Flexible Quantum Dot Light-emitting Diodes Research Articles

Manipulating exciton confinement for stable and efficient flexible quantum dot light-emitting diodes

Flexible quantum dot light-emitting diodes (QLEDs) show great promise for the next generation of flexible, wearable, and artificial intelligence display applications. However, the performance of flexible QLEDs still lags behind that of rigid substrate devices, hindering their commercialization for display applications. Here we report the superior performance of flexible QLEDs based on efficient red ZnCdSe/ZnS/ZnSe QDs (A-QDs) with anti-type-I nanostructures. We reveal that using ZnS as an intermediate shell can effectively confine the exciton wavefunction to the inner core, reducing the surface sensitivity of the QDs and maintaining its excellent emission properties. These flexible QLEDs exhibit a peak external quantum efficiency of 23.0% and a long lifetime of 63,050 h, respectively. The anti-type-I nanostructure of A-QDs in the device simultaneously suppresses defect-induced nonradiative recombination and balances carrier injection, achieving the most excellent performance of flexible QLEDs ever reported. This study provides new insights into achieving superior performance in flexible QD-based electroluminescent devices.

(Invited) Toward Ultrathin Flexible Quantum Dot Light-Emitting Diodes and Photodetectors for the Wearable Electronics

Flexible optoelectronic devices, encompassing light-emitting diodes (LEDs) and photodetectors, capable of seamlessly transforming their shapes, represent a prominent trend in next-generation electronics. Quantum dots, widely employed as emitters and light absorption layers, are chosen for their high luminous performance, size-dependent color tunability, and excellent light absorption properties. Moreover, their solution processability and ultrathin form factor make them particularly appealing for the development of ultrathin wearable optoelectronic devices.Here, we introduce ultrathin flexible quantum dot light-emitting diodes and photodetectors designed for wearable electronics. Utilizing intaglio transfer printing, we can produce high-definition red-green-blue quantum dot LEDs, suitable for integration into skin-attachable displays. Moreover, our ultrathin, self-powered, heavy-metal-free photodetectors, based on copper indium selenide nanoparticles, showcase outstanding optical performance (specific detectivity: 2.10 × 1012 Jones at zero-bias) and find application in wearable photoplethysmography (PPG) sensors.

Flexible Substrate-Compatible and Efficiency-Improved Quantum-Dot Light-Emitting Diodes with Reduced Annealing Temperature of NiOx Hole-Injecting Layer

The growing demand for wearable and attachable displays has sparked significant interest in flexible quantum-dot light-emitting diodes (QLEDs). However, the challenges of fabricating and operating QLEDs on flexible substrates persist due to the lack of stable and low-temperature processable charge-injection/-transporting layers with aligned energy levels. In this study, we utilized NiOx nanoparticles that are compatible with flexible substrates as a hole-injection layer (HIL). To enhance the work function of the NiOx HIL, we introduced a self-assembled dipole modifier called 4-(trifluoromethyl)benzoic acid (4–CF3–BA) onto the surface of the NiOx nanoparticles. The incorporation of the dipole molecules through adsorption treatment has significantly changed the wettability and electronic characteristics of NiOx nanoparticles, resulting in the formation of NiO(OH) at the interface and a shift in vacuum level. The alteration of surface electronic states of the NiOx nanoparticles not only improves the carrier balance by reducing the hole injection barrier but also prevents exciton quenching by passivating defects in the film. Consequently, the NiOx-based red QLEDs with interfacial modification demonstrate a maximum current efficiency of 16.1 cd/A and a peak external quantum efficiency of 10.3%. This represents a nearly twofold efficiency enhancement compared to control devices. The mild fabrication requirements and low annealing temperatures suggest potential applications of dipole molecule-modified NiOx nanoparticles in flexible optoelectronic devices.

