Controlling charge balance using non-conjugated polymer interlayer in quantum dot light-emitting diodes

The balance of electron–hole charge carriers in quantum dot (QD) light-emitting diodes (QLEDs) is an important factor to achieve high efficiency. However, poor interfacial properties between QDs and their adjacent layers are likely to deteriorate the electron–hole charge balance, resulting in the poor performance of a QLED. In this paper, we report an enhanced efficiency in red-emitting inverted QLEDs by modifying the interface properties between QDs and ZnO electron transport layer (ETL) using a thin layer of non-conjugated polymer, poly(4-vinylpyridine) (PVPy). Based on the precise control of the electrical properties with PVPy, the maximum efficiency of the QLED is enhanced by 30% compared to the device without a PVPy layer. In particular, the efficiency at low current density region is significantly increased. We investigate the effect of the PVPy interlayer on the performance of QLEDs and find that this thin layer not only shifts the energy levels of the underlying ZnO ETL, but also effectively blocks the leakage current at the ETL/QD interface.     

Efficient Charge Injection in Organic Field‐Effect Transistors Enabled by Low‐Temperature Atomic Layer Deposition of Ultrathin VOx Interlayer

Charge injection at metal/organic interface is a critical issue for organic electronic devices in general as poor charge injection would cause high contact resistance and severely limit the performance of organic devices. In this work, a new approach is presented to enhance the charge injection by using atomic layer deposition (ALD) to prepare an ultrathin vanadium oxide (VO_x) layer as an efficient hole injection interlayer for organic field‐effect transistors (OFETs). Since organic materials are generally delicate, a gentle low‐temperature ALD process is necessary for compatibility. Therefore, a new low‐temperature ALD process is developed for VO_x at 50 °C using a highly volatile vanadium precursor of tetrakis(dimethylamino)vanadium and non‐oxidizing water as the oxygen source. The process is able to prepare highly smooth, uniform, and conformal VO_x thin films with precise control of film thickness. With this ALD process, it is further demonstrated that the ALD VO_x interlayer is able to remarkably reduce the interface contact resistance, and, therefore, significantly enhance the device performance of OFETs. Multiple combinations of the metal/VO_x/organic interface (i.e., Cu/VO_x/pentacene, Au/VO_x/pentacene, and Au/VO_x/BOPAnt) are examined, and the results uniformly show the effectiveness of reducing the contact resistance in all cases, which, therefore, highlights the broad promise of this ALD approach for organic devices applications in general.     

The origins in the transformation of ambipolar to n-type pentacene-based organic field-effect transistors

With aluminum (Al) source–drain electrodes, the transfer characteristics of pentacene-based organic field-effect transistors (OFETs) change from ambipolar to n-type after 24 h of storage in a nitrogen-filled glove box Chang et al. (2011) [16]. The time-dependent decrease of hole current is associated with the interfacial reaction at the Al source–drain electrodes and pentacene, which was studied by in-situ ultraviolet photoemission spectroscopy and X-ray photoelectron spectroscopy in this work. Experimental results indicate that the interface of the Al and pentacene is partially oxidized, but the similar oxidation was not observed at the interface of the pentacene and silver. The time-dependent oxidization of Al and pentacene creates an interfacial barrier to suppress the hole injection from Al electrodes (extraction of electrons from pentacene). However, it shows minor effect in the injection of electrons from Al electrode. Since the rate of oxidation is related to the contact area of the pentacene and Al, co-evaporating a thin Al:pentacene interlayer between the pentacene and Al electrodes expands the contact surface and accelerates the reaction, which is suitable for the fabrication of n-type only pentacene-based OFETs. This study highlights the impact of the interfacial reaction in Al/pentacene interface for the transformation of ambipolar to n-type OFETs.     

Bipolar charge transport in organic field-effect transistors: Enabling high mobilities and transport of photo-generated charge carriers by a molecular passivation layer

High mobility bipolar charge carrier transport in organic field-effect transistors (OFETs) can be enabled by a molecular passivation layer and selective electrode materials. Using tetratetracontane as passivation layer bipolar transport was realised in the organic semiconductors copper-phthalocyanine, diindenoperylene, pentacene, TIPS-pentacene and sexithiophene and mobilities of up to 0.1 cm²/V s were achieved for both electrons and holes. Furthermore, the trap and injection behaviour was analysed leading to a more general understanding of the transport levels of the used molecular semiconductors and their limitations for electron and hole transport in OFETs. With this knowledge the transistor operation can be further improved by applying two different electrode materials and a light-emitting transistor was demonstrated.Additionally, the effect of illumination on organic field-effect transistors was investigated for unipolar and bipolar devices. We find that the behaviour of photo-excited electrons and holes depends on the interface between the insulator and the semiconductor and the choice of contact materials. Whereas filling of electron traps by photo-generated charges and the related accumulation field are the reason for changes in charge carrier transport upon illumination without passivation layer, both types of charge carriers can be transported also in unipolar OFETs, if a passivation layer is present.     

