Lay-Lay Chua

General observation of n-type field-effect behaviour in organic semiconductors

Organic semiconductors have been the subject of active research for over a decade now, with applications emerging in light-emitting displays and printable electronic circuits. One characteristic feature of these materials is the strong trapping of electrons but not holes: organic field-effect transistors (FETs) typically show p-type, but not n-type, conduction even with the appropriate low-work-function electrodes, except for a few special high-electron-affinity or low-bandgap organic semiconductors. Here we demonstrate that the use of an appropriate hydroxyl-free gate dielectric—such as a divinyltetramethylsiloxane-bis(benzocyclobutene) derivative (BCB; ref. 6)—can yield n-channel FET conduction in most conjugated polymers. The FET electron mobilities thus obtained reveal that electrons are considerably more mobile in these materials than previously thought. Electron mobilities of the order of 10-3 to 10-2 cm2 V-1 s-1 have been measured in a number of polyfluorene copolymers and in a dialkyl-substituted poly(p-phenylenevinylene), all in the unaligned state. We further show that the reason why n-type behaviour has previously been so elusive is the trapping of electrons at the semiconductor–dielectric interface by hydroxyl groups, present in the form of silanols in the case of the commonly used SiO2 dielectric. These findings should therefore open up new opportunities for organic complementary metal-oxide semiconductor (CMOS) circuits, in which both p-type and n-type behaviours are harnessed.

High-stability ultrathin spin-on benzocyclobutene gate dielectric for polymer field-effect transistors

Using a thermal-crosslinkable siloxane bisbenzocyclobutene, high quality spin-on (solutionprocessable) gate dielectric layers as thin as 50 nm have been fabricated over the semiconductor layer for polymer field-effect transistors. This was demonstrated on a poly(9,9-dialkylfluorene-alt-triarylamine) as p-channel semiconductor, with a surfactantion-exchanged poly(3,4-ethylenedioxythiophene)-polystyrenesulfonate complex as top-gate electrode. The devices operate at a low voltage with a field-effect mobility of few 10−4 cm2/Vs, and can be continuously operated at 120 °C.

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.

High internal quantum efficiency in fullerene solar cells based on crosslinked polymer donor networks

The power conversion efficiency of organic photovoltaic cells depends crucially on the morphology of their donor–acceptor heterostructure. Although tremendous progress has been made to develop new materials that better cover the solar spectrum, this heterostructure is still formed by a primitive spontaneous demixing that is rather sensitive to processing and hence difficult to realize consistently over large areas. Here we report that the desired interpenetrating heterostructure with built-in phase contiguity can be fabricated by acceptor doping into a lightly crosslinked polymer donor network. The resultant nanotemplated network is highly reproducible and resilient to phase coarsening. For the regioregular poly(3-hexylthiophene):phenyl-C61-butyrate methyl ester donor–acceptor model system, we obtained 20% improvement in power conversion efficiency over conventional demixed biblend devices. We reached very high internal quantum efficiencies of up to 0.9 electron per photon at zero bias, over an unprecedentedly wide composition space. Detailed analysis of the power conversion, power absorbed and internal quantum efficiency landscapes reveals the separate contributions of optical interference and donor–acceptor morphology effects.

Suppressing recombination in polymer photovoltaic devices via energy-level cascades.

An energy cascading structure is designed in a polymer photovoltaic device to suppress recombination and improve quantum yields. By the insertion of a thin polymer interlayer with intermediate energy levels, electrons and holes can effectively shuttle away from each other while being spatially separated from recombination. An increase in open-circuit voltage and short-circuit current are observed in modified devices.

Polyfluorene-based light-emitting diodes with an azide photocross-linked poly(3,4-ethylene dioxythiophene):(polystyrene sulfonic acid) hole-injecting layer

We used a water-soluble bis(fluorinated phenyl azide) to cross-link a poly(ethylene dioxythiophene):poly(styrene sulphonic acid) (PEDOT:PSS), hole-injection layer, with a view to its future use with water-soluble emitters. To enable direct comparison with conventional PEDOT:PSS, we studied the cross-linked films in diodes incorporating the organic-solvent soluble polymer poly(9,9′-dioctylfluorene-alt-benzothiadiazole). Kelvin probe characterization of the PEDOT:PSS and electroabsorption measurements of the devices consistently show a 0.2eV increase of the PEDOT:PSS work function upon cross-linking. We also observe a 70-fold reduction in resistivity, an increase of the current above threshold and a decrease of the “leakage” current below threshold.

Doped polymer semiconductors with ultrahigh and ultralow work functions for ohmic contacts

To make high-performance semiconductor devices, a good ohmic contact between the electrode and the semiconductor layer is required to inject the maximum current density across the contact. Achieving ohmic contacts requires electrodes with high and low work functions to inject holes and electrons respectively, where the work function is the minimum energy required to remove an electron from the Fermi level of the electrode to the vacuum level. However, it is challenging to produce electrically conducting films with sufficiently high or low work functions, especially for solution-processed semiconductor devices. Hole-doped polymer organic semiconductors are available in a limited work-function range, but hole-doped materials with ultrahigh work functions and, especially, electron-doped materials with low to ultralow work functions are not yet available. The key challenges are stabilizing the thin films against de-doping and suppressing dopant migration. Here we report a general strategy to overcome these limitations and achieve solution-processed doped films over a wide range of work functions (3.0–5.8 electronvolts), by charge-doping of conjugated polyelectrolytes and then internal ion-exchange to give self-compensated heavily doped polymers. Mobile carriers on the polymer backbone in these materials are compensated by covalently bonded counter-ions. Although our self-compensated doped polymers superficially resemble self-doped polymers, they are generated by separate charge-carrier doping and compensation steps, which enables the use of strong dopants to access extreme work functions. We demonstrate solution-processed ohmic contacts for high-performance organic light-emitting diodes, solar cells, photodiodes and transistors, including ohmic injection of both carrier types into polyfluorene—the benchmark wide-bandgap blue-light-emitting polymer organic semiconductor. We also show that metal electrodes can be transformed into highly efficient hole- and electron-injection contacts via the self-assembly of these doped polyelectrolytes. This consequently allows ambipolar field-effect transistors to be transformed into high-performance p- and n-channel transistors. Our strategy provides a method for producing ohmic contacts not only for organic semiconductors, but potentially for other advanced semiconductors as well, including perovskites, quantum dots, nanotubes and two-dimensional materials.

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.

Organic double-gate field-effect transistors: Logic-AND operation

A unipolar double-gate field-effect transistor (DG-FET) with AND logic functionality is demonstrated. This operation regime arises through a symmetric electrostatic coupling of two conduction channels via the intrinsic semiconductor layer. According to simulation, this mode of operation is general and not limited to organic devices. These DG-FETs provide for two-signal modulation in a single device of a shared active region, and are thus versatile building blocks for logic, memories, sensing, data transmission and light-emitting FETs. When the two gates are tied together somewhat reminiscent of Si FinFETs, these devices can achieve considerably deeper gate modulation than possible with single gating.