, Elisa
A1  - Heeney, Martin
A1  - Durrant, James
A1  - Kim, Ji-Seon
T1  - Impact of Fullerene Intercalation on Structural and Thermal Properties of Organic Photovoltaic Blends
JF  - The journal of physical chemistry : C, Nanomaterials and interfaces
N2  - The performance of organic photovoltaic blend devices is critically dependent on the polymer:fullerene interface. These interfaces are expected to impact the structural and thermal properties of the polymer with regards to the conjugated backbone planarity and transition temperatures during annealing/cooling processes. Here, we report the impact of fullerene intercalation on structural and thermal properties of poly(2,5-bis(3-tetradecylthiophen-2-yOthieno[3,2-b]thiophene (PBTTT), a highly stable material known to exhibit liquid crystalline behavior. We undertake a detailed systematic study of the extent of intercalation in the PBTTT:fullerene blend, considering the use of four different fullerene derivatives and also varying the loading ratios. Resonant Raman spectroscopy allows morphology in situ during controlled heating and cooling. We find that small fullerene molecules readily intercalate into PBTTT crystallites, resulting in a planarization of the polymer backbone, but high fullerene loading ratios or larger fullerenes result in nonintercalated domains. During cooling from melt, nonintercalated blend films are found to return to their original morphology and reproduce all thermal transitions on cooling with minimal hysteresis. Intercalated blend films show significant hysteresis on cooling due to the crystallized fullerene attempting to reintercalate. The strongest hysteresis is for intercalated blend films with excess fullerene loading ratio, which form a distinct nanoribbon morphology and exhibit a reduced geminate recombination rate. These results reveal that careful consideration should be taken during device fabrication, as postdeposition thermal treatments significantly impact the charge generation and recombination dynamics.
Y1  - 2017
U6  - https://doi.org/10.1021/acs.jpcc.7b05893
SN  - 1932-7447
VL  - 121
SP  - 20976
EP  - 20985
PB  - American Chemical Society
CY  - Washington
ER  - 
TY  - JOUR
A1  - Marin-Beloqui, Jose
A1  - Zhang, Guanran
A1  - Guo, Junjun
A1  - Shaikh, Jordan
A1  - Wohrer, Thibaut
A1  - Hosseini, Seyed Mehrdad
A1  - Sun, Bowen
A1  - Shipp, James
A1  - Auty, Alexander J.
A1  - Chekulaev, Dimitri
A1  - Ye, Jun
A1  - Chin, Yi-Chun
A1  - Sullivan, Michael B.
A1  - Mozer, Attila J.
A1  - Kim, Ji-Seon
A1  - Shoaee, Safa
A1  - Clarke, Tracey M.
T1  - Insight into the origin of trapping in polymer/fullerene blends with a systematic alteration of the fullerene to higher adducts
JF  - Journal of physical chemistry C
N2  - The bimolecular recombination characteristics of conjugated polymer poly[(4,4'-bis(2-ethylhexyl)dithieno[3,2-b:2',3'-d]silole)-2,6-diyl-alt-(2,5-bis 3-tetradecylthiophen-2-y1 thiazolo 5,4-d thiazole)-2,5diy1] (PDTSiTTz) blended with the fullerene series PC60BM, ICMA, ICBA, and ICTA have been investigated using microsecond and femtosecond transient absorption spectroscopy, in conjunction with electroluminescence measurements and ambient photoemission spectroscopy. The non-Langevin polymer PDTSiTTz allows an inspection of intrinsic bimolecular recombination rates uninhibited by diffusion, while the low oscillator strengths of fullerenes allow polymer features to dominate, and we compare our results to those of the well-known polymer Si-PCPDTBT. Using mu s-TAS, we have shown that the trap -limited decay dynamics of the PDTSiTTz polaron becomes progressively slower across the fullerene series, while those of Si-PCPDTBT are invariant. Electroluminescence measurements showed an unusual double peak in pristine PDTSiTTz, attributed to a low energy intragap charge transfer state, likely interchain in nature. Furthermore, while the pristine PDTSiTTz showed a broad, low-intensity density of states, the ICBA and ICTA blends presented a virtually identical DOS to Si-PCPDTBT and its blends. This has been attributed to a shift from a delocalized, interchain highest occupied molecular orbital (HOMO) in the pristine material to a dithienosilole-centered HOMO in the blends, likely a result of the bulky fullerenes increasing interchain separation. This HOMO localization had a side effect of progressively shifting the polymer HOMO to shallower energies, which was correlated with the observed decrease in bimolecular recombination rate and increased "trap" depth. However, since the density of tail states remained the same, this suggests that the traditional viewpoint of "trapping" being dominated by tail states may not encompass the full picture and that the breadth of the DOS may also have a strong influence on bimolecular recombination.
Y1  - 2022
U6  - https://doi.org/10.1021/acs.jpcc.1c10378
SN  - 1932-7447
SN  - 1932-7455
VL  - 126
IS  - 5
SP  - 2708
EP  - 2719
PB  - American Chemical Society
CY  - Washington
ER  -