Efficient and bright polymer light emitting field effect transistors

Light emitting field effect transistors (LEFETs) are emerging as a multi-functional class of optoelectronic devices. LEFETs can simultaneously execute light emission and the standard logic functions of a transistor in a single architecture. However, current LEFET architectures deliver either high brightness or high efficiency but not both concurrently, thus limiting their use in technological applications. Here we show an LEFET device strategy that simultaneously improves brightness and efficiency. The key step change in LEFET performance arises from the bottom gate top-contact device architecture in which the source/drain electrodes are semitransparent and the active channel contains a bi-layer comprising of a high mobility charge-transporting polymer, and a yellow–green emissive polymer. A record external quantum efficiency (EQE) of 2.1% at 1000 cd/m² is demonstrated for polymer based bilayer LEFETs.     

Solution‐Processed Zinc Oxide as High‐Performance Air‐Stable Electron Injector in Organic Ambipolar Light‐Emitting Field‐Effect Transistors

Electron injection from the source–drain electrodes limits the performance of many n‐type organic field‐effect transistors (OFETs), particularly those based on organic semiconductors with electron affinities less than 3.5 eV. Here, it is shown that modification of gold source–drain electrodes with an overlying solution‐deposited, patterned layer of an n‐type metal oxide such as zinc oxide (ZnO) provides an efficient electron‐injecting contact, which avoids the use of unstable low‐work‐function metals and is compatible with high‐resolution patterning techniques such as photolithography. Ambipolar light‐emitting field‐effect transistors (LEFETs) based on green‐light‐emitting poly(9,9‐dioctylfluorene‐alt‐benzothiadiazole) (F8BT) and blue‐light‐emitting poly(9,9‐dioctylfluorene) (F8) with electron‐injecting gold/ZnO and hole‐injecting gold electrodes show significantly lower electron threshold voltages and several orders of magnitude higher ambipolar currents, and hence light emission intensities, than devices with bare gold electrodes. Moreover, different solution‐deposited metal oxide injection layers are compared. By spin‐coating ZnO from a low‐temperature precursor, processing temperatures could be reduced to 150 °C. Ultraviolet photoemission spectroscopy (UPS) shows that the improvement in transistor performance is due to reduction of the electron injection barrier at the interface between the organic semiconductor and ZnO/Au compared to bare gold electrodes.     

Unlocking the full potential of light emitting field-effect transistors by engineering charge injection layers

Light emitting field-effect transistors (LEFETs) are a class of next generation devices which combine the switching properties of field-effect transistors (FETs) with light emitting capabilities of organic light-emitting diodes (OLEDs) in a single device architecture. Current LEFET architectures suffer from inefficient charge injection of electrons and holes from the source and drain electrodes, leading to unbalanced charge transport and hence poor device performance. Here we report a simple fabrication method for LEFETs that delivers asymmetric source and drain electrodes comprised of low and high work function materials. The interdigitated low and high work function source–drain electrodes consist of combinations of organic materials, salts, metal oxides and metals. Using this method we were able to obtain a maximum EQE of up to 1.2% in a single layer device with Super Yellow as the active material.     

Organic Light‐Emitting Transistors Containing a Laterally Arranged Heterojunction

An approach to produce organic light‐emitting transistors (OLETs) containing a laterally arranged heterojunction structure, which minimizes exciton quenching at the metal electrodes, is described. This device configuration provides an organic light‐emitting diode (OLED) structure where the anode (source) electrode, hole‐transport material (field‐effect material), light‐emitting material, and cathode (drain) electrode are laterally arranged, thus offering a chance to control the electroluminescent intensity by changing the gate bias. Pentacene and tris(8‐quinolinolato)aluminum (Alq₃) are employed as the field‐effect and light‐emitting materials, respectively. The laterally arranged heterojunction structures are achieved by successively inclined deposition of the field‐effect and light‐emitting materials. After deposition of pentacene, a narrow gap of about 10–20 nm between the drain electrode and pentacene was obtained, thereby creating an opportunity to fabricate a laterally arranged heterojunction. In the OLETs, unsymmetrical source and drain electrodes, that is, Au and LiF/Al ones, are used to ensure efficient injection of holes and electrons. Visible‐light emission from OLETs is observed under ambient atmosphere. This result is ascribed to efficient carrier injection and transport, formation of a heterojunction, as well as good luminescence from the organic emissive layer. The device structure serves as an excellent model system for OLETs and demonstrates a general concept of adjusting the charge‐carrier injection and transport, as well as the electroluminescent properties, by forming laterally arranged heterojunctions.     

