Interface Modification to Improve Hole‐Injection Properties in Organic Electronic Devices

The performance of organic electronic devices is often limited by injection. In this paper, improvement of hole injection in organic electronic devices by conditioning of the interface between the hole‐conducting layer (buffer layer) and the active organic semiconductor layer is demonstrated. The conditioning is performed by spin‐coating poly(9,9‐dioctyl‐fluorene‐co‐N‐ (4‐butylphenyl)‐diphenylamine) (TFB) on top of the poly(3,4‐ethylene dioxythiophene): poly(styrene sulfonate) (PEDOT:PSS) buffer layer, followed by an organic solvent wash, which results in a TFB residue on the surface of the PEDOT:PSS. Changes in the hole‐injection energy barriers, bulk charge‐transport properties, and current–voltage characteristics observed in a representative PFO‐based (PFO: poly(9,9‐dioctylfluorene)) diode suggest that conditioning of PEDOT:PSS surface with TFB creates a stepped electronic profile that dramatically improves the hole‐injection properties of organic electronic devices.     

Using Self‐Assembling Dipole Molecules to Improve Hole Injection in Conjugated Polymers

Surface modification of indium‐tin‐oxide (ITO)‐coated substrates through the use of self‐assembled monolayers (SAMs) of molecules with permanent dipole moments has been used to control the ITO work function and device performance in polymer light‐emitting diodes based on a polyfluorene hole transporting copolymer. Measured current–voltage characteristics of the devices reveal greatly increased hole injection currents from the SAM‐altered electrodes with higher work function, in agreement with an expected reduction in the barrier for hole injection. In particular, it is shown that the SAM‐modified electrode with the highest work function provides an ohmic contact for hole injection into the studied polymer. Injection from the widely used poly(2,3‐ethylenedioxythiophene)/polystyrenesulphonic acid (PEDOT:PSS)‐coated ITO anode system, is less efficient compared with some of the studied SAM‐coated ITO anodes despite the significantly higher work function measured by a Kelvin probe. This apparently anomalous situation is attributed to the inhomogenities in the injection processes that occur over the area of the device when the PEDOT:PSS‐coated ITO electrode is used.     

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.     

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.     

High‐Efficiency and Stable Quantum Dot Light‐Emitting Diodes Enabled by a Solution‐Processed Metal‐Doped Nickel Oxide Hole Injection Interfacial Layer

Stabilization is one critical issue that needs to be improved for future application of colloidal quantum dot (QD)‐based light‐emitting diodes (QLEDs). This study reports highly efficient and stable QLEDs based on solution‐processsed, metal‐doped nickel oxide films as hole injection layer (HIL). Several kinds of metal dopants (Li, Mg, and Cu) are introduced to improve the hole injection capability of NiO films. The resulting device with Cu:NiO HIL exhibits superior performance compared to the state‐of‐the‐art poly(3,4‐ethylenedioxythiophene):poly(styrene‐sulfonate) (PEDOT:PSS)‐based QLEDs, with a maximum current efficiency and external quantum efficiency of 45.7 cd A^?1 and 10.5%, respectively. These are the highest values reported so far for QLEDs with PEDOT:PSS‐free normal structure. Meanwhile, the resulting QLED shows a half‐life time of 87 h at an initial luminance of 5000 cd m^?2, almost fourfold longer than that of the PEDOT:PSS‐based device.     

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.     

Composite film of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) and MoO3 as an efficient hole injection layer for polymer light-emitting diodes

We demonstrate improved performances in polymer light-emitting diodes (PLEDs) using a composite film of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) and MoO₃ powder as a hole injection layer. The PLED with the composite film exhibits the current efficiency of 13.5 cd/A, driving voltage of 3.4 V, and half lifetime of 108.1 h, while those values of the PLED with a pristine PEDOT:PSS was 11.3 cd/A, 3.8 V, and 41.5 h, respectively. We also analyze the morphological, optical and electrical properties of the composite films by atomic force microscopy (AFM), UV–Vis-IR absorption, and ultraviolet photoemission spectroscopy (UPS). This work suggests that mixing MoO₃ into PEDOT:PSS is a simple and promising technique for use solution-based devices as an hole injection layer.     

