Rui-Qi Png

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.

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.

Influence of interfacial area on exciton separation and polaron recombination in nanostructured bilayer all-polymer solar cells.

The macroscopic device performance of organic solar cells is governed by interface physics on a nanometer scale. A comb-like bilayer all-polymer morphology featuring a controlled enhancement in donor-acceptor interfacial area is employed as a model system to investigate the fundamental processes of exciton separation and polaron recombination in these devices. The different nanostructures are characterized locally by SEM/AFM, and the buried interdigitating interface of the final device architecture is statistically verified on a large area via advanced grazing incidence X-ray scattering techniques. The results show equally enhanced harvesting of photoexcitons in both donor and acceptor materials directly correlated to the total enhancement of interfacial area. Apart from this beneficial effect, the enhanced interface leads to significantly increased polaron recombination losses both around the open-circuit voltage and maximum power point, which is determined in complement with diode dark current characteristics, impedance spectroscopy, and transient photovoltage measurements. From these findings, it is inferred that a spatially optimized comb-like donor-acceptor nanonetwork alone is not the ideal morphology even though often postulated. Instead, the energetic landscape has to be considered. A perfect morphology for an excitonic solar cell must be spatially and energetically optimized with respect to the donor-acceptor interface.

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.

Solution-processed conjugated polymer organic p-i-n light-emitting diodes with high built-in potential by solution- and solid-state doping

Polymer p-i-n homojunction light-emitting diodes (LEDs) comprising p-doped poly(dioctylfluorene-alt-benzothiadiazole) (F8BT) hole-injection, intrinsic F8BT emitter, and n-doped F8BT electron-injection layers have been demonstrated. A thin F8BT film was photocrosslinked and bulk p-doped by nitronium oxidation, then overcoated with an F8BT layer which was then surface n-doped by contact printing with naphthalenide on an elastomeric stamp. These LEDs exhibit high built-in potential (Vbi=2.2 V), efficient bipolar injection, and greatly improved external electroluminescence efficiency compared to control devices without the p-i-n structure. A modulated photocurrent technique was used to measure this Vbi, which systematically improves with diode structure.

Effective work functions for the evaporated metal/organic semiconductor contacts from in-situ diode flatband potential measurements

The diode built-in potentials (Vbi) of several polymer organic semiconductor (OSC) thin films [(2,5-dialkoxy-substituted poly(p-phenylenevinylene), poly(9,9-dialkylfluorene), poly(9,9-dialkylfluorene-alt-phenylene(N-phenyl)iminophenylene), and poly(9,9-dialkylfluorene-alt-benzothiadiazole)] sandwiched between p-doped poly(3,4-ethylenedioxythiophene) (PEDT:PSSH) and evaporated metal contacts have been measured by bias-dependent electromodulated absorption (EA) spectroscopy of the Stark-shifted π–π* band. From these values and the vacuum-level offsets at the PEDT:PSSH contacts evaluated by sub-gap EA spectroscopy, the following effective work functions for the buried evaporated metal contacts have been obtained: Al 3.4 ± 0.1, Ag 3.7 ± 0.1, Au 4.4 ± 0.1, and Ca 2.4 ± 0.1 eV. These work functions are smaller than those of the “clean” metal surfaces by up to 0.8 eV, and are substantially independent of the OSC in the absence of charge transfer.

Polarization effects on energy-level alignment at the interfaces of polymer organic semiconductor films

The thickness-dependent evolutions of the Fermi level EF and ionization potential Ip of ultrathin films of regioregular poly(3-hexylthiophene) and poly[2,5-bis(3-tetradecylthiophene-2-yl)thieno[3,2-b]thiophene], deposited as edge-on π-stacked lamellae on gold and on p-doped poly(3,4-ethylenedioxythiophene) electrodes, have been measured by ultraviolet photoemission spectroscopy. The Ip increases by 0.3 eV on going from a monolayer film to a few-nanometer-thick film. Correspondingly, the EF pinning depth increases from 0.2 eV to 0.5 eV. This valence “band bending” which occurs for a constant vacuum level can be quantitatively modeled by microelectrostatic self-consistent polarization field calculations that incorporate both substrate and organic semiconductor film effects. The EF pinning to the first monolayer is relatively shallow.