Conjugated‐Polymer‐Based Lateral Heterostructures Defined by High‐Resolution Photolithography

Solution processing of polymer semiconductors provides a new paradigm for large‐area electronics manufacturing on flexible substrates, but it also severely restricts the realization of interesting advanced device architectures, such as lateral heterostructures with defined interfaces, which are easily accessible with inorganic materials using photolithography. This is because polymer semiconductors degrade, swell, or dissolve during conventional photoresist processing. Here a versatile, high‐resolution photolithographic method is demonstrated for patterning of polymer semiconductors and exemplify this with high‐performance p‐type and n‐type field‐effect transistors (FETs) in both bottom‐ and top‐gate architectures, as well as ambipolar light‐emitting field‐effect transistors (LEFETs), in which the recombination zone can be pinned at a photolithographically defined lateral heterojunction between two semiconducting polymers. The technique therefore enables the realization of a broad range of novel device architectures while retaining optimum materials performance.     

Recent Developments and Novel Applications of Thin Film,Light‐Emitting Transistors

Light‐emitting field‐effect transistors (LEFETs) combine switching and amplification with light emission and thus represent an interesting optoelectronic device. They are not limited anymore to a few examples and specific materials but are nearly universal for a wide range of semiconductors, from organic to inorganic and nanoscale. This review introduces the basic working principles of lateral unipolar and ambipolar LEFETs and discusses recent examples based on various solution‐processed semiconducting materials. Applications beyond simple light emission are presented and possible future directions for light‐emitting transistors with added functionalities are outlined.     

Programmable polymer light emitting transistors with ferroelectric polarization-enhanced channel current and light emission

We present a voltage programmable polymer light emitting field-effect transistor (LEFET), consisting of a green emitting polymer (F8BT), and a ferroelectric polymer, P(VDF-TrFE), as the gate dielectric. We show by both experimental observations and numerical modeling that, when the ferroelectric gate dielectric is polarized in opposite directions at the drain and source sides of the channel, respectively, both electron and hole currents are enhanced, resulting in more charge recombination and ～10 times higher light emission in a ferroelectric LEFET, compared to the device with non-ferroelectric gate. As a result of the ferroelectric poling, our ferroelectric LEFETs exhibit repeated programmability in light emission, and an external quantum efficiency (EQE) of up to 1.06%. Numerical modeling reveals that the remnant polarization charge of the ferroelectric layer tends to ‘pin’ the position of the recombination zone, paving the way to integrate specific optical out-coupling structures in the channel of these devices to further increase the brightness.     

Charge transport and recombination in heterostructure organic light emitting transistors

Light-emitting field effect transistors (LEFETs) are a class of organic optoelectronic device capable of simultaneously delivering the electrical switching characteristics of a transistor and the light emission of a diode. We report on the temperature dependence of the charge transport and emissive properties in a model organic heterostructure LEFET system from 300 K to 135 K. We study parameters such as carrier mobility, brightness, and external quantum efficiency (EQE), and observe clear thermally activated behaviour for transport and injection. Overall, the EQE increases with decreasing temperature and conversely the brightness decreases. These contrary effects can be explained by a higher recombination efficiency occurring at lower temperatures, and this insight delivers new knowledge concerning the optimisation of both the transport and emissive properties in LEFETs.     

Emission Color Tuning in Ambipolar Organic Single‐Crystal Field‐Effect Transistors by Dye‐Doping

The effect of dye‐doping in ambipolar light‐emitting organic field‐effect transistors (LE‐OFETs) is investigated from the standpoint of the carrier mobilities and the electroluminescence (EL) characteristics under ambipolar operation. Dye‐doping of organic crystals permits not only tuning of the emission color but also significantly increases the efficiency of ambipolar LE‐OFETs. A rather high external EL quantum efficiency (～0.64%) of one order of magnitude higher than that of a pure p‐distyrylbenzene (P3V2) single crystal is obtained by tetracene doping. The doping of tetracene molecules into a host P3V2 crystal has almost no effect on the electron mobility and the dominant carrier recombination process in the tetracene‐doped P3V2 crystal involves direct carrier recombination on the tetracene molecules.     