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.     

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.     

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.     

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.     

Fine Control of Perovskite Crystallization and Reducing Luminescence Quenching Using Self‐Doped Polyaniline Hole Injection Layer for Efficient Perovskite Light‐Emitting Diodes

Organic–inorganic hybrid perovskites (OHPs) are promising emitters for light‐emitting diodes (LEDs) due to the high color purity, low cost, and simple synthesis. However, the electroluminescent efficiency of polycrystalline OHP LEDs (PeLEDs) is often limited by poor surface morphology, small exciton binding energy, and long exciton diffusion length of large‐grain OHP films caused by uncontrolled crystallization. Here, crystallization of methylammonium lead bromide (MAPbBr₃) is finely controlled by using a polar solvent‐soluble self‐doped conducting polymer, poly(styrenesulfonate)‐grafted polyaniline (PSS‐g‐PANI), as a hole injection layer (HIL) to induce granular structure, which makes charge carriers spatially confined more effectively than columnar structure induced by the conventional poly(3,4‐ethylenedioythiphene):polystyrenesulfonate (PEDOT:PSS). Moreover, lower acidity of PSS‐g‐PANI than PEDOT:PSS reduces indium tin oxide (ITO) etching, which releases metallic In species that cause exciton quenching. Finally, doubled device efficiency of 14.3 cd A^‐1 is achieved for PSS‐g‐PANI‐based polycrystalline MAPbBr₃ PeLEDs compared to that for PEDOT:PSS‐based PeLEDs (7.07 cd A^‐1). Furthermore, PSS‐g‐PANI demonstrates high efficiency of 37.6 cd A^‐1 in formamidinium lead bromide nanoparticle LEDs. The results provide an avenue to both control the crystallization kinetics and reduce the migration of In released from ITO by forming OIP films favorable for more radiative luminescence using the polar solvent‐soluble and low‐acidity polymeric HIL.     

Investigation of the Effects of Doping and Post‐Deposition Treatments on the Conductivity,Morphology, and Work Function of Poly(3,4‐ethylenedioxythiophene)/Poly(styrene sulfonate) Films

We investigate the influence of annealing conditions on the physical properties of thin films of poly(3,4‐ethylenedioxythiophene)/poly(styrene sulfonate) (PEDOT/PSS). In particular, we describe how annealing temperature, the ambient gas, and choice of dopant affect the conductivity, morphology, and work function of the films. Two specific dopants are considered, sorbitol and glycerol, and broad guidelines are developed for using PEDOT/PSS as a hole‐injection electrode in polymeric light‐emitting devices, solar cells, and photodetectors.     

Fluorescent,Carrier‐Trapping Dopants for Highly Efficient Single‐Layer Polyfluorene LEDs

Two fluorescent molecules with an alkynylanthracene core and pyrene end‐cappers have been synthesized and fully characterized. Carbazole moieties are introduced into one molecule at the C9 position of the fluorene linkages to enhance the hole‐transport ability of the molecule and to reduce intermolecular interactions. Both compounds exhibit high thermal stabilities and narrow energy bandgaps. Single‐layer polymer light‐emitting diodes (PLEDs) based on poly(9,9‐dioctylfluorene) (PFO) doped with the synthesized compounds exhibit excellent performance. A PLED with 0.2 % of dopant 7 had a high luminance efficiency of 10.7 ± 0.3 cd A^–1 as well as a brightness of 1400 cd m^–2 at a current density of 13 mA cm^–2, and a low turn on voltage (3.1 V) at a brightness of 10 cd m^–2. A maximum brightness of 20 500 ± 1400 cd m^–2 at 7 V was also measured. The high efficiency of the device's performance is attributed to the good electron and hole trapping ability of the dopants, which possess suitable energy levels as compared to those of PFO.     

