Research into organic field effect transistors (OFETs) has made significant advances—both scientifically and technologically—during the last decade, and the first products will soon enter the market. Printed electronic circuits using organic resistors, diodes and transistors may become cheap alternatives to silicon-based systems, especially in large-area applications. A key parameter for device operation, besides long term stability, is the reproducibility of the current–voltage behavior, which may be affected by hysteresis phenomena. Hysteresis effects are often observed in organic transistors during sweeps of the gate voltage (V
 GS). This hysteresis can originate in various ways, but comparative scientific investigations are rare and a comprehensive picture of “hysteresis phenomena” in OFETs is still missing. This review provides an overview of the physical effects that cause hysteresis and discusses the importance of such effects in OFETs in a comparative manner.

Current versus gate voltage hysteresis in organic field effect transistors

The structure of emeraldine salt and emeraldine bases with different molar weight and their behavior in electrochemical doping was studied by different spectroscopic and spectroelectrochemical techniques. By Fourier transform infrared (FTIR) spectroscopy, the branching of the polymer chain at tri- and tetrasubstituted benzene rings as well as the presence of small amounts of phenazine units are shown. The branching of the polymer chains increases with the increasing of the molar weight of emeraldines. The optical transitions in protonated and unprotonated emeraldine were studied by ultraviolet–visible near-infrared (UV–vis NIR) spectroscopy. By comparison of the electron spin resonance (ESR) spectra of emeraldine in protic solvents and acidic solutions, the emeraldine bases are shown to be to some extent protonated. Applying in situ ESR–UV–vis NIR spectroelectrochemistry, the charged states in emeraldines upon p-doping were investigated considering the influence of the nonideal “linear” polymer structures...

How linear is "linear" polyaniline?

The structure and stabilization of charged states during p-doping of polyaniline (PANI) were studied by in situATR-FTIR spectroelectrochemistry. The role of phenazine-like units in several copolymers of aniline and a phenazine derivative (3,7-diamino-5-phenylphenazinium chloride, phenosafranine) was investigated by spectroelectrochemistry. PANI and three copolymers with different aniline to phenosafranine ratio were electrochemically prepared. FTIR spectra of as-prepared polymers as well as in situFTIR spectra during the oxidation of the polymers give evidence of the presence of phenazine-like units in the structure of electrochemically prepared PANI, as shown by vibrations of the phenazine rings. New bands corresponding to the in-plane and out-of-plane C–H vibration of 1,2,4-trisubstituted benzene nuclei in the phenazine skeleton are found at 1033, 957, 880, 766 and 681 cm−1. The potential dependence of IR bands observed during oxidation of the polymers was compared to that of the ESR intensity and the absorption data and points to the diamagnetic species like π-dimers formed at higher oxidation level of PANI. This charged state is shown to be fixed at the link of the phenazine-like units with the linear segments of PANI.

The stabilization of charged states at phenazine-like units in polyaniline under p-doping: an in situ ATR-FTIR spectroelectrochemical study.

In situ spectroelectrochemistry is of high importance for the characterization of doping reactions in pi-conjugated polymers. In this paper we present the results of simultaneous ESR and UV-vis-NIR measurements performed in situ during electrochemical p- and n-doping of polyazulene (PAz). In previous studies on p-doping of PAz the assignment of the optical absorption bands to specific charge carriers have been somewhat controversial, therefore the aim of this study is to clarify the nature of the doping-induced charge carriers and their corresponding optical absorption bands by in situ ESR-UV-vis-NIR spectroelectrochemistry. PAz was polymerized in two different potential ranges in order to obtain films with different structures and morphologies. On the basis of our spectroelectrochemical results we propose that polarons and polaron pairs are formed during p-doping in the two different types of PAz films electrodeposited on ITO. For studying n-doping of PAz, a Pt electrode was used. The ESR signal first decreased in intensity at low doping levels and then increased in intensity at higher doping levels pointing to the formation of new paramagnetic species. At high negative potentials there occurred an additional line broadening of the ESR signal indicating the existence of rather localized negative charge carriers.

The nature of the charge carriers in polyazulene as studied by in situ electron spin resonance-UV-visible-near-infrared spectroscopy.

Photo-induced charge transfer in fullerene–oligothiophene dyads – A quantum-chemical study

Equilibrium and kinetics are compared for conjugated polymers, supposing the charged states are either polarons (Ps) and bipolarons (BPs) or polarons and polaron pairs (PPs). For low concentrations equilibrium and kinetics are virtually indistinguishable. Both are essentially different for high concentrations due to the fact that the extension of the bipolaron is almost the same as that of one polaron whereas the polaron pair has the extension of two polarons. As a result, the polaron concentration, i.e. the spin concentration, shows for a system with bipolarons a maximum and decreases for continuing increase of the potential. This dependence corresponds to results of ESR spectroelectrochemistry. In contrast, for the system with PPs both P and PP concentrations saturate at high potentials. Thus, the PP model is only reasonable if an additional subsequent second oxidation step is possible. The kinetics of the formation and dissociation of PPs or BPs, is essentially the same for concentrations that can be achieved in accumulation layers in organic MOS devices. The estimated relaxation times point to the formation and dissociation of either BPs or PPs as processes that can either cause or influence hysteresis effects in polymeric MOS capacitors, which can be described by an interface charge, depending on the sweep direction in the capacitance-voltage measurements.

A. Petr

Papers

Bipolarons or Polaron Pairs in Conducting Polymers: Equilibrium and Kinetics* , **