Electron-Deficient Polycyclic Molecules via Ring Fusion for n-Type Organic Electrochemical Transistors.

The primary challenge for n-type small-molecule organic electrochemical transistors (OECTs) is to improve their electron mobilities and thus the key figure of merit µC*. Nevertheless, few reports in OECTs have specially proposed to address this issue. Herein, we report a 10-ring-fused polycyclic π-system consisting of the core of naphthalene bis-isatin dimer and the terminal moieties of rhodanine, which features intramolecular noncovalent interactions, high π-delocalization and strong electron-deficient characteristics. We find that this extended π-conjugated system using the ring fusion strategy displays improved electron mobilities up to 0.043 cm2 V-1 s-1 compared to our previously reported small molecule gNR, and thereby leads to a remarkable µC* of 10.3 F cm-1 V-1 s-1 in n-type OECTs, which is the highest value reported to date for small-molecule OECTs. This work highlights the importance of π-conjugation extension in polycyclic-fused molecules for enhancing the performance of n-type small-molecule OECTs.

Backbone coplanarity manipulation via hydrogen bonding to boost the n-type performance of polymeric mixed conductors operating in aqueous electrolyte.

The development of high-performance n-type semiconducting polymers remains a significant challenge. Reported here is the construction of a coplanar backbone via intramolecular hydrogen bonds to dramatically enhance the performance of n-type polymeric mixed conductors operating in aqueous electrolyte. Specifically, glycolated naphthalene tetracarboxylicdiimide (gNDI) couples with vinylene and thiophene to give gNDI-V and gNDI-T, respectively. The hydrogen bonding functionalities are fused to the backbone to ensure a more coplanar backbone and much tighter π-π stacking of gNDI-V than gNDI-T, which is evidenced by density functional theory simulations and grazing-incidence wide-angle X-ray scattering. Importantly, these copolymers are fabricated as the active layer of the aqueous-based electrochromic devices and organic electrochemical transistors (OECTs). gNDI-V exhibits a larger electrochromic contrast (ΔT = 30%) and a higher coloration efficiency (1988 cm2 C-1) than gNDI-T owing to its more efficient ionic-electronic coupling. Moreover, gNDI-V gives the highest electron mobility (0.014 cm2 V-1 s-1) and µC* (2.31 FV-1 cm-1 s-1) reported to date for NDI-based copolymers in OECTs, attributed to the improved thin-film crystallinity and molecular packing promoted by hydrogen bonds. Overall, this work marks a remarkable advance in the n-type polymeric mixed conductors and the hydrogen bond functionalization strategy opens up an avenue to access desirable performance metrics for aqueous-based electrochemical devices.

Tunable control of the performance of aqueous-based electrochemical devices by post-polymerization functionalization.

Functionalized polymeric mixed ionic-electronic conductors (PMIECs) are highly desired for the development of electrochemical applications, yet are hindered by the limited conventional synthesis techniques. Here, we propose a "graft-onto-polymer" synthesis strategy by post-polymerization functionalization (GOP-PPF) to prepare a family of PMIECs sharing the same backbone while functionalized with varying ethylene glycol (EG) compositions (two, four, and six EG repeating units). Unlike the typical procedure, GOP-PPF uses a nucleophilic aromatic substitution reaction for the facile and versatile attachment of functional units to a pre-synthesized conjugated-polymer precursor. Importantly, these redox-active PMIECs are investigated as a platform for energy storage devices and organic electrochemical transistors (OECTs) in aqueous media. The ion diffusivity, charge mobility and charge-storage capacity can be significantly improved by optimizing the EG composition. Specifically, g2T2-gBT6 containing the highest EG density gives the highest charge-storage capacity exceeding 180 F g-1 among the polymer series, resulting from the improved ion diffusivity. Moreover, g2T2-gBT4 with four EG repeating units exhibits a superior performance compared to its two analogues in OECTs, associated with a high µC* up to 359 F V-1 cm-1 s-1, owing to the optimal balance between ionic-electronic coupling and charge mobility. Through the GOP-PPF, PMIECs can be tailored to access desirable performance metrics at the molecular level.

Efficient n-Type Small-Molecule Mixed Ion-Electron Conductors and Application in Hydrogen Peroxide Sensors.