Employing microspectroscopy to track charge trapping in operating pentacene OFETs

Ultrathin pentacene films resemble benchmark and model materials for organic field-effect transistors (OFETs). We employ scanning transmission X-ray microspectroscopy (STXM) and confocal Raman microspectroscopy as highly resolving probes to obtain insight into the correlation of morphology and charge transport in pentacene OFETs. By combining the operation-induced intensity increase in Raman-active bands with micromorphology, we are able to visualize charge-induced effects, in particular charge trapping in pentacene OFETs during operation. The high sensitivity and specificity of Raman microscopy allows to distinguish between orientation and charge-induced effects and thus to locate the trapped charges at grain boundaries.     

Tuning Contact Resistance in Top‐Contact p‐Type and n‐Type Organic Field Effect Transistors by Self‐Generated Interlayers

Contact resistance significantly limits the performance of organic field‐effect transistors (OFETs). Positioning interlayers at the metal/organic interface can tune the effective work‐function and reduce contact resistance. Myriad techniques offer interlayer processing onto the metal pads in bottom‐contact OFETs. However, most methods are not suitable for deposition on organic films and incompatible with top‐contact OFET architectures. Here, a simple and versatile methodology is demonstrated for interlayer processing in both p‐ and n‐type devices that is also suitable for top‐contact OFETs. In this approach, judiciously selected interlayer molecules are co‐deposited as additives in the semiconducting polymer active layer. During top contact deposition, the additive molecules migrate from within the bulk film to the organic/metal interface due to additive‐metal interactions. Migration continues until a thin continuous interlayer is completed. Formation of the interlayer is confirmed by X‐ray photoelectron spectroscopy (XPS) and cross‐section scanning transmission electron microscopy (STEM), and its effect on contact resistance by device measurements and transfer line method (TLM) analysis. It is shown that self‐generated interlayers that reduce contact resistance in p‐type devices, increase that of n‐type devices, and vice versa, confirming the role of additives as interlayer materials that modulate the effective work‐function of the organic/metal interface.     

Improved ambipolar charge injection in organic field-effect transistors with low cost metal electrode using polymer sorted semiconducting carbon nanotubes

Solution-processed thin film transistors can be implemented using simple and low cost fabrication, and are the best candidates for commercialization due to their application to a range of wearable electronics. We report an ambipolar charge injection interlayer that can improve both hole and electron injection in organic field-effect transistors (OFETs) with inexpensive source-drain electrodes. The solution processed ambipolar injection layer is fabricated by selective dispersion of semiconducting single walled carbon nanotubes using poly(9,9-dioctylfluorene). OFETs with molybdenum (Mo) contacts and interlayer (Mo/interlayer OFETs) exhibit superior performance, including higher hole and electron mobilities, device yield, lower threshold voltages, and lower trap densities than those of bare transistors. While OFETs with Mo contacts show unipolar p-type behaviour, Mo/interlayer OFETs display ambipolar transport due to significant enhancement of electron injection. In the p-type region, transistor performance is comparable to devices with gold (Au). Hole mobility is increased approximately ten-fold over devices with only Mo contacts. The electron mobility of Mo/interlayer OFETs is 0.05 cm²V⁻¹s⁻¹, which is higher than devices with Au electrodes. The p-type contact resistances of Mo/interlayer OFETs are half those of OFETs with Mo contacts. Trap density in Mo/interlayer OFETs is one order magnitude lower than that of pristine devices. We also demonstrate that this approach is extendible to other metals (nickel) and n-type semiconductors with different energy levels. Injection by tunnelling is suggested as the mechanism of ambipolar injection.     

