Electron‐Enhanced Hole Injection in Blue Polyfluorene‐Based Polymer Light‐Emitting Diodes

It has recently been reported that, after electrical conditioning, an ohmic hole contact is formed in poly(9,9‐dioctylfluorene) (PFO)‐based polymer light‐emitting diodes (PLED), despite the large hole‐injection barrier obtained with a poly(styrene sulfonic acid)‐doped poly(3,4‐ethylenedioxythiophene) (PEDOT:PSS) anode. We demonstrate that the initial current at low voltages in a PEDOT:PSS/PFO‐based PLED is electron dominated. The voltage at which the hole injection is enhanced strongly depends on the electron‐transport properties of the device, which can be modified by the replacement of reactive end groups by monomers in the synthesis. Our measurements reveal that the switching voltage of the PLED is governed by the electron concentration at the PEDOT:PSS/PFO contact. The switching effect in PFO is only observed for a PEDOT:PSS hole contact and not for other anodes such as indium tin oxide or Ag.     

Anode Interfacial Tuning via Electron‐Blocking/Hole‐Transport Layers and Indium Tin Oxide Surface Treatment in Bulk‐Heterojunction Organic Photovoltaic Cells

The effects of anode/active layer interface modification in bulk‐heterojunction organic photovoltaic (OPV) cells is investigated using poly(3,4‐ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) and/or a hole‐transporting/electron‐blocking blend of 4,4′‐bis[(p‐trichlorosilylpropylphenyl)‐phenylamino]biphenyl (TPDSi₂) and poly[9,9‐dioctylfluorene‐co‐N‐[4‐(3‐methylpropyl)]‐diphenylamine] (TFB) as interfacial layers (IFLs). Current–voltage data in the dark and AM1.5G light show that the TPDSi₂:TFB IFL yields MDMO‐PPV:PCBM OPVs with substantially increased open‐circuit voltage (V_oc), power conversion efficiency, and thermal stability versus devices having no IFL or PEDOT:PSS. Using PEDOT:PSS and TPDSi₂:TFB together in the same cell greatly reduces dark current and produces the highest V_oc (0.91 V) by combining the electron‐blocking effects of both layers. ITO anode pre‐treatment was investigated by X‐ray photoelectron spectroscopy to understand why oxygen plasma, UV ozone, and solvent cleaning markedly affect cell response in combination with each IFL. O₂ plasma and UV ozone treatment most effectively clean the ITO surface and are found most effective in preparing the surface for PEDOT:PSS deposition; UV ozone produces optimum solar cells with the TPDSi₂:TFB IFL. Solvent cleaning leaves significant residual carbon contamination on the ITO and is best followed by O₂ plasma or UV ozone treatment.     

Hole Injection in a Model Fluorene–Triarylamine Copolymer

Recent developments in synthesis and purification have yielded conjugated polymers with hole mobilities exceeding 0.01 cm² V^?1 s^?1. Essential to harvesting the potential of these materials in organic light emitting diodes (OLEDs) is the identification of suitable ohmic contacts. Using a model fluorene copolymer that shows high‐mobility, non‐dispersive hole transport, it is demonstrated that electrodes commonly used as anodes in OLEDs are very poor hole injectors. Injection from Au and indium tin oxide anodes is limited by energy barriers of 0.75 and 0.65 eV, respectively, and the injected current is found to be temperature independent—a prediction that was not reproduced by the leading injection model for disordered organic semiconductors. Injection from a poly(3,4‐ethylenedioxythiophene) doped with poly(styrenesulfonate) (PEDOT:PSS) anode, on the other hand, is found to become less efficient with electric field, a behavior which is currently not understood. In thinner poly[(9,9′‐dioctylfluorenyl‐2,7‐diyl)‐co‐(4,4′‐(N‐(4‐sec‐butyl))diphenylamine)] films, which are of relevance to OLEDs, ohmic losses on the PEDOT:PSS layer are found to limit the flow of current. These results illustrate the opportunity to further improve the performance of OLEDs as well as the challenge posed by high mobility conjugated polymers for the design of hole injection layers.     