Switchable Supercapacitors with Transistor‐Like Gating Characteristics (G‐Cap)

A novel three‐electrode electrolyte supercapacitor (electric double‐layer capacitor [EDLC]) architecture in which a symmetrical interdigital “working” two‐electrode micro‐supercapacitor array (W‐Cap) is paired with a third “gate” electrode that reversibly depletes/injects electrolyte ions into the system controlling the “working” capacity effectively is described. All three electrodes are based on precursor‐derived nanoporous carbons with well‐defined specific surface area (735 m² g^?1). The interdigitated architecture of the W‐Cap is precisely manufactured using 3D printing. The W‐Cap operating with a proton conducting PVA/H₂SO₄‐hydrogel electrolyte and high capacitance (6.9 mF cm^?2) can be repeatedly switched “on” and “off”. By applying a low DC bias potential (?0.5 V) at the gate electrode, the AC electroadsorption in the coupled interdigital nanoporous carbon electrodes of the W‐Cap is effectively suppressed leading to a stark capacity drop by two orders of magnitude from an “on” to an “off” state. The switchable micro‐supercapacitor is the first of its kind. This general concept is suitable for implementing a broad range of nanoporous materials and advanced electrolytes expanding its functions and applications in future. The integration of intelligent functions into EDLC devices has extensive implications for diverse areas such as capacitive energy management, microelectronics, iontronics, and neuromodulation.     

Controlling Electron and Hole Charge Injection in Ambipolar Organic Field‐Effect Transistors by Self‐Assembled Monolayers

Controlling contact resistance in organic field‐effect transistors (OFETs) is one of the major hurdles to achieve transistor scaling and dimensional reduction. In particular in the context of ambipolar and/or light‐emitting OFETs it is a difficult challenge to obtain efficient injection of both electrons and holes from one injecting electrode such as gold since organic semiconductors have intrinsically large band gaps resulting in significant injection barrier heights for at least one type of carrier. Here, systematic control of electron and hole contact resistance in poly(9,9‐di‐n‐octylfluorene‐alt‐benzothiadiazole) ambipolar OFETs using thiol‐based self‐assembled monolayers (SAMs) is demonstrated. In contrast to common believe, it is found that for a certain SAM the injection of both electrons and holes can be improved. This simultaneous enhancement of electron and hole injection cannot be explained by SAM‐induced work‐function modifications because the surface dipole induced by the SAM on the metal surface lowers the injection barrier only for one type of carrier, but increases it for the other. These investigations reveal that other key factors also affect contact resistance, including i) interfacial tunneling through the SAM, ii) SAM‐induced modifications of interface morphology, and iii) the interface electronic structure. Of particular importance for top‐gate OFET geometry is iv) the active polymer layer thickness that dominates the electrode/polymer contact resistance. Therefore, a consistent explanation of how SAM electrode modification is able to improve both electron and hole injection in ambipolar OFETs requires considering all mentioned factors.     

Top‐Emission Organic Light‐Emitting Diode with a Novel Copper/Graphene Composite Anode

The relatively high sheet resistance of graphene compared with indium tin oxide (ITO) blocks the applications of graphene as transparent electrodes in organic light‐emitting diodes. A novel copper (Cu)/graphene composite electrode is presented and employed as the anode of a top‐emission organic light‐emitting diode with the structure of Cu/graphene/V₂O₅/NPB/Alq₃/Alq₃: C545T/Bphen: Cs₂CO₃/Sm/Au. The Cu/graphene composite electrodes are fabricated by growing graphene directly on Cu substrates via the chemical vapor deposition method without any transfer process. The maxima of current efficiency and power efficiency of a typical Cu/graphene composite anode device reach 6.1 cd/A and 7.6 lm/W, respectively, which are markedly higher than those of the control devices with a graphene anode, a Cu anode or an ITO anode. The low sheet resistance of the composite electrode, the high quality of graphene without any transfer process and the avoidance of wave guiding loss in glass or polyethylene terephthalate substrates result in the improvements of light emission efficiencies.     