Formation of Nanoislands on Conducting Poly(3,4‐ethylenedioxythiophene) Films by High‐Energy‐Ion Irradiation: Applications as Field Emitters and Capacitor Electrodes

Nanoislands have been fabricated on the surface of conducting poly(3,4‐ethylenedioxythiophene) (PEDOT) films doped with poly(4‐styrenesulfonate) (PSS) using high‐energy (≈ 1–3 MeV) Cl²⁺ ion irradiation. Scanning electron microscopy and atomic force microscopy confirm the direct formation of nanoislands with diameters ranging from 50 to 300 nm and heights ranging from 40 to 120 nm. From our analysis, we propose that the formation of nanoislands might be due to micelle formation of the polymeric stabilizer poly(sodium 4‐styrenesulfonate) (PSS‐Na) surrounding the nuclei in the PEDOT/PSS via the high‐energy‐ion irradiation. We observe similar results for high‐energy‐ion irradiated polyaniline doped with PSS‐Na. On using the nanoislands as nanotip emitters of a field‐emission display, an increase in the current density of about five orders of magnitude is observed. Cyclic voltammetry of the PEDOT/PSS electrode with the nanoislands as the electrode shows enhanced capacitance compared with that of the PEDOT/PSS film that contains no nanostructure.     

Achieving High Efficiency and Improved Stability in ITO‐Free Transparent Organic Light‐Emitting Diodes with Conductive Polymer Electrodes

Efficient transparent organic light‐emitting diodes (OLEDs) with improved stability based on conductive, transparent poly(3,4‐ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) electrodes are reported. Based on optical simulations, the device structures are carefully optimized by tuning the thickness of doped transport layers and electrodes. As a result, the performance of PEDOT:PSS‐based OLEDs reaches that of indium tin oxide (ITO)‐based reference devices. The efficiency and the long‐term stability of PEDOT:PSS‐based OLEDs are significantly improved. The structure engineering demonstrated in this study greatly enhances the overall performances of ITO‐free transparent OLEDs in terms of efficiency, lifetime, and transmittance. These results indicate that PEDOT:PSS‐based OLEDs have a promising future for practical applications in low‐cost and flexible device manufacturing.     

Charge‐Transporting Polymers based on Phenylbenzoimidazole Moieties

A series of novel styrene functionalized monomers with phenylbenzo[d]imidazole units and the corresponding homopolymers are prepared. These side‐chain polymers show high glass‐transition temperatures that even exceed the corresponding value for the common electron‐transporting material 1,3,5‐tris(1‐phenyl‐1H‐benzo[d]imidazol‐2‐yl)benzene (TPBI). Similar electronic behavior between the polymers and TPBI is shown. The polymers are used as matrices for phosphorescent dopants. The fabricated devices exhibit current efficiencies up to 38.5 cd A^?1 at 100 cd m^?2 and maximum luminances of 7400 cd m^?2 at 10 V with a minimum turn‐on voltage as low as 2.70 V in single‐layer devices with an ITO/PEDOT:PSS anode (ITO = indium tin oxide, PEDOT:PSS = poly(3,4‐ethylenedioxythiophene) doped with poly(styrenesulfonate)) and a CsF/Ca/Ag cathode.     

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.     

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.     

Improving Performance and Stability of Flexible Planar‐Heterojunction Perovskite Solar Cells Using Polymeric Hole‐Transport Material

For realizing flexible perovskite solar cells (PSCs), it is important to develop low‐temperature processable interlayer materials with excellent charge transporting properties. Herein, a novel polymeric hole‐transport material based on 1,4‐bis(4‐sulfonatobutoxy)benzene and thiophene moieties (PhNa‐1T) and its application as a hole‐transport layer (HTL) material of high‐performance inverted‐type flexible PSCs are introduced. Compared with the conventionally used poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), the incorporation of PhNa‐1T into HTL of the PSC device is demonstrated to be more effective for improving charge extraction from the perovskite absorber to the HTL and suppressing charge recombination in the bulk perovskite and HTL/perovskite interface. As a result, the flexible PSC using PhNa‐1T achieves high photovoltaic performances with an impressive power conversion efficiency of 14.7%. This is, to the best of our knowledge, among the highest performances reported to date for inverted‐type flexible PSCs. Moreover, the PhNa‐1T‐based flexible PSC shows much improved stability under an ambient condition than PEDOT:PSS‐based PSC. It is believed that PhNa‐1T is a promising candidate as an HTL material for high‐performance flexible PSCs.