Solution-processed quantum dot light-emitting diodes with PANI:PSS hole-transport interlayers

For solution-processed quantum dot light-emitting devices (QD-LEDs), poly(3,4-ethylenedioxythiophene) polystyrene sulfonate/poly(N-vinylcarbozole) (PEDOT:PSS/PVK) bilayers have been widely used as the hole injection/transport layer. The high work function of the hole transport layer is crucial for high electroluminescence efficiency with balanced electron/hole charge injection. Herein, we report improvement of the performance of QD-LEDs by inserting a polyaniline (PANI)-poly (p-styrenesulfonic acid) (PSS) (PANI:PSS) hole-transport layer between the PVK and PEDOT:PSS layers. The insertion of the PANI:PSS layer significantly shifted the electronic energy levels of the PVK layers to lower values, which reduced the energy barrier of holes traveling to the QD layer by 0.22 eV. The QD-LEDs with PANI:PSS interlayer exhibited superior electric and electroluminescent characteristics. The hole-only devices with PANI:PSS interlayer also presented high hole injection and transport capability. Ultraviolet photoelectron spectroscopy (UPS) was used to investigate the electronic energy level alignment of the QD-LEDs with/without the PANI:PSS interlayer. The device performance results of QD-LEDs and hole-only devices indicated enhanced electric and electroluminescent characteristics for the PANI:PSS-inserted QD-LEDs with high hole conduction capability, in agreement with UPS findings.     

Simultaneous enhancement of the efficiency and stability of organic solar cells using PEDOT:PSS grafted with a PEGME buffer layer

We report a simple processing method to simultaneously improve the efficiency and stability of organic solar cells (OSCs). Poly(4-styrene sulfonate)-doped poly(3,4-ethylenedioxy-thiophene (PEDOT:PSS), widely used as hole transport layer (HTL) in OSCs, tends to accelerate the degradation of devices because of its hygroscopic and acidic properties. In this regard, we have modified PEDOT:PSS to reduce its hygroscopic and acidic properties through a condensation reaction between PEDOT:PSS and poly(ethylene glycol) methyl ether (PEGME) in order to improve the efficiency and stability of OSCs. As a result, the power conversion efficiency (PCE) increased by 21%, from 2.57% up to 3.11%. A better energy level alignment by the reduced work function of the modified PEDOT:PSS with a highest occupied molecular orbital (HOMO) level of poly(3-hexylthiophene-2,5-diyl) (P3HT) is considered the origin of the improved the efficiency. The half-life of OSCs with PEDOT:PSS modified with PEGME buffer layer also increased up to 3.5 times compared to that of devices with pristine PEDOT:PSS buffer layer.     

Energy level alignment and morphology of interfaces between molecular and polymeric organic semiconductors

Ultraviolet photoelectron spectroscopy (UPS) was used to determine the energy level alignment at organic–organic conductor–semiconductor and semiconductor–semiconductor hetero-interfaces that are relevant for organic optoelectronic devices. Such interfaces were formed by in situ vacuum sublimation of small molecular materials [C₆₀ and pentacene (PEN)] and ex situ spin-coating of poly(3-hexylthiophene) (P3HT), all on the common substrate poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT:PSS). We found that the deposition sequence had a significant impact on the interface energetics. The hole injection barrier (HIB) of C₆₀ on PEDOT:PSS could be changed from 1.0 eV (moderate hole injection) to 1.7 eV (good electron injection) by introducing a layer of P3HT. The HIB of P3HT/PEDOT:PSS was increased by 0.35 eV due to an interfacial PEN layer. However, PEN deposited on PEDOT:PSS and P3HT/PEDOT:PSS exhibited the same value. These observations are explained by material-dependent dipoles at the interfaces towards PEDOT:PSS and substrate dependent inter-molecular conformation.     

