Why PEDOT:PSS Should Not Be Used for Raman Sensing of Redox States (and How It Could Be).

Poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) has been recently proposed for Raman sensing of redox-active species in solution. Here, we investigated the rationale of this approach through systematic experiments, in which the Raman spectrum of PEDOT:PSS was analyzed in the presence of either nonoxidizing or oxidizing electrolytes. The results demonstrated that Raman spectra precisely reflect the conformation of PEDOT units and their interactions with PSS. Two different responses were observed. In the case of oxidizing electrolytes, the effect of charge transfer is accurately transduced in Raman spectrum changes. On the other hand, reduction induces a progressive separation between the PEDOT and PSS chains, which decreases their mutual interaction. This stimulus determines characteristic variations in the intensity, shape, and position of the Raman spectra. However, we demonstrated that the same effects can be obtained either by increasing the concentration of nonoxidizing electrolytes or by deprotonating PSS chains. This poses severe limitations to the use of PEDOT:PSS for this type of Raman sensing. This study allows us to revise most of the Raman results reported in the literature with a clear model, setting a new basis for investigating the dynamics of mixed electronic/ionic charge transfer in conductive polymers.

Ion buffering and interface charge enable high performance electronics with organic electrochemical transistors.

Organic electrochemical transistors rely on ionic-electronic volumetric interaction to provide a seamless interface between biology and electronics with outstanding signal amplification. Despite their huge potential, further progress is limited owing to the lack of understanding of the device fundamentals. Here, we investigate organic electrochemical transistors in a wide range of experimental conditions by combining electrical analyses and device modeling. We show that the measurements can be quantitatively explained by nanoscale ionic-electronic charge interaction, giving rise to ion buffering and interface charge compensation. The investigation systematically explains and unifies a wide range of experiments, providing the rationale for the development of high-performance electronics. Unipolar inverters - universal building blocks for electronics - with gain larger than 100 are demonstrated. This is the highest gain ever reported, enabling the design of devices and circuits with enhanced performance and opening opportunities for the next-generation integrated bioelectronics and neuromorphic computing.

High-sensitivity ion detection at low voltages with current-driven organic electrochemical transistors.

Ions dissolved in aqueous media play a fundamental role in plants, animals, and humans. Therefore, the in situ quantification of the ion concentration in aqueous media is gathering relevant interest in several fields including biomedical diagnostics, environmental monitoring, healthcare products, water and food test and control, agriculture industry and security. The fundamental limitation of the state-of-art transistor-based approaches is the intrinsic trade-off between sensitivity, ion concentration range and operating voltage. Here we show a current-driven configuration based on organic electrochemical transistors that overcomes this fundamental limit. The measured ion sensitivity exceeds by one order of magnitude the Nernst limit at an operating voltage of few hundred millivolts. The ion sensitivity normalized to the supply voltage is larger than 1200 mV V-1 dec-1, which is the largest value ever reported for ion-sensitive transistors. The proposed approach is general and can be extended to any transistor technology, thus opening opportunities for high-performance bioelectronics.

Ultra-high gain diffusion-driven organic transistor.

Emerging large-area technologies based on organic transistors are enabling the fabrication of low-cost flexible circuits, smart sensors and biomedical devices. High-gain transistors are essential for the development of large-scale circuit integration, high-sensitivity sensors and signal amplification in sensing systems. Unfortunately, organic field-effect transistors show limited gain, usually of the order of tens, because of the large contact resistance and channel-length modulation. Here we show a new organic field-effect transistor architecture with a gain larger than 700. This is the highest gain ever reported for organic field-effect transistors. In the proposed organic field-effect transistor, the charge injection and extraction at the metal-semiconductor contacts are driven by the charge diffusion. The ideal conditions of ohmic contacts with negligible contact resistance and flat current saturation are demonstrated. The approach is general and can be extended to any thin-film technology opening unprecedented opportunities for the development of high-performance flexible electronics.