Insight into the charge transport and degradation mechanisms in organic transistors operating at elevated temperatures in air

Operational stability of organic devices at above-room-temperatures in ambient environment is of imminent practical importance. In this report, we have investigated the charge transport and degradation mechanisms in pentacene based organic field effect transistors (OFETs) operating in the temperatures ranging from 25 °C to 150 °C under ambient conditions. The thin film characterizations techniques (X-ray photoelectron spectroscopy, X-ray diffraction and atomic force microscopy) were used to establish the structural and chemical stability of pentacene thin films at temperatures up to 150 °C in ambient conditions. The electrical behavior of OFETs varies differently in different temperature bracket. Mobility, at temperatures below 110 °C, is found to be thermally activated in presence of traps and temperature independent in absence of traps. At temperatures above 110 °C mobility degrades due to polymorphism in pentacene or interfacial properties. The degradation of mobility is compensated with the decrease in threshold voltage at high temperatures and OFETs are operational at temperatures as high as 190 °C. 70 °C has been identified as the optimum temperature of operation for our OFETs where both device behavior and material properties are stable enough to ensure sustainable performance.     

Prolonged lifetime of polymer solar cells with amphiphilic monolayers modified cathodes

The short lifetime and low stability of polymer solar cells (PSCs) devices limit their feasibility for commercial use. Modification of the interfacial electron-transport layers (ETL) has been demonstrated as an effective way to enhance power conversion efficiency (PCE) and device stability. In this work, two types of monolayers consisting of amphiphilic molecules (sodium stearate or sodium oleate - a major constituent of “soap”) are introduced as novel ETLs in polymer: PCBM based PSCs. Significant improvement of PCE was demonstrated and an extended operational lifetime by 5–25 times was achieved. We attributed the improved performance to the interface modification by the amphiphilic molecular layers. The amphiphilic interfacial layers established a better contact between the active layer and the cathode by reducing the roughness and forming a compact dipole at the interface, which facilitates charge generation, charge transport to, and charge collection at the electrodes, thereby enhancing the device efficiency and stability. This versatile interface modification approach has shown to be an immediate and promising means to improve the performance of PSCs.     

Tuning Interfacial Properties by Spontaneously Generated Organic Interlayers in Top‐Contact‐Structured Organic Transistors

Controlling the interfacial properties between the electrode and active layer in organic field‐effect transistors (OFETs) can significantly affect their contact properties, resulting in improvements in device performance. However, it is difficult to apply to top‐contact‐structured OFETs (one of the most useful device structures) because of serious damage to the organic active layer by exposing solvent. Here, a spontaneously controlled approach is explored for optimizing the interface between the top‐contacted source/drain electrode and the polymer active layer to improve the contact resistance (R_C). To achieve this goal, a small amount of interface‐functionalizing species is blended with the p‐type polymer semiconductor and functionalized at the interface region at once through a thermal process. The R_C values dramatically decrease after introduction of the interfacial functionalization to 15.9 kΩ cm, compared to the 113.4 kΩ cm for the pristine case. In addition, the average field‐effect mobilities of the OFET devices increase more than three times, to a maximum value of 0.25 cm² V^?1 s^?1 compared to the pristine case (0.041 cm² V^?1 s^?1), and the threshold voltages also converge to zero. This study overcomes all the shortcomings observed in the existing results related to controlling the interface of top‐contact OFETs by solving the discomfort of the interface optimization process.     

Quantitative Determination of Charge Transport Interface at Vertically Phase Separated Soluble Acene/Polymer Blends

Interfacial structure is critical for optimizing the electrical properties of organic field-effect transistors. In this study, the interfacial structures of 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene)/polymer blends are nondestructively determined by the complementary neutron and X-ray reflectivity. The TIPS-pentacene/deuterated poly(methylmethacrylate) (d-PMMA) blends exhibit a vertically phase-separated structure with a molecularly sharp interface (interfacial roughness ≈5 Å), whereas the TIPS-pentacene/d-polystyrene (d-PS) blend intermix near the interface. Ultrahigh molecular weight d-PMMA leads to the formation of surface-segregated hexagonal spherulites of TIPS-pentacene owing to the thermodynamic factors (e.g., surface/interface energy, polarity, and viscosity) of the blending materials. The well-developed hexagonal spherulites of TIPS-pentacene on molecularly sharp d-PMMA interface result in higher field-effect mobility as compared to the dendritic crystals from d-PS blends because of the higher perfectness, coverage, and interfacial roughness of the TIPS-pentacene crystals. The approach used in this study facilitates the understanding of the charge transport mechanism at the phase-separated interfaces in soluble acene/polymer blends.     