In‐Situ Switching from Barrier‐Limited to Ohmic Anodes for Efficient Organic Optoelectronics

Injection and extraction of charges through ohmic contacts are required for efficient operation of semiconductor devices. Treatment using polar non‐solvents switches polar anode surfaces, including PEDOT:PSS and ITO, from barrier‐limited hole injection and extraction to ohmic behaviour. This is caused by an in‐situ modification of the anode surface that is buried under a layer of organic semiconductor. The exposure to methanol removes polar hydroxyl groups from the buried anode interface, and permanently increases the work function by 0.2–0.3 eV. In the case of ITO/PEDOT:PSS/PBDTTT‐CT:PC71BM/Al photovoltaic devices, the higher work function promotes charge transfer, leading to p‐doping of the organic semiconductor at the interface. This results in a two‐fold increase in hole extraction rates which raises both the fill factor and the open‐circuit voltage, leading to high power conversion efficiency of 7.4%. In ITO/PEDOT:PSS/F8BT/Al polymer light‐emitting diodes, where the organic semiconductor's HOMO level lies deeper than the anode Fermi level, the increased work function enhances hole injection efficiency and luminance intensity by 3 orders of magnitude. In particular, hole injection rates from PEDOT:PSS anodes are equivalent to those achievable using MoO₃. These findings exemplify the importance of work function control as a tool for improved electrode design, and open new routes to device interfacial optimization using facile solvent processing techniques. Such simple, persistent, treatments pave the way towards low cost manufacturing of efficient organic optoelectronic devices.     

Conjugated Small Molecule for Efficient Hole Transport in High‐Performance p‐i‐n Type Perovskite Solar Cells

The π‐conjugated organic small molecule 4,4′‐cyclohexylidenebis[N,N‐bis(4‐methylphenyl) benzenamine] (TAPC) has been explored as an efficient hole transport material to replace poly(3,4‐ethylenedio‐xythiophene):poly(styrenesulfonate) (PEDOT:PSS) in the preparation of p‐i‐n type CH₃NH₃PbI₃ perovskite solar cells. Smooth, uniform, and hydrophobic TAPC hole transport layers can be facilely deposited through solution casting without the need for any dopants. The power conversion efficiency of perovskite solar cells shows very weak TAPC layer thickness dependence across the range from 5 to 90 nm. Thermal annealing enables improved hole conductivity and efficient charge transport through an increase in TAPC crystallinity. The perovskite photoactive layer cast onto thermally annealed TAPC displays large grains and low residual PbI₂, leading to a high charge recombination resistance. After optimization, a stabilized power conversion efficiency of 18.80% is achieved with marginal hysteresis, much higher than the value of 12.90% achieved using PEDOT:PSS. The TAPC‐based devices also demonstrate superior stability compared with the PEDOT:PSS‐based devices when stored in ambient circumstances, with a relatively high humidity ranging from 50 to 85%.     

Highly Efficient Hole Injection Using Polymeric Anode Materials for Small‐Molecule Organic Light‐Emitting Diodes

A novel, highly efficient hole injection material based on a conducting polymer polythienothiophene (PTT) doped with poly(perfluoroethylene‐perfluoroethersulfonic acid) (PFFSA) in organic light‐emitting diodes (OLEDs) is demonstrated. Both current–voltage and dark‐injection‐current transient data of hole‐only devices demonstrate high hole‐injection efficiency employing PTT:PFFSA polymers with different organic charge‐transporting materials used in fluorescent and phosphorescent organic light‐emitting diodes. It is further demonstrated that PTT:PFFSA polymer formulations applied as the hole injection layer (HIL) in OLEDs reduce operating voltages and increase brightness significantly. Hole injection from PTT:PFFSA is found to be much more efficient than from typical small molecule HILs such as copper phthalocyanine (CuPc) or polymer HILs such as polyethylene dioxythiophene: polystyrene sulfonate (PEDOT‐PSS). OLED devices employing PTT:PFFSA polymer also demonstrate significantly longer lifetime and more stable operating voltages compared to devices using CuPc.     

PEDOT:PSS‐Assisted Exfoliation and Functionalization of 2D Nanosheets for High‐Performance Organic Solar Cells

Here, a facial and scalable method for efficient exfoliation of bulk transition metal dichalcogenides (TMD) and graphite in aqueous solution with poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) to prepare single‐ and few‐layer nanosheets is demonstrated. Importantly, these TMD nanosheets retain the single crystalline characteristic, which is essential for application in organic solar cells (OSCs). The hybrid PEDOT:PSS/WS₂ ink prepared by a simple centrifugation is directly integrated as a hole extraction layer for high‐performance OSCs. Compared with PEDOT:PSS, the PEDOT:PSS/WS₂‐based devices provide a remarkable power conversion efficiency due to the “island” morphology and benzoid–quinoid transition. This study not only demonstrates a novel method for preparing single‐ and few‐layer TMD and graphene nanosheets but also paves a way for their applications without further complicated processing.     