Optimizing Ag films towards efficient flexible quantum-dot light-emitting diodes

Metal film electrodes are frequently adopted in flexible quantum-dot light-emitting diodes (FQLEDs) to form microcavity structures, which accelerate the recombination of excitons and thereby enhancing the efficiency of devices, especially under high driving current density. However, metal films prepared by thermal evaporation grow according to the Volmer-Weber nucleation mechanism, thereby resulting in the formation of numerous metal islands on the target substrate. The serious leakage current and light scattering (hence weakened microcavity effect) caused by these islands lead to inefficient FQLEDs. Here we fabricated a highly uniform and smooth Ag-based flexible electrode by utilizing an ultrathin polyethyleneimine as the nucleation-inducing seed layer. A smooth surface with a root-mean-square of approximately 3.7 nm and an ultralow sheet resistance of 3.65 Ω sq−1 have been obtained for the Ag film with a thickness of only 16 nm. Thus, a high-efficiency FQLED is achieved with the maximum external quantum efficiency up to 25.6 %. Furthermore, this device exhibits ultralow efficiency roll-off, characterized by the external quantum efficiency of over 20 % across an extremely wide luminance range, from 300 to 160,000 cd m−2, meeting all display and lighting requirements.

Flexible Quantum-Dot Light-Emitting Diodes Using Embedded Silver Mesh Transparent Electrodes Manufactured by an Ultraprecise Deposition Method.

Transparent conductive electrodes (TCEs) fabricated onto flexible substrates are crucial parts of organic-light-emitting diodes (OLEDs), which are vastly utilized for display and lightning applications. Indium tin oxide (ITO), which is so far the most popular material for transparent and conductive electrodes, is found to be an unsuitable candidate for flexible devices mostly due to its brittleness. Here, we present a novel approach for the fabrication of transparent, conductive, and flexible electrodes for optoelectronic applications made of silver metal mesh by an ultraprecise deposition (UPD) method. The fabricated mesh exhibits an 80% (λ = 550 nm) optical transmittance and a sheet resistance of 11 Ω/sq. The Ag-mesh embedded into the polymer is implemented as an anode for a quantum-dot light-emitting diode (QLED) in order to assess its performance. The fabricated QLED is characterized by the maximum external quantum efficiency (EQE) of 2% and a current efficiency (CE) of 6 cd/A, reaching the maximum luminance (L) of 3200 cd/m2 at a current density of 100 mA/cm2. This method shows a fast and relatively simple approach to fabricate optoelectronic devices without the need for special treatment and sophisticated equipment.

Enhanced performance of flexible quantum dot light-emitting diodes using a low-temperature processed PTAA hole transport layer

Low-temperature processing is important for improving the stability and performance of flexible quantum dot light-emitting diodes (QLEDs). In this study, QLEDs were fabricated using poly[bis(4-phenyl) (2,4,6-trimethylphenyl)amine] (PTAA) as a suitable hole transport layer (HTL) material owing to its low-temperature processability and vanadium oxide as the low-temperature solution-processable hole injection layer material. The maximum luminance and highest current efficiency of the QLEDs on a glass substrate with an optimal PTAA HTL was 8.9 × 104 Cd/m2 and 15.9 Cd/A, respectively, which was comparable to that of conventional devices. The QLEDs on a flexible substrate showed a maximum luminance of 5.4 × 104 Cd/m2 and highest current efficiency of 5.1 Cd/A. X-ray and ultraviolet photoelectron spectroscopies were used to investigate the chemical state and interfacial electronic structure according to the materials and the state changes of the HTL, respectively. The interfacial electronic structure showed that PTAA exhibited a better hole transport ability owing to its low hole injection barrier ({Phi }_{{text{h}}}). Moreover, QLEDs with a PTAA HTL could operate as photosensors under reverse bias conditions. These results indicate that the low-temperature-processed PTAA HTL is suitable for improving the performance of flexible QLEDs.

Efficient flexible quantum-dot light-emitting diodes with unipolar charge injection.

The exfoliation between the electrode film and the adjacent functional layer is still a big challenge for the flexible light emitting diodes, especially for the devices dependent on the direct charge injection from the electrodes. To address this issue, we design a flexible quantum-dot light-emitting diodes (QLEDs) with a charge-generation layer (CGL) on the bottom electrode as the electron supplier. The CGL consisting of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)/ZnO can provide sufficient electron injection into the QDs, enabling a balanced charge injection. As a result, the CGL-based QLED exhibits a peak external quantum efficiency 18.6%, over 25% enhancement in comparison with the device with ZnO as the electron transport layer. Moreover, the residual electrons in the ZnO can be pulled back to the PEDOT:PSS/ZnO interface by the storage holes in the CGL, which are released and accelerates the electron injection during the next driving voltage pulse, hence improving the electroluminescence response speed of the QLEDs.