Enhanced performance of inverted perovskite solar cells using solution-processed carboxylic potassium salt as cathode buffer layer

Using a novel solution-processed carboxylic potassium salt (F-R-COOK) as cathode buffer layer (CBL), a power conversion efficiency (PCE) of 14.37% is obtained, which is more than 51% increase compared with that of the Ag-only device under similar fabrication conditions. The test result of single electron devices and Electrochemical impedance spectroscopy (EIS) measurements demonstrate that the interlayer decreases charge transport resistance. Ultraviolet photoelectron spectroscopy (UPS) measurements are used to study the interfacial effects induced by the new CBL. It is found that F-R-COOK can reduce the work function of the Ag electrode by forming desired interfacial dipoles. Our work indicates the promising applications of F-R-COOK based CBL in perovskite solar cells and may provide some insights into the design and synthesis of new interfacial materials to further improve the device performance.     

Efficiency enhancement of ZnO based inverted BHJ solar cells via interface engineering using C70 modifier

The interface quality of ZnO and the photoactive polymer blend is of utmost importance in the performance of organic-inorganic hybrid photovoltaic devices. The chemically prepared ZnO electron transporting layer often produce surfaces unacceptable for efficient electron extraction and understate the photovoltaic performance. Herein, we propose a facile interfacial modification technique to enhance the charge collection efficiency of ZnO cathode electrode by efficiently bridging the superficial troughs and ridges of ZnO with the photoactive PCDTBT: PC₇₁BM polymer blend. The investigations show that vacuum sublimated C₇₀ interlayer efficiently fills the gaps between ZnO and the polymer blend reducing accumulation of the charges at the interface and thus minimizing the recombination probability. It also plays a very crucial role in passivating ZnO electrode against interfacial traps due to adsorbed chemical species. The inclusion of C₇₀ interlayer into the devices led to a substantial increase in device performance with PCE reaching close to 4%, an increment by a factor of 2 compared to the control devices. Our investigations aim towards showing the efficacy of C₇₀ small molecule in significantly enhancing the PCE of ZnO based BHJ solar cells fabricated and measured in ambient conditions rather than setting benchmark efficiency for the configured device. However, better performances for the devices are conceivable by performing the fabrication and measurement in controlled inert atmosphere.     

Variations in Hole Injection due to Fast and Slow Interfacial Traps in Polymer Light‐Emitting Diodes with Interlayers

Detailed studies on the effect of placing a thin (10 nm) solution‐processable interlayer between a light‐emitting polymer (LEP) layer and a poly(3,4‐ethylenedioxythiophene)/poly(styrenesulfonic)‐acid‐coated indium tin oxide anode is reported; particular attention is directed at the effects on the hole injection into three different LEPs. All three different interlayer polymers have low ionization potentials, which are similar to those of the LEPs, so the observed changes in hole injection are not due to variations in injection barrier height. It is instead shown that changes are due to variations in hole trapping at the injecting interface, which is responsible for varying the hole current by up to two orders of magnitude. Transient measurements show the presence of very fast interfacial traps, which fill the moment charge is injected from the anode. These can be considered as injection pathway dead‐ends, effectively reducing the active contact surface area. This is followed by slower interfacial traps, which fill on timescales longer than the carrier transit time across the device, further reducing the total current. The interlayers may increase or decrease the trap densities depending on the particular LEP involved, indicating the dominant role of interfacial chain morphology in injection. Penetration of the interlayer into the LEP layer can also occur, resulting in additional changes in the bulk LEP transport properties.     

Side-Chain Functionalized Polymer Hole-Transporting Materials with Defect Passivation Effect for Highly Efficient Inverted Quasi-2D Perovskite Solar Cells

Compared with inverted 3D perovskite solar cell (PSCs), inverted quasi-2D PSCs have advantages in device stability, but the device efficiency is still lagging behind. Constructing polymer hole-transporting materials (HTMs) with passivation functions to improve the buried interface and crystallization properties of perovskite films is one of the effective strategies to improve the performance of inverted quasi-2D PSCs. Herein, two novel side-chain functionalized polymer HTMs containing methylthio-based passivation groups are designed, named PVCz-SMeTPA and PVCz-SMeDAD, for inverted quasi-2D PSCs. Benefited from the non-conjugated flexible backbone bearing functionalized side-chain groups, the polymer HTMs exhibit excellent film-forming properties, well-matched energy levels and improved charge mobility, which facilitates the charge extraction and transport between HTM and quasi-2D perovskite layer. More importantly, by introducing methylthio units, the polymer HTMs can enhance the contact and interactions with quasi-2D perovskite, and further passivating the buried interface defects and assisting the deposition of high-quality perovskite. Due to the suppressed interfacial non-radiative recombination, the inverted quasi-2D PSCs using PVCz-SMeTPA and PVCz-SMeDAD achieve impressive power conversion efficiency (PCE) of 21.41% and 20.63% with open-circuit voltage of 1.23 and 1.22 V, respectively. Furthermore, the PVCz-SMeTPA based inverted quasi-2D PSCs also exhibits negligible hysteresis and considerably improved thermal and long-term stability.     