Cooperative Effect of GO and Glucose on PEDOT:PSS for High VOC and Hysteresis‐Free Solution‐Processed Perovskite Solar Cells

Hybrid organic–inorganic halide perovskites have emerged at the forefront of solution‐processable photovoltaic devices. Being the perovskite precursor mixture a complex equilibrium of species, it is very difficult to predict/control their interactions with different substrates, thus the final film properties and device performances. Here the wettability of CH₃NH₃PbI₃ (MAPbI₃) onto poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) hole transporting layer is improved by exploiting the cooperative effect of graphene oxide (GO) and glucose inclusion. The glucose, in addition, triggers the reduction of GO, enhancing the conductivity of the PEDOT:PSS+GO+glucose based nanocomposite. The relevance of this approach toward photovoltaic applications is demonstrated by fabricating a hysteresis‐free MAPbI₃ solar cells displaying a ≈37% improvement in power conversion efficiency if compared to a device grown onto pristine PEDOT:PSS. Most importantly, V_OC reaches values over 1.05 V that are among the highest ever reported for PEDOT:PSS p‐i‐n device architecture, suggesting minimal recombination losses, high hole‐selectivity, and reduced trap density at the PEDOT:PSS along with optimized MAPbI₃ coverage.     

Boosting Performance of Non‐Fullerene Organic Solar Cells by 2D g‐C3N4 Doped PEDOT:PSS

The power‐conversion efficiency (PCE) of single‐junction organic solar cells (OSCs) has exceeded 16% thanks to the development of non‐fullerene acceptor materials and morphological optimization of active layer. In addition, interfacial engineering always plays a crucial role in further improving the performance of OSCs based on a well‐established active‐layer system. Doping of graphitic carbon nitride (g‐C₃N₄) into poly(3,4‐ethylene‐dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) as a hole transport layer (HTL) for PM6:Y6‐based OSCs is reported, boosting the PCE to almost 16.4%. After being added into the PEDOT:PSS, the g‐C₃N₄ as a Bronsted base can be protonated, weakening the shield effect of insulating PSS on conductive PEDOT, which enables exposures of more PEDOT chains on the surface of PEDOT:PSS core‐shell structure, and thus increasing the conductivity. Therefore, at the interface between g‐C₃N₄ doped HTL and PM6:Y6 layer, the charge transport is improved and the charge recombination is suppressed, leading to the increases of fill factor and short‐circuit current density of devices. This work demonstrates that doping g‐C₃N₄ into PEDOT:PSS is an efficient strategy to increase the conductivity of HTL, resulting in higher OSC performance.     

High efficiency bulk heterojunction organic solar cell by using high conductivity modified PEDOT: PSS as a buffer layer

In this paper,bulk heterojunction solar cells with poly-(3-hexylthiophene)(P3HT):[6,6]-phenyl-C61-butyric-acid-methylester(PCBM) as an active layer and modified poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)(PEDOT:PSS) as a buffer layer are fabricated.The buffer layer is modified by adding 1% to 5% dimethyl sulfoxide(DMSO) into PEDOT:PSS solution before spin-coating.The conductivity of modified PEDOT:PSS and the performance of solar cells with modified PEDOT:PSS are measured.The highest conductivity of modified PEDOT:PSS with 4% DMSO can achieve 89.693 S/cm.The performance of organic solar cell with PEDOT:PSS modified by 4% DMSO is the best.The 4% DMSOmodified-PEDOT:PSS cell has a power conversion efficiency of 3.34%,V oc of 5.7 V,J sc of 14.56 mA/cm 2 and filling factor(FF) of 40.34%.     

