Gitish K. Dutta

A Thienoisoindigo-Naphthalene Polymer with Ultrahigh Mobility of 14.4 cm2/V·s That Substantially Exceeds Benchmark Values for Amorphous Silicon Semiconductors

By considering the qualitative benefits associated with solution rheology and mechanical properties of polymer semiconductors, it is expected that polymer-based electronic devices will soon enter our daily lives as indispensable elements in a myriad of flexible and ultra low-cost flat panel displays. Despite more than a decade of research focused on designing and synthesizing state-of-the-art polymer semiconductors for improving charge transport characteristics, the current mobility values are still not sufficient for many practical applications. The confident mobility in excess of ∼10 cm(2)/V·s is the most important requirement for enabling the realization of the aforementioned near-future products. We report on an easily attainable donor-acceptor (D-A) polymer semiconductor: poly(thienoisoindigo-alt-naphthalene) (PTIIG-Np). An unprecedented mobility of 14.4 cm(2)/V·s, by using PTIIG-Np with a high-k gate dielectric poly(vinylidenefluoride-trifluoroethylene) (P(VDF-TrFE)), is achieved from a simple coating processing, which is of a magnitude that is very difficult to obtain with conventional TFTs by means of molecular engineering. This work, therefore, represents a major step toward truly viable plastic electronics.

Synthesis of PCDTBT-based fluorinated polymers for high open-circuit voltage in organic photovoltaics: towards an understanding of relationships between polymer energy levels engineering and ideal morphology control.

The introduction of fluorine (F) atoms onto conjugated polymer backbone has verified to be an effective way to enhance the overall performance of polymer-based bulk-heterojunction (BHJ) solar cells, but the underlying working principles are not yet fully uncovered. As our attempt to further understand the impact of F, herein we have reported two novel fluorinated analogues of PCDTBT, namely, PCDTFBT (1F) and PCDT2FBT (2F), through inclusion of either one or two F atoms into the benzothiadiazole (BT) unit of the polymer backbone and the characterization of their physical properties, especially their performance in solar cells. Together with a profound effect of fluorination on the optical property, nature of charge transport, and molecular organization, F atoms are effective in lowering both the HOMO and LUMO levels of the polymers without a large change in the energy bandgaps. PCDTFBT-based BHJ solar cell shows a power conversion efficiency (PCE) of 3.96 % with high open-circuit voltage (VOC) of 0.95 V, mainly due to the deep HOMO level (-5.54 eV). To the best of our knowledge, the resulting VOC is comparable to the record VOC values in single junction devices. Furthermore, to our delight, the best PCDTFBT-based device, prepared using 2 % v/v diphenyl ether (DPE) additive, reaches the PCE of 4.29 %. On the other hand, doubly-fluorinated polymer PCDT2FBT shows the only moderate PCE of 2.07 % with a decrease in VOC (0.88 V), in spite of the further lowering of the HOMO level (-5.67 eV) with raising the number of F atoms. Thus, our results highlight that an improvement in efficiency by tuning the energy levels of the polymers by means of molecular design can be expected only if their truly optimized morphologies with fullerene in BHJ systems are materialized.

Synthesis of fluorinated analogues of a practical polymer TQ for improved open-circuit voltages in polymer solar cells

In an attempt to further lower the HOMO of a cost-effective polymer poly(2,3-bis-(3-octyloxyphenyl)quinoxaline-5,8-dyl-alt-thiophene-2,5-diyl) (TQ) by adding F atoms onto the existing quinoxaline acceptor within the polymer backbone, we have synthesized two structurally identical fluorinated analogues of TQ (TQ-F (single F) and TQ-FF (double F)), except for the number of F atoms. The effects of inclusion of F atoms on the optical properties, nature of charge transport, and molecular organization are thoroughly investigated. The resulting two fluorinated polymers show a decrease in both the HOMO and the LUMO energy levels relative to non-fluorinated TQ. Moreover, the fluorination of the polymer backbone has lowered the HOMOs more than the LUMOs, slightly widening the energy bandgaps as the number of F atoms increases. Thus, use of these polymers in bulk-heterojunction (BHJ) solar cells, in all cases, leads to large VOC values. The power conversion efficiency (PCE) of the optimized PSCs based on TQ-F reaches 4.41%. In addition, it is interesting to note that, despite TQ-FF having the PCE that is lower than that of TQ-F, an unprecedentedly high VOC of 1.00 V is achieved, which is nearly equal to the highest VOC values ever reported for polymers.

Channel II photocurrent quantification in narrow optical gap polymer-fullerene solar cells with complimentary acceptor absorption

Most charge generation studies on organic solar cells focus on the conventional mode of photocurrent generation derived from light absorption in the electron donor component (so called channel I). In contrast, relatively little attention has been paid to the alternate generation pathway: light absorption in the electron acceptor followed by photo-induced hole transfer (channel II). By using the narrow optical gap polymer poly(3,6-dithieno[3,2-b]thiophen-2-yl)-2,5-bis(2-octyldodecyl)-pyrrolo-[3,4-c]pyrrole-1,4-dione-5′,5″-diyl-alt-4,8-bis(dodecyloxy)benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl with two complimentary fullerene absorbers; phenyl-C61-butyric acid methyl ester, and phenyl-C71-butyric acid methyl ester (70-PCBM), we have been able to quantify the photocurrent generated each of the mechanisms and find a significant fraction (>30%), which is derived in particular from 70-PCBM light absorption.

Medium bandgap copolymers based on carbazole and quinoxaline exceeding 1.0 V open-circuit voltages

Open-circuit voltage (VOC) is an important parameter in determining the performance of polymer solar cells (PSCs). Given the desire for superior VOC values in PSCs, we have designed and synthesized a series of ‘medium bandgap’ donor–acceptor (D–A) copolymers containing carbazole (Cz) and quinoxaline (Qx) (PCzDT-Qx, PCzDT-fQx, and PCzDT-ffQx). As a result of their deep-lying HOMO levels (−5.45 to −5.61 eV), high VOC values are achieved in PSCs with the resulting copolymers, despite the expense of short-circuit current density (JSC) and fill factor (FF) parameters. In this study, in addition to the best power-conversion efficiency (PCE) of up to 4.03% from PCzDT-fQx-based on PSCs, we have demonstrated a VOC value exceeding 1.0 V with PSCs of PCzDT-ffQx, which is among the highest VOC values achieved to date. Moreover, a comprehensive investigation on the mechanism of charge recombination and transport characteristics can determine a clear structure–property correlation in this class of molecules, which is helpful for designing better materials with maximum VOC without scarifying other key photovoltaic parameters.