Graduate Student, University of Massachusetts Amherst
Design of cheaper-alternative small molecule acceptors for organic solar cells.
Power conversion efficiency (PCE) has surpassed 10% for single junction organic solar cells (OSCs) mainly through the design and synthesis of novel donor materials, the optimization of film morphology and the evolution of the devices. However, the development of novel acceptor materials is relatively sluggish compared with the donor compounds. Nowadays, fullerene derivatives, such as PC61BM and PC71BM, are still the dominant acceptors due to their superior charge transporting properties. Unfortunately, these two acceptors suffer from some intrinsic shortcomings such as limited absorption, difficult functionalization, and high production cost. Therefore, developing novel non-fullerene acceptors that can overcome the above-mentioned disadvantages is highly desirable. As a matter of fact, research on non-fullerene acceptors has made considerable progress in the last two years and a highest PCE of around 12% has been achieved.
Abstract: A new organic small molecule, DRTB-T, that incorporates a two-dimensional tri-alkylthienyl-substituted benzodithiophene core building block was designed and synthesized. DRTB-T has a band gap (Egopt) of 2.0 eV with a low-lying highest occupied molecular orbital (HOMO) level of -5.51 eV. Non-fullerene small-molecule solar cells consisting of DRTB-T and a non-fullerene acceptor (IC-C6IDT-IC) were constructed, and the morphology of the active layer was fine-tuned by solvent vapor annealing (SVA). The device showed a record 9.08% power conversion efficiency (PCE) with a high open-circuit voltage (Voc = 0.98 V). This is the highest PCE for a non-fullerene small-molecule organic solar cell (NFSM-OSC) reported to date. Our notable results demonstrate that the molecular design of a wide band gap (WBG) donor to create a well-matched donor-acceptor pair with a low band gap (LBG) non-fullerene small-molecule acceptor, as well as subtle morphological control, provides great potential to realize high-performance NFSM-OSCs.
Pub.: 14 Jan '17, Pinned: 27 Jun '17
Abstract: Polycyclic aromatic hydrocarbons (PAHs) have been widely explored as molecular semiconductors in organic electronic devices such as field-effect transistors or solar cells. However, their tendency to undergo photooxidation is a primary limitation to their practical applications. Bistetracene derivatives have recently been demonstrated to possess much larger photooxidation stability than the widely investigated pentacene and rubrene, while maintaining high charge-carrier mobilities. Here, using several levels of density functional theory, we identify the origin of the increased stability of bistetracene with respect to molecular oxygen by systematically investigating the [4 + 2] cycloaddition (Diels–Alder) photooxidation reaction mechanism. Importantly, our computational results indicate that endoperoxide formation in bis(2-(trimethylsilyl)ethynyl) bistetracene (BT) occurs not on the ring with least aromaticity, but rather on the ring with smallest distortion energy. This feature was subsequently confirmed by experimental NMR analyses. The oxidation activation barriers of bistetracene, pentacene, and rubrene are found to be 17.7, 13.6, and 14.4 kcal/mol, respectively, in agreement with the observed order of stability of these molecules with respect to oxidation reactions in solution. In the cases of BT and pentacene, the rates of electron transfer to create charged species (PAH+ and O2–) are at least two orders of magnitude lower than that of the charge recombination process (back to PAH and O2); for rubrene, both of these processes are calculated to be of the same order of magnitude, in agreement with experimental electron paramagnetic resonance spectroscopy observations.
Pub.: 15 Nov '16, Pinned: 27 Jun '17
Abstract: We demonstrate a new method to reverse the polarity and charge transport behavior of naphthalenediimide (NDI)-based copolymers by inserting a vinylene linker between the donor and acceptor units. The vinylene linkers minimize the intrinsic steric congestion between the NDI and thiophene moieties to prompt backbone planarity. The polymers with vinylene linkers exhibit electron n-channel transport characteristics under vacuum, similar to the benchmark polymer, P(NDI2OD-T2). To our surprise, when the polymers are measured in air, the dominant carrier type switches from n- to p-type and yield hole mobilities up to 0.45 cm2 V–1 s–1 with hole to electron mobility ratio of three (μh/μe, ∼3), which indicates that the hole density in the active layer can be significantly increased by exposure to air. This increase is consistent with the intrinsic more delocalized nature of the highest occupied molecular orbital of the charged vinylene polymer, as estimated by density functional theory (DFT) calculations, which facilitates hole transport within the polymer chains. This is the first demonstration of an efficient NDI-based hole semiconducting polymer, which will enable new developments in all-polymer solar cells, complementary circuits, and dopable polymers for use in thermoelectrics.
Pub.: 04 Nov '16, Pinned: 27 Jun '17