Influence of PEDOT:PSS buffer layer on the performance of organic photocoupler

We have fabricated an organic photocoupler with organic light-emitting diodes （OLEDs） with 520 nm emissive wavelength as the input light source and a photodiode （PD） based on poly（3-hexylthiophene） （P3HT）：1-（3-methoxycarbonyl）propyl- 1-phenyl-（6,6）-C61 （PCBM） as the detector. The influences of buffer layer （PEDOT：PSS） on output current （Iout）, current transfer ratio （CTR） and time response characteristics of the photocoupler device were studied. Through our experiments, It is found that the output current linearly increases with the input current, the max output current and CTR of the devices with PEDOT：PSS buffer layer are 2 times and 7 times than that of the devices without buffer layer respectively, which show that the existence of buffer layer can enhance the output photocurrent efficiently. Moreover, the existence of PEDOT：PSS eliminates the time delay of the devices.     

Highly Conductive and Transparent PEDOT:PSS Films with a Fluorosurfactant for Stretchable and Flexible Transparent Electrodes

Highly conductive and transparent poly‐(3,4‐ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS) films, incorporating a fluorosurfactant as an additive, have been prepared for stretchable and transparent electrodes. The fluorosurfactant‐treated PEDOT:PSS films show a 35% improvement in sheet resistance (R_s) compared to untreated films. In addition, the fluorosurfactant renders PEDOT:PSS solutions amenable for deposition on hydrophobic surfaces, including pre‐deposited, annealed films of PEDOT:PSS (enabling the deposition of thick, highly conductive, multilayer films) and stretchable poly(dimethylsiloxane) (PDMS) substrates (enabling stretchable electronics). Four‐layer PEDOT:PSS films have an R_s of 46 Ω per square with 82% transmittance (at 550 nm). These films, deposited on a pre‐strained PDMS substrate and buckled, are shown to be reversibly stretchable, with no change to R_s, during the course of over 5000 cycles of 0 to 10% strain. Using the multilayer PEDOT:PSS films as anodes, indium tin oxide (ITO)‐free organic photovoltaics are prepared and shown to have power conversion efficiencies comparable to that of devices with ITO as the anode. These results show that these highly conductive PEDOT:PSS films can not only be used as transparent electrodes in novel devices (where ITO cannot be used), such as stretchable OPVs, but also have the potential to replace ITO in conventional devices.     

基于PEDOT:PSS掺杂MoO3修饰有机电致发光器件性能的研究

有机电致发光器件因具有质量轻、亮度高、柔性 、宽视角和响应速度快等优点已经成 为下一代平板显示和照明领域的潜在主流技术。本文证实了MoO₃掺杂于PEDOT:PSS作为空 穴注入 层时,可以改善器件性能。与未掺杂器件相比,掺杂器件的亮度和效率显著提高,启亮电压 降低0.5 V。AFM,透光性和单空穴器件实验表明,当在ITO和空穴传 输层之间插入PEDOT:PSS :MoO₃后,由于修饰了ITO表面膜形貌,增加了绿光区透光性以及降低了空穴注入层电阻 从而提高了器件的性能。     

Methanol treatment on low-conductive PEDOT:PSS to enhance the PLED's performance

In order to achieve high device efficiency in blue-emitting polymer light-emitting diodes (PLED) and white-emitting PLED, low-conductive PEDOT:PSS Clevios™ P CH 8000 (8000) has been used to replace widely adopted high-conductive PEDOT:PSS Clevios™ P Al 4083 (4083). In a blue PLED with poly (dibenzothiophene-S,S-dioxide-co-9,9-dioctyl-2,7-fluorene) (PF-FSO) as the emission layer, though the 8000 device has a higher efficiency and a lower turn-on voltage than the 4083 device, the 8000 device exhibits low peak luminance, sharp efficiency roll-off, and permanent degradation of the emission material. By analyzing the hole-only device and the X-ray photoelectron spectroscopy spectra, it's revealed that the insulating PSS layer on 8000 surface is responsible for the inefficient hole injection. A simple methanol treatment on the 8000 surface effectively removes the redundant PSS. Without the insulating PSS layer, the hole injection becomes efficient which extends the recombination zone. As the result, the methanol-treated 8000 device not only retains low turn-on voltage and the high device efficiency of the untreated 8000 device, but also achieves the peak luminance, mild efficiency roll-off, and device stability of the 4083 device.     