Unravelling the bending stability of flexible quantum-dot light-emitting diodes

The bending stability is still the central obstacle to the practical applications of flexible quantum-dot light-emitting diodes (QLED). Here, we examine the influence of every functional layer, including electrodes, charge injection/transport layers, and emission layer, on the photoelectrical properties of the QLEDs during the bending fatigue test. It is demonstrated that the bottom substrate and top metal electrode play a critical role in determining the bending stability of flexible QLEDs. The bending stability of the QLED can be improved obviously by controlling the elastic modulus and surface roughness of the substrate with a poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) modifying layer inserted between PET/ITO/Ag/ITO and ZnO electron-transport layer. The PEDOT:PSS layer not only reduces the surface roughness, but also causes the neutral mechanical plane of the PET/ITO/Ag/ITO multilayer to move towards the surface of the substrate. The twofold effect of this PEDOT:PSS modifying layer improves the bending stability of the device. Moreover, the device efficiency is also enhanced from 17.9 to 20.4 cd A−1 with the insertion of PEDOT:PSS layer.

Flexible CdSe/ZnS Quantum-Dot Light-Emitting Diodes with Higher Efficiency than Rigid Devices.

Fabrication of high-performance, flexible quantum-dot light-emitting diodes (QLEDs) requires the reliable manufacture of a flexible transparent electrode to replace the conventional brittle indium tin oxide (ITO) transparent electrode, along with flexible substrate planarization. We deposited a transparent oxide/metal/oxide (OMO) electrode on a polymer planarization layer and co-optimized both layers. The visible transmittance of the OMO electrode on a polyethylene terephthalate substrate increased markedly. Good electron supply and injection into an electron-transporting layer were achieved using WOX/Ag/ WOX and MoOx/Ag/MoOX OMO electrodes. High-performance flexible QLEDs were fabricated from these electrodes; a QLED with a MoOX/Ag/ MoOX cathode and an SU-8 planarization layer had a current efficiency of 30.3 cd/A and luminance more than 7 × 104 cd/m2. The current efficiency was significantly higher than that of a rigid QLED with an ITO cathode and was higher than current efficiency values obtained from previously reported QLEDs that utilized the same quantum-dot and electron-transporting layer materials as our study.

Fabrication of Large-Area Uniform Nanometer-Thick Functional Layers and Their Stacks for Flexible Quantum Dot Light-Emitting Diodes.

Large-area fabrication and stacking of various nanometer-thick functional layers from solutions is essentially important for the construction of flexible thin-film optoelectronic devices, but very challenging. The existing fabrication methods suffer from either non-uniformity caused by the coffee-ring effect or serious solution waste (excess of 90% for spin coating), and are hard to scale up and create stacks. Here, it is shown that centrifugal casting is a universal, scalable, and efficient method to fabricate uniform nanometer-thick films and their stacks of various materials. The coffee-ring effect is effectively suppressed, the solution utilization ratio is higher than ≈61%, and the films/stacks show a smooth surface/high-quality interface. Using this method, flexible quantum dot light-emitting diode displays with uniform luminance in a large lighting area of ≈115 cm2 that have not been achieved even on rigid substrates by the existing methods, are realized. This efficient and low-cost solution processing method paves a way for large-area fabrication of various flexible thin-film optoelectronic devices.

Flexible quantum dot light-emitting diodes without sacrificing optical and electrical performance

Quantum dot light-emitting diodes (QLEDs) has been developed toward flexibility without sacrificing optical and electrical performances as in the case of organic light-emitting diodes (OLEDs) display. The biggest challenge is replacing the conventional rigid or brittle electrodes, which has not been successful in the QLEDs yet. In this study, the flexible QLEDs without degradation of both optical and electrical performances are demonstrated to exhibit excellent light-emitting properties (maximum luminance of 14,330 cd/m2 and maximum current efficiency of 20.77 cd/A) with a low turn-on voltage of 3.5 V. The double-layered graphene of stepwise-tuned workfunctions was developed as a flexible and transparent anode. The top layer of a graphene film is oxidized by the oxygen plasma, which promotes wettability of the hydrophilic hole injection layer (HIL) and enhances the rate of hole injection by mediating the workfunctions between HIL and the pristine graphene anode. The color shift as a function of brightness could be minimized due to the balanced charge injection through this new electrode. The flexibility of QLEDs could be accomplished with mixture of an Al film and Ag nanowires as a cathode. No significant degradation of flexible QLED performances could be observed through a bending test involving even 1,000 bends.

Emerging Self-Emissive Technologies for Flexible Displays.