Organozinc Compounds as Effective Dielectric Modification Layers for Polymer Field‐Effect Transistors

The interface between the organic semiconductor and dielectric plays an important role in determining the device performance of organic field‐effect transistors (OFETs). Although self‐assembled monolayers (SAMs) made from organosilanes have been widely used for dielectric modification to improve the device performance of OFETs, they suffer from incontinuous and lack uniform coverage of the dielectric layer. Here, it is reported that by introduction of a solution‐processed organozinc compound as a dielectric modification layer between the dielectric and the silane SAM, improved surface morphology and reduced surface polarity can be achieved. The organozinc compound originates from the reaction between diethylzinc and the cyclohexanone solvent, which leads to formation of zinc carboxylates. Being annealed at different temperatures, organozinc compound exists in various forms in the solid films. With organozinc modification, p‐type polymer FETs show a high charge carrier mobility that is about two‐fold larger than a control device that does not contain the organozinc compound, both for devices with a positive threshold voltage and for those with a negative one. After organozinc compound modification, the threshold voltage of polymer FETs can either be altered to approach zero or remain unchanged depending on positive or negative threshold voltage they have.     

Organic Field Effect Transistors Based on Graphene and Hexagonal Boron Nitride Heterostructures

Enhancing the device performance of single crystal organic field effect transistors (OFETs) requires both optimized engineering of efficient injection of the carriers through the contact and improvement of the dielectric interface for reduction of traps and scattering centers. Since the accumulation and flow of charge carriers in operating organic FETs takes place in the first few layers of the semiconductor next to the dielectric, the mobility can be easily degraded by surface roughness, charge traps, and foreign molecules at the interface. Here, a novel structure for high‐performance rubrene OFETs is demonstrated that uses graphene and hexagonal boron nitride (hBN) as the contacting electrodes and gate dielectric layer, respectively. These hetero‐stacked OFETs are fabricated by lithography‐free dry‐transfer method that allows the transfer of graphene and hBN on top of an organic single crystal, forming atomically sharp interfaces and efficient charge carrier‐injection electrodes without damage or contamination. The resulting heterostructured OFETs exhibit both high mobility and low operating gate voltage, opening up new strategy to make high‐performance OFETs and great potential for flexible electronics.     

Temperature gradient controlled crystal growth from TIPS pentacene-poly(α-methyl styrene) blends for improving performance of organic thin film transistors

6,13-bis(triisopropylsilylethynyl) pentacene (TIPS pentacene) from simple drop casting typically forms crystals with random orientation and poor areal coverage, which leads to device-to-device performance variation of organic thin film transistors (OTFTs). Previously, a temperature gradient technique was developed to address these problems. However, this approach simultaneously introduced thermal cracks due to the thermally induced stress during crystallization. These thermal cracks accounted for a reduction of charge transport, thereby impacting the device performance of TIPS pentacene based OTFTs. In this work, an insulating polymer, poly(α-methyl styrene) (PαMS) was blended with TIPS pentacene to relieve the thermal stress and effectively prevent the generation of thermal cracks. The results demonstrate that the incorporation of PαMS polymer combined with the temperature gradient technique improves both the hole mobility and performance consistency of TIPS pentacene based OTFTs.     

Modulating Charge Transport from Thermally Activated to “Band-Like” Through Interfacial Bottom-Up Binding Capability of Bilayer Polymer Dielectrics

The disordered chain arrangement of polymer dielectrics has complex both internal and external effects on system performance, which generally stimulates the weak acquisition and grain boundaries of vapor-deposited organic small molecule films (VDOSMFs) with thermally activated charge transport. As a result, achieving “band-like” transmission of VDOSMs on polymer dielectrics is attempting to prove to be a major challenge. Three types of bi-polymer dielectrics are developed to modulate charge transport from thermally activated mode to “band-like” transport at the interfacial level. The bottom consisting of a polyimide layer is critical to interfacial modulation, which shows the selectively binding capability with up-dielectric layers to realize the modulation of charge transport, as corroborated by interface characterization and density functional-based tight-binding calculation. The findings provide an effective strategy for modulating the charge transport through polymer dielectric engineering and also recommend a podium to further comprehend the electrical characteristics of small molecules in organic thin-film transistors.