An official website of the United States government
Abstract Organic electrochemical transistors (OECTs) are the building blocks of biosensors, neuromorphic devices, and complementary circuits. One rule in the materials design for OECTs is the inclusion of a hydrophilic component in the chemical structure to enable ion transport in the film. Here, it is shown that the ladder‐type, side‐chain free polymer poly(benzimidazobenzophenanthroline) (BBL) performs significantly better in OECTs than the donor–acceptor type copolymer bearing hydrophilic ethylene glycol side chains (P‐90). A combination of electrochemical techniques reveals that BBL exhibits a more efficient ion‐to‐electron coupling and higher OECT mobility than P‐90. In situ atomic force microscopy scans evidence that BBL, which swells negligibly in electrolytes, undergoes a drastic and permanent change in morphology upon electrochemical doping. In contrast, P‐90 substantially swells when immersed in electrolytes and shows moderate morphology changes induced by dopant ions. Ex situ grazing incidence wide‐angle X‐ray scattering suggests that the particular packing of BBL crystallites is minimally affected after doping, in contrast to P‐90. BBL's ability to show exceptional mixed transport is due to the crystallites’ connectivity, which resists water uptake. This side chain‐free route for the design of mixed conductors could bring the n‐type OECT performance closer to the bar set by their p‐type counterparts.
more »
« less
Influence of Molecular Weight on the Organic Electrochemical Transistor Performance of Ladder‐Type Conjugated Polymers
Abstract Organic electrochemical transistors (OECTs) hold promise for developing a variety of high‐performance (bio‐)electronic devices/circuits. While OECTs based on p‐type semiconductors have achieved tremendous progress in recent years, n‐type OECTs still suffer from low performance, hampering the development of power‐efficient electronics. Here, it is demonstrated that fine‐tuning the molecular weight of the rigid, ladder‐type n‐type polymer poly(benzimidazobenzophenanthroline) (BBL) by only one order of magnitude (from 4.9 to 51 kDa) enables the development of n‐type OECTs with record‐high geometry‐normalized transconductance (gm,norm ≈ 11 S cm−1) and electron mobility × volumetric capacitance (µC* ≈ 26 F cm−1 V−1s−1), fast temporal response (0.38 ms), and low threshold voltage (0.15 V). This enhancement in OECT performance is ascribed to a more efficient intermolecular charge transport in high‐molecular‐weight BBL than in the low‐molecular‐weight counterpart. OECT‐based complementary inverters are also demonstrated with record‐high voltage gains of up to 100 V V−1and ultralow power consumption down to 0.32 nW, depending on the supply voltage. These devices are among the best sub‐1 V complementary inverters reported to date. These findings demonstrate the importance of molecular weight in optimizing the OECT performance of rigid organic mixed ionic–electronic conductors and open for a new generation of power‐efficient organic (bio‐)electronic devices.
more »
« less
- Award ID(s):
- 2003518
- PAR ID:
- 10446547
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Materials
- Volume:
- 34
- Issue:
- 4
- ISSN:
- 0935-9648
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
The commercially available polyelectrolyte complex poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) is ubiquitous in organic and hybrid electronics. As such, it has often been used as a benchmark material for fundamental studies and the development of new electronic devices. Yet, most studies on PEDOT:PSS have focused on its electronic conductivity in dry environments, with less consideration given to its ion transport, coupled ionic-electronic transport, and charge storage properties in aqueous environments. These properties are essential for applications in bioelectronics (sensors, actuators), charge storage devices, and electrochromic displays. Importantly, past studies on mixed ionic-electronic transport in PEDOT:PSS neglected to consider how the molecular structure of PSS affects mixed ionic-electronic transport. Herein, we therefore investigated the effect of the molecular weight and size distribution of PSS on the electronic properties and morphology of PEDOT:PSS both in dry and aqueous environments, and overall performance in organic electrochemical transistors (OECTs). Using reversible addition–fragmentation chain transfer (RAFT) polymerization with two different chain transfer agents, six PSS samples with monomodal, narrow ( Đ = 1.1) and broad ( Đ = 1.7) size distributions and varying molecular weights were synthesized and used as matrices for PEDOT. We found that using higher molecular weight of PSS ( M n = 145 