Featuring a combination of ultrathin and lightweight properties, excellent mechanical flexibility, low power-consumption, and widely tunable saturated emission, flexible displays have opened up a new possibility for optoelectronics. The demands for flexible displays are growing on a continual basis due not only to their successful commercialization but, more importantly, their endless possibilities for wearable integrated systems. Up to now, self-emissive technologies for displays, flexible active-matrix organic light-emitting diodes (flex-AMOLED), flexible quantum dot light-emitting diodes (flex-QLEDs), and flexible perovskite light-emitting diodes (flex-PeLEDs) have been widely reported, but despite the significant progress made in these technologies, enormous obstacles and challenges remain for the vision of truly wearable applications, in particular with flex-QLEDs and flex-PeLEDs. Here, a review of the recent progress of all three self-emissive technologies for flexible displays is conducted, including the emissive active materials, device structures and approaches to manufacturing, the flexible substrates, and conductive electrodes, as well as the encapsulation techniques. The fast-paced improvement made to the efficiency of flexible devices in recent years is also summarized. The review concludes by making suggestions on the future development in this area, and is expected to help researchers in gaining a comprehensive understanding about the newly emerging technologies for flexible displays.

Low-temperature and solution-processable inorganic hole injection layer for flexible quantum-dot light-emitting diodes

A low-temperature solution-processable inorganic vanadium oxide (V2O5) hole injection layer (HIL) was synthesized for flexible quantum-dot light-emitting diodes (QLEDs). Efficient hole injection characteristics were observed in the hole-only devices; furthermore, the process temperature of V2O5 was as low as 30 °C. We investigated the source of the efficient hole injection behavior using ultraviolet and x-ray photoelectron spectroscopy. The density of gap states was found to increase in accordance with process temperature reduction. Therefore, QLEDs with low-temperature solution-processable V2O5 HILs were fabricated on a glass substrate, which showed excellent characteristics. The maximum luminance and luminous efficiency of the device were 56,717 Cd/m2 and 4.03 Cd/A, respectively. Due to the low-temperature process of the V2O5 HIL, it was also possible to fabricate QLEDs on a flexible plastic substrate without mechanical or thermal deformation of the substrate. Our results suggest that the low-temperature V2O5 inorganic HIL is a feasible alternative to organic HILs for flexible QLEDs.

A low-temperature-annealed and UV-ozone-enhanced combustion derived nickel oxide hole injection layer for flexible quantum dot light-emitting diodes.

Sol-gel derived nickel oxide (NiOx) has been extensively investigated as the hole injection layer (HIL) for many optoelectronic devices because of its advantages of high environmental stability and low cost fabrication. Conventional sol-gel synthesis of NiOx requires high annealing temperature to convert precursors into crystal lattices, which limits its application in flexible devices. To address this issue, a low-temperature (150 °C) combustion method is used to synthesize NiOx. Besides, UV-ozone treatment is further performed to improve the electrical properties of low-temperature-grown NiOx, which leads to the formation of nickel oxyhydroxide (NiO(OH)) surface dipoles and Ni vacancies and thus modifies the energy structure and increases the conductivity of NiOx. Moreover, the formation of surface NiO(OH) induces a vacuum level shift and thus reduces the hole injection barrier. Owing to the enhanced hole injection, solution-processed green QLEDs with optimized UV-ozone treated NiOx HILs exhibit maximum current efficiencies of 45.8 cd A-1 and external quantum efficiencies of 10.9%, which outperform those of the devices with poly(3,4-ethylene dioxythiophene) : poly(4-styrenesulfonate) (PEDOT:PSS) HILs. Meanwhile, these devices also show better long-term stability with a 3.2-fold longer half-life time than that of the PEDOT:PSS-based devices. The demonstrated low-temperature-annealed and UV-ozone enhanced NiOx HILs would enable the realization of flexible QLEDs with high brightness, efficiency and stability.

Aqueous solution-processed molybdenum oxide as an efficient hole injection layer for flexible quantum dot light emitting diodes

In this paper, the aqueous solution-processed molybdenum oxide (sMoOx) as an efficient hole injection layer for flexible quantum dot light emitting diodes (QLEDs) was prepared using a simple, low-cost and non-toxic solution method. Compared to the traditional device used poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) as hole injection layer, the flexible QLED with modified sMoOx film has a higher maximum current efficiency, 5.46 cd/A. In addition, the stability and lifetime of flexible devices are improved effectively with the use of inorganic molybdenum oxide as hole injection layer, and they presented excellent flexibility through the repeated mechanical bending test at 5 mm radius of curvature.