Coreless Fiber‐Based Whispering‐Gallery‐Mode Assisted Lasing from Colloidal Quantum Well Solids

Whispering gallery mode (WGM) resonators are shown to hold great promise to achieve high‐performance lasing using colloidal semiconductor nanocrystals (NCs) in solution phase. However, the low packing density of such colloidal gain media in the solution phase results in increased lasing thresholds and poor lasing stability in these WGM lasers. To address these issues, here optical gain in colloidal quantum wells (CQWs) is proposed and shown in the form of high‐density close‐packed solid films constructed around a coreless fiber incorporating the resulting whispering gallery modes to induce gain and waveguiding modes of the fiber to funnel and collect light. In this work, a practical method is presented to produce the first CQW‐WGM laser using an optical fiber as the WGM cavity platform operating at low thresholds of ≈188 µJ cm^?2 and ≈1.39 mJ cm^?2 under one‐ and two‐photon absorption pumped, respectively, accompanied with a record low waveguide loss coefficient of ≈7 cm^?1 and a high net modal gain coefficient of ≈485 cm^?1. The spectral characteristics of the proposed CQW‐WGM resonator are supported with a numerical model of full electromagnetic solution. This unique CQW‐WGM cavity architecture offers new opportunities to achieve simple high‐performance optical resonators for colloidal lasers.     

Schottky‐Barrier‐Controllable Graphene Electrode to Boost Rectification in Organic Vertical P–N Junction Photodiodes

Monolayer graphene is used as an electrode to develop novel electronic device architectures that exploit the unique, atomically thin structure of the material with a low density of states at its charge neutrality point. For example, a single semiconductor layer stacked onto graphene can provide a semiconductor–electrode junction with a tunable injection barrier, which is the basis for a primitive transistor architecture known as the Schottky barrier field‐effect transistor. This work demonstrates the next level of complexity in a vertical graphene–semiconductor architecture. Specifically, an organic vertical p‐n junction (p‐type pentacene/n‐type N,N′‐dioctyl‐3,4,9,10‐perylenedicarboximide (PTCDI‐C₈)) on top of a graphene electrode constituting a novel gate‐tunable photodiode device structure is fabricated. The model device confirms that controlling the Schottky barrier height at the pentacene–graphene junction can (i) suppress the dark current density and (ii) enhance the photocurrent of the device, both of which are critical to improve the performance of a photodiode.     

Integrating Efficient Optical Gain in High‐Mobility Organic Semiconductors for Multifunctional Optoelectronic Applications

Simultaneously integrating efficient optical gain and high charge carrier mobility in organic semiconductors for multifunctional optoelectronic applications is challenging. Here, a new thiophene/phenylene derivative, 5,5′‐bis(2,2‐diphenylvinyl)‐bithiophene (BDPV2T), containing an appropriate butterfly molecular configuration in a π‐conjugated structure, is designed to achieve both solid‐state emission and charge transport properties. The prepared BDPV2T crystals exhibit excellent light‐emitting characteristics with a photoluminescence quantum yield of 30%, low light‐amplification threshold of 8 kW cm^?2, high optical net gain up to 70 cm^?1, and high charge carrier mobility up to 1 cm² V^?1 s^?1 in their J‐aggregate single crystals. These BDPV2T single crystal characteristics ensure their application potential for photodetectors, field‐effect transistors, and light‐emitting transistors. High optoelectronic performances are achieved with photoresponsivity of 2.0 × 10³ A W^?1 and light on/off ratio of 5.4 × 10⁵ in photodetectors, and efficient ambipolar charge transport (µ_h: 0.14 cm² V^?1 s^?1, µ_e: 0.02 cm² V^?1 s^?1) and electroluminescence characteristics in light‐emitting transistors. The remarkably integrated optoelectronic properties of BDPV2T suggest it is a promising candidate for organic multifunctional and electrically pumped laser applications.     

Ambipolar Light‐Emitting Transistors of a Tetracene Single Crystal

The first ambipolar light‐emitting transistor of an organic molecular semiconductor single crystal, tetracene, is demonstrated. In the device configuration, electrons and holes injected from separate magnesium and gold electrodes recombined radiatively within the channel. By varying the applied voltages, the position of the recombination/emission zone could be moved to any position along the channel. Because of the changes made to the device structure, including the use of single crystals and polymer dielectric layers and the adoption of an inert‐atmosphere fabrication process, the set of materials that can be used for light‐emitting transistors has been expanded to include monomeric molecular semiconductors.     