kg mol −1 ) and broad dispersity led to OECTs with the highest transconductance (up to 16 mS) and [ μC *] values (∼140 F cm −1 V −1 s −1 ) in PEDOT:PSS, despite having a lower volumetric capacitance ( C * = 35 ± 4 F cm −3 ). The differences were best explained by studying the microstructure of the films by atomic force microscopy (AFM). We found that heterogeneities in the PEDOT:PSS films (interconnected and large PEDOT- and PSS-rich domains) obtained from high molecular weight and high dispersity PSS led to higher charge mobility ( μ OECT ∼ 4 cm 2 V −1 s −1 ) and hence transconductance. These studies highlight the importance of considering molecular weight and size distribution in organic mixed ionic-electronic conductor, and could pave the way to designing high performance organic electronics for biological interfaces.more » « less
-
Abstract Conducting polymers, such as thep-doped poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS), have enabled the development of an array of opto- and bio-electronics devices. However, to make these technologies truly pervasive, stable and easily processable,n-doped conducting polymers are also needed. Despite major efforts, non-type equivalents to the benchmark PEDOT:PSS exist to date. Here, we report on the development of poly(benzimidazobenzophenanthroline):poly(ethyleneimine) (BBL:PEI) as an ethanol-basedn-type conductive ink. BBL:PEI thin films yield ann-type electrical conductivity reaching 8 S cm−1, along with excellent thermal, ambient, and solvent stability. This printablen-type mixed ion-electron conductor has several technological implications for realizing high-performance organic electronic devices, as demonstrated for organic thermoelectric generators with record high power output andn-type organic electrochemical transistors with a unique depletion mode of operation. BBL:PEI inks hold promise for the development of next-generation bioelectronics and wearable devices, in particular targeting novel functionality, efficiency, and power performance.more » « less
-
Abstract Organic electrochemical transistors (OECTs) exhibit strong potential for various applications in bioelectronics, especially as miniaturized, point‐of‐care biosensors, because of their efficient transducing ability. To date, however, the majority of reported OECTs have relied on p‐type (hole transporting) polymer mixed conductors, due to the limited number of n‐type (electron transporting) materials suitable for operation in aqueous electrolytes, and the low performance of those which exist. It is shown that a simple solvent‐engineering approach boosts the performance of OECTs comprising an n‐type, naphthalenediimide‐based copolymer in the channel. The addition of acetone, a rather bad solvent for the copolymer, in the chloroform‐based polymer solution leads to a three‐fold increase in OECT transconductance, as a result of the simultaneous increase in volumetric capacitance and electron mobility in the channel. The enhanced electrochemical activity of the polymer film allows high‐performance glucose sensors with a detection limit of 10 × 10−6mof glucose and a dynamic range of more than eight orders of magnitude. The approach proposed introduces a new tool for concurrently improving the conduction of ionic and electronic charge carriers in polymer mixed conductors, which can be utilized for a number of bioelectronic applications relying on efficient OECT operation.more » « less
-
Abstract Organic electrochemical transistors (OECTs) have shown promise as transducers and amplifiers of minute electronic potentials due to their large transconductances. Tuning the OECT threshold voltage is important to achieve low‐powered devices with amplification properties within the desired operational voltage range. However, traditional design approaches have struggled to decouple channel and materials properties from threshold voltage, thereby compromising on several other OECT performance metrics, such as electrochemical stability, transconductance, and dynamic range. In this work, simple solution‐processing methods are utilized to chemically dope polymer gate electrodes, thereby controlling their work function, which in turn tunes the operation voltage range of the OECTs without perturbing their channel properties. Chemical doping of initially air‐sensitive polymer electrodes further improves their electrochemical stability in ambient conditions. Thus, OECTs that are simultaneously low‐powered and electrochemically resistant to oxidative side reactions under ambient conditions are demonstrated. This approach shows that threshold voltage, which is once interwoven with other OECT properties, can in fact be an independent design parameter, expanding the design space of OECTs.more » « less