Inverted Device Architecture for Enhanced Performance of Flexible Silicon Quantum Dot Light-Emitting Diode.

Here we report for the first time highly flexible quantum dot light-emitting diodes (QLEDs), in which a layer of red-emitting colloidal silicon quantum dots (SiQDs) works as the optically active component, by replacing a rigid glass substrate with a thin sheet of polyethylene terephthalate (PET). The enhanced optical performance for electroluminescence (EL) at room temperature in air is achieved by taking advantage of the inverted device structure. Our QLEDs do not exhibit parasitic EL emissions from the neighboring compositional layers or surface states of QDs over a wide range of driving voltages and do not exhibit a shift in the EL peak position as the operational voltage increases. Compared to the previous Si-QLEDs with a conventional device structure, our QLED has a longer device operational lifetime and a long-lived EQE value. The currently obtained brightness (∼5000 cd/m2), the 3.1% external quantum efficiency (EQE), and a turn-on voltage as low as 3.5 V are sufficiently high to encourage further developments of Si-QLEDs.

Improve the surface of silver nanowire transparent electrode using a double-layer structure for the quantum-dot light-emitting diodes

We developed a double-layer structured transparent electrode for use in flexible quantum-dot light-emitting diodes (QLEDs). Silver nanowires (AgNWs) and highly conductive poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) were coated on a transparent substrate to obtain a highly conductive and flexible transparent electrode. The highly conductive PEDOT:PSS improved the surface roughness of the AgNWs transparent electrode film as well as the surface coverage area of the film. The double-layer structured transparent electrode showed superior mechanical properties than conventional indium–tin oxide (ITO) and AgNWs transparent electrodes. QLEDs with the double-layer structured transparent electrode also showed good reliability under cyclic bending conditions. These results indicate that the double-layer structured AgNWs/PEDOT:PSS transparent electrode described here is a feasible alternative to ITO transparent electrodes for flexible QLEDs.

Intaglio-type random silver networks as the cathodes for efficient full-solution processed flexible quantum-dot light-emitting diodes.

Flexible quantum-dot light-emitting diodes (FQLEDs) hold great promise as a leading display and lighting technology due to their light weight, low-cost, and saturated emission color. However, there remain many challenges in the development of high quality electrodes on flexible substrates for device fabrication and operation. In this work, we present a robust flexible transparent conductive film with embedded random Ag networks in the PET substrate (named PRAN). The PRAN composite film exhibits an average transmittance of 85%, and the sheet resistance reaches near 5.3 Ω sq-1 without any obvious change after bending 3000 times, indicating excellent flexibility of this type of conductive film. A highly conductive poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) layer was employed to smooth the surface of the PRAN electrode. Consequently, FQLEDs based on these flexible electrodes are successfully fabricated and the peak power efficiencies of 42.3, 101.9, and 6.4 lm W-1 are achieved for the red, green and blue devices, respectively. To the best of our knowledge, these are the best efficiencies for the FQLEDs reported to date. These results lay the foundation of the realization of ITO-free, high-efficiency FQLEDs for use in flexible lighting and display applications.

Polyethylenimine Ethoxylated-Mediated All-Solution-Processed High-Performance Flexible Inverted Quantum Dot-Light-Emitting Device.

We report on an all-solution-processed fabrication of highly efficient green quantum dot-light-emitting diodes (QLEDs) with an inverted architecture, where an interfacial polymeric surface modifier of polyethylenimine ethoxylated (PEIE) is inserted between a quantum dot (QD) emitting layer (EML) and a hole transport layer (HTL), and a MoOx hole injection layer is solution deposited on top of the HTL. Among the inverted QLEDs with varied PEIE thicknesses, the device with an optimal PEIE thickness of 15.5 nm shows record maximum efficiency values of 65.3 cd/A in current efficiency and 15.6% in external quantum efficiency (EQE). All-solution-processed fabrication of inverted QLED is further implemented on a flexible platform by developing a high-performing transparent conducting composite film of ZnO nanoparticles-overcoated on Ag nanowires. The resulting flexible inverted device possesses 35.1 cd/A in current efficiency and 8.4% in EQE, which are also the highest efficiency values ever reported in flexible QLEDs.