High Performance p‐ and n‐Type Light‐Emitting Field‐Effect Transistors Employing Thermally Activated Delayed Fluorescence

Light‐emitting field‐effect transistors (LEFETs) are an emerging type of devices that combine light‐emitting properties with logical switching function. One of the factors limiting their efficiency stems from the spin statistics of electrically generated excitons. Only 25% of them, short lived singlet states, are capable of light emission, with the other 75% being long lived triplet states that are wasted as heat due to spin‐forbidden processes. Traditionally, the way to overcome this limitation is to use phosphorescent materials as additional emission channel harnessing the triplet excitons. Here, an alternative strategy for triplet usage in LEFETs in the form of thermally activated delayed fluorescence (TADF) is presented. Devices employing a TADF capable material, 4CzIPN (2,4,5,6‐tetra[9H‐carbazol‐9‐yl]isophthalonitrile), in both n‐type and p‐type configurations are shown. They manifest excellent electrical characteristics, consistent brightness in the range of 100–1,000 cd m^‐2 and external quantum efficiency (EQE) of up to 0.1%, which is comparable to the equivalent organic light‐emitting diode (OLED) based on the same materials. Simulation identifies the poor light out‐coupling as the main reason for lower than expected EQEs. Transmission measurements show it can be partially alleviated using a more transparent top contact, however more structural optimization is needed to tap the full potential of the device.     

Optically‐Pumped Lasing in Hybrid Organic–Inorganic Light‐Emitting Diodes

Here, the use of metal oxide layers both for charge transport and injection into an emissive semiconducting polymer and also for the control of the in‐plane waveguided optical modes in light‐emitting diodes (LEDs) is reported. The high refractive index of zinc oxide is used to confine these modes away from the absorbing electrodes, and include a nano‐imprinted grating in the polymer layer to introduce distributed feedback and enhance optical out‐coupling. These structures show a large increase in the luminescence efficiency over conventional devices, with photoluminescence efficiency increased by up to 45%. Furthermore, optically‐pumped lasing in hybrid oxide polymer LEDs is demonstrated. A tuneable lasing emission is also obtained in a single device structure by employing a graduated thickness of a zinc oxide inter‐layer. This demonstrates the scope for using such architectures to improve the external efficiency of organic semiconductor LEDs, and opens new possibilities for the realization of polymer injection lasers.     

Non‐Lithographic Fabrication of All‐2D α‐MoTe2 Dual Gate Transistors

As one of the emerging new transition‐metal dichalcogenides materials, molybdenum ditelluride (α‐MoTe₂) is attracting much attention due to its optical and electrical properties. This study fabricates all‐2D MoTe₂‐based field effect transistors (FETs) on glass, using thin hexagonal boron nitride and thin graphene in consideration of good dielectric/channel interface and source/drain contacts, respectively. Distinguished from previous works, in this study, all 2D FETs with α‐MoTe₂ nanoflakes are dual‐gated for driving higher current. Moreover, for the present 2D dual gate FET fabrications on glass, all thermal annealing and lithography processes are intentionally exempted for fully non‐lithographic method using only van der Waal's forces. The dual‐gate MoTe₂ FET displays quite a high hole and electron mobility over ≈20 cm² V^?1 s^?1 along with ON/OFF ratio of ≈10⁵ in maximum as an ambipolar FET and also demonstrates high drain current of a few tens‐to‐hundred μA at a low operation voltage. It appears promising enough to drive organic light emitting diode pixels and NOR logic functions on glass.     

Low‐Threshold Organic Semiconductor Lasers with the Aid of Phosphorescent Ir(III) Complexes as Triplet Sensitizers

Organic semiconductor lasers (OSLs) have emerged as particularly challenging. One of the major issues preventing the successful realization of lasing from organic emitters under electrically pumped conditions is the inevitable population of triplet excitons. Herein, a novel concept is presented to construct triplet–singlet guest–host gain systems with incorporating iridium complexes as the triplet sensitizers and a fluorescent conjugated polymer as the gain media to achieve light amplification. The direct triplet–singlet energy transfer process is confirmed by photoluminescence excitation spectra, photoinduced absorption spectroscopy, and fluorescence transients of the blend samples. Successful light amplification with a threefold lower amplified spontaneous emission threshold and much better lasing performance is demonstrated for the resulting triplet–singlet guest–host system as compared with the corresponding gain system without triplet sensitizers. Moreover, under electrically driven conditions, the fluorescent organic light‐emitting diodes (OLEDs) based on the triplet–singlet guest–host systems with “triplet sensitizers” exhibit enhanced electrical performance relative to those without. The work suggests an effective general methodology to utilize both the singlet and triplet excitons to contribute to the light amplification with excellent electrical performance in OLEDs, opening prospects toward attempting electrically pumped OSLs.