Small-molecule semiconductors used as the channel of organic electrochemical transistors (OECTs) have been rarely reported despite their inherent advantages of well-defined molecular weight, convenient scale-up synthesis, and good performance reproducibility. Herein, three small molecules based on perylene diimides are readily prepared for n-type OECTs. The final molecules show preferred energy levels, tunable backbone conformation, and high film crystallinity, rendering them good n-type dopability, favorable volumetric capacities, and substantial electron mobilities. Consequently, the OECTs afford a record-low threshold voltage of 0.05 V and a normalized peak transconductance of 4.52 × 10-2 S cm-1, as well as impressive long-term cycling stability. Significantly, the OECTs utilized for hydrogen peroxide sensing are further demonstrated with a detection limit of 0.75 µM. This work opens the possibility of developing nonfullerene small molecules as superior n-type OECT materials and provides important insights for designing high-performance small-molecule mixed ion-electron conductors for OECTs and (bio)sensors.

High-Transconductance, Highly Elastic, Durable and Recyclable All-Polymer Electrochemical Transistors with 3D Micro-Engineered Interfaces.

Organic electrochemical transistors (OECTs) have emerged as versatile platforms for broad applications spanning from flexible and wearable integrated circuits to biomedical monitoring to neuromorphic computing. A variety of materials and tailored micro/nanostructures have recently been developed to realized stretchable OECTs, however, a solid-state OECT with high elasticity has not been demonstrated to date. Herein, we present a general platform developed for the facile generation of highly elastic all-polymer OECTs with high transconductance (up to 12.7 mS), long-term mechanical and environmental durability, and sustainability. Rapid prototyping of these devices was achieved simply by transfer printing lithium bis(trifluoromethane)sulfonimide doped poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate) (PEDOT:PSS/LiTFSI) microstructures onto a resilient gelatin-based gel electrolyte, in which both depletion-mode and enhancement-mode OECTs were produced using various active channels. Remarkably, the elaborate 3D architectures of the PEDOT:PSS were engineered, and an imprinted 3D-microstructured channel/electrolyte interface combined with wrinkled electrodes provided performance that was retained (> 70%) through biaxial stretching of 100% strain and after 1000 repeated cycles of 80% strain. Furthermore, the anti-drying and degradable gelatin and the self-crosslinked PEDOT:PSS/LiTFSI jointly enabled stability during > 4 months of storage and on-demand disposal and recycling. This work thus represents a straightforward approach towards high-performance stretchable organic electronics for wearable/implantable/neuromorphic/sustainable applications.

High-Performance Polymer Solar Cells Based on a Wide-Bandgap Polymer Containing Pyrrolo[3,4-f]benzotriazole-5,7-dione with a Power Conversion Efficiency of 8.63.

A novel donor-acceptor type conjugated polymer based on a building block of 4,8-di(thien-2-yl)-6-octyl-2-octyl-5H-pyrrolo[3,4-f]benzotriazole-5,7(6H)-dione (TZBI) as the acceptor unit and 4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)-benzo-[1,2-b:4,5-b']dithiophene as the donor unit, named as PTZBIBDT, is developed and used as an electron-donating material in bulk-heterojunction polymer solar cells. The resulting copolymer exhibits a wide bandgap of 1.81 eV along with relatively deep highest occupied molecular orbital energy level of -5.34 eV. Based on the optimized processing conditions, including thermal annealing, and the use of a water/alcohol cathode interlayer, the single-junction polymer solar cell based on PTZBIBDT:PC71BM ([6,6]-phenyl-C71-butyric acid methyl ester) blend film affords a power conversion efficiency of 8.63% with an open-circuit voltage of 0.87 V, a short circuit current of 13.50 mA cm-2, and a fill factor of 73.95%, which is among the highest values reported for wide-bandgap polymers-based single-junction organic solar cells. The morphology studies on the PTZBIBDT:PC71BM blend film indicate that a fibrillar network can be formed and the extent of phase separation can be mani-pulated by thermal annealing. These results indicate that the TZBI unit is a very promising building block for the synthesis of wide-bandgap polymers for high-performance single-junction and tandem (or multijunction) organic solar cells.

A series of new medium-bandgap conjugated polymers based on naphtho[1,2-c:5,6-c]bis(2-octyl-[1,2,3]triazole) for high-performance polymer solar cells.

A series of novel conjugated copolymers based on naphtho[1,2-c:5,6-c]bis(2-octyl-[1,2,3]triazole) (TZNT) are synthesized. These copolymers exhibit medium bandgaps of ≈1.9 eV. One of them demonstrates a high performance of up to 6.10% power conversion efficiency in a bulk-heterojunction (BHJ) solar-cell device. The performance can be further enhanced to 7.11% when applied in an inverted device architecture, using PF3 N-OX as an interfacial modifier.