Bright Blue Solution Processed Triple‐Layer Polymer Light‐Emitting Diodes Realized by Thermal Layer Stabilization and Orthogonal Solvents

The realization of fully solution processed multilayer polymer light‐emitting diodes (PLEDs) constitutes the pivotal point to push PLED technology to its full potential. Herein, a fully solution processed triple‐layer PLED realized by combining two different deposition strategies is presented. The approach allows a successive deposition of more than two polymeric layers without extensively redissolving already present layers. For that purpose, a poly(9,9‐dioctyl‐fluorene‐co‐N‐(4‐butylphenyl)‐diphenylamine) (TFB) layer is stabilized by a hard‐bake process as hole transport layer on top of poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS). As emitting layer, a deep blue emitting pyrene‐triphenylamine copolymer is deposited from toluene solution. To complete the device assembly 9,9‐bis(3‐(5′,6′‐bis(4‐(polyethylene glycol)phenyl)‐[1,1′:4′,1″‐terphenyl]‐2′‐yl)propyl)‐9′,9′‐dioctyl‐2,7‐polyfluorene (PEGPF), a novel polyfluorene‐type polymer with polar sidechains, which acts as the electron transport layer, is deposited from methanol in an orthogonal solvent approach. Atomic force microscopy verifies that all deposited layers stay perfectly intact with respect to morphology and layer thickness upon multiple solvent treatments. Photoelectron spectroscopy reveals that the offsets of the respective frontier energy levels at the individual polymer interfaces lead to a charge carrier confinement in the emitting layer, thus enhancing the exciton formation probability in the device stack. The solution processed PLED‐stack exhibits bright blue light emission with a maximum luminance of 16 540 cd m^?2 and a maximum device efficiency of 1.42 cd A^?1, which denotes a five‐fold increase compared to corresponding single‐layer devices and demonstrates the potential of the presented concept.     

Decohesion Kinetics of PEDOT:PSS Conducting Polymer Films

The highly conductive polymer PEDOT:PSS is a widely used hole transport layer and transparent electrode in organic electronic devices. To date, the mechanical and fracture properties of this conductive polymer layer are not well understood. Notably, the decohesion rate of the PEDOT:PSS layer and its sensitivity to moist environments has not been reported, which is central in determining the lifetimes of organic electronic devices. Here, it is demonstrated that the decohesion rate is highly sensitive to the ambient moisture content, temperature, and mechanical stress. The kinetic mechanisms are elucidated using atomistic bond rupture models and the decohesion process is shown to be facilitated by a chemical reaction between water molecules from the environment and strained hydrogen bonds. Hydrogen bonds are the predominant bonding mechanism between individual PEDOT:PSS grains within the layer and cause a significant loss in cohesion when they are broken. Understanding the decohesion kinetics and mechanisms in these films is essential for the mechanical integrity of devices containing PEDOT:PSS layers and yields general guidelines for the design of more reliable organic electronic devices.     

Over 16.7% Efficiency Organic‐Silicon Heterojunction Solar Cells with Solution‐Processed Dopant‐Free Contacts for Both Polarities

Realization of synchronous improvement in optical management and electrical engineering is necessary to achieve high‐performance photovoltaic device. However, inherent challenges are faced in organic‐silicon heterojunction solar cells (HSCs) due to the poor contact property of polymer on structured silicon surface. Herein, a remarkable efficiency boost from 12.6% to over 16.7% in poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate)/n‐silicon (PEDOT:PSS/n‐Si) HSCs by independent optimization of hole‐/electron‐selective contacts only relying on solution‐based processes is realized. A bilayer PEDOT:PSS film with different functionalizations is utilized to synchronously realize conformal contact and effective carrier collection on textured Si surface, making the photogenerated carriers be well separated at heterojunction interface. Meanwhile, fullerene derivative is used as electron‐transporting layer at the rear n‐Si/Al interface to reduce the contact barrier. The study of carriers' transport and independent optimization on separately contacted layers may lead to an effective and simplified path to fabricate high‐performance organic‐silicon heterojunction devices.