Perq-Jon Chia

High-performance polymer semiconducting heterostructure devices by nitrene-mediated photocrosslinking of alkyl side chains

Heterostructures are central to the efficient manipulation of charge carriers, excitons and photons for high-performance semiconductor devices. Although these can be formed by stepwise evaporation of molecular semiconductors, they are a considerable challenge for polymers owing to re-dissolution of the underlying layers. Here we demonstrate a simple and versatile photocrosslinking methodology based on sterically hindered bis(fluorophenyl azide)s. The photocrosslinking efficiency is high and dominated by alkyl side-chain insertion reactions, which do not degrade semiconductor properties. We demonstrate two new back-infiltrated and contiguous interpenetrating donor-acceptor heterostructures for photovoltaic applications that inherently overcome internal recombination losses by ensuring path continuity to give high carrier-collection efficiency. This provides the appropriate morphology for high-efficiency polymer-based photovoltaics. We also demonstrate photopatternable polymer-based field-effect transistors and light-emitting diodes, and highly efficient separate-confinement-heterostructure light-emitting diodes. These results open the way to the general development of high-performance polymer semiconductor heterostructures that have not previously been thought possible.

Low frequency noise analysis on organic thin film transistors

Bottom-contact organic field-effect transistors (OFETs) based on poly(3-hexylthiophene) with different channel lengths were fabricated under different substrate pretreatment process conditions. These OFET devices were characterized using low frequency noise (LFN) spectroscopy, and the device performance parameters were correlated with the level of LFN. It is observed that the devices with higher noise levels showed poorer device properties when compared with the devices operated at same Ids of the same channel length. It is also observed that the noise level increased with the increase in channel length for devices with the same pretreatment conditions, which is due to increased trapping and detrapping in the channel material interface domain. The OFET device operating around the threshold voltage Vth will have a 1/f noise slope that is flatter, having a gradient that is smaller in magnitude. The threshold voltage of a device can thus be observed to be at the gate voltage in which 1/f noise intensity is t...

Solvent effects and multiple aggregate states in high-mobility organic field-effect transistors based on poly(bithiophene-alt-thienothiophene)

Franck–Condon absorption analysis reveals the existence of several aggregate states in poly(2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT) thin films which impact their recrystallization and the attainable field-effect mobility (μFET). Poor solvents (toluene and mixed-xylenes) lock in both disordered and well-ordered states that cannot be annealed away even in the liquid crystalline phase. This reduces μFET and increases mobility activation energies compared with films from good solvents (chlorobenzene and o-dichlorobenzene). Despite its poor solubility characteristics, PBTTT can be ink-jet printed in dilute chlorobenzene, and devices can be operated unencapsulated in ambient, in the dark (>105cycles over several days) with only a moderate mobility loss.

Electromigration of the conducting polymer in organic semiconductor devices and its stabilization by cross-linking

X-ray photoelectron spectroscopy (XPS) measurement of the ratio of poly(3,4-ethylenedioxythiophene) (PEDT) to polystyrenesulfonate (PSS) reveals accumulation of PEDT+ at the interface between the PEDT:PSSH hole-injection layer and the organic semiconductor during diode operation. This ionic drift of PEDT+ occurs even at low fields of 1Vcm−1, which will have an impact on the operational stability of the characteristics of organic light-emitting diodes. XPS and Raman spectroscopy indicate that dedoping of PEDT+ does not occur significantly in hole-only devices. Cross-linking at the 1mol% level can stabilize the conducting polymer sufficiently against electromigration.

Determination of the interface δ-hole density in a blue-emitting organic semiconductor diode by electromodulated absorption spectroscopy

The hole density at the interface of a poly(fluorene-alt-triarylamine) (TFB) with p-doped poly(3,4-ethylenedioxythiophene) (PEDT) anodes has been determined from electromodulation of the TFB subgap polaron band. At 295 K, this δ-hole density σOSC is approximately 1×1012 cm−2, for which the current–voltage characteristics indicate an Ohmic contact. However at 30 K, σOSC falls to 2×1011 cm−2, and the contact characteristics approach the injecting-blocking boundary. The PEDT/TFB vacuum offset inside the device is inferred to be 0.1 eV, and so the Fermi level is not as deeply pinned in the TFB gap as suggested by ultraviolet photoemission measurements.

Impact of self-assembled monolayer on low frequency noise of organic thin film transistors

Bottom-contact organic field-effect transistors (FETs) based on regioregular poly(3-hexylthiophene) were fabricated with different surface treatments and were evaluated using a low frequency noise (LFN) spectroscopy. The oxygen-plasma (OP) treated device shows the highest mobility with the lowest current fluctuation. Octadecyltrichlorosilane and perfluorodecyldimetylchlorosilane treated device gives a higher noise compared with the OP treated device. Hexamethyldisilazane treated devices show the highest noise but the lowest mobility. The LFN results are correlated with organic FET device mobility and stability, proved by channel material crystallinity and degree of dislocations analysis. LFN measurement provides a nondisruptive and direct methodology to characterize device performance.

Robust reproducible large-area molecular rectifier junctions

Stable rectifying molecular junctions have been obtained by sandwiching self-assembled monolayer films containing “push-pull” donor-π-acceptor (D-π-A) moieties between Au and poly(3,4-ethylenedioxythiophene) electrodes. These D-π-A moieties possess moderate molecular dipoles, but assemble into films with nearly zero dipole moment due to adoption of high average tilt angles. Nevertheless reproducible and well-behaved rectifications (ratio up to 3.3) in the expected polarity were obtained. At low biases, the current-voltage characteristics follow Simmon’s tunneling theory with reasonable barrier heights and an effective tunnel mass of ∼0.5me. This suggests that asymmetric tunneling, and not carrier injection, is the origin of the rectification.

Chemical reversability of the electrical dedoping of conducting polymers : An organic chemically erasable programmable read-only memory

The loss of electronic conductivity of p-doped poly(3,4-ethylenedioxythiophene) at high electrical bias is shown to be chemically reversible upon redoping with iodine vapor. This provides further confirmation that the initial loss of conductivity arises from the injection-induced dedoping mechanism. Repeat “write-erase” cycles are possible, which gives a rudimentary organic chemically erasable programmable read-only memory. Transient measurements show that the write time (i.e., time for loss of conductivity) decreases from thousands of seconds just above the critical electric field of 50kVcm–1 to millisecond well above this value but below the onset of electrochemical destruction.