RESUMEN
Despite the significant progress that has been made in recent years in improving the performance of quantum dot light-emitting devices (QLEDs), the effect of charge imbalance and excess carriers on excitons in red (R) vs green (G) vs blue (B) QLEDs has not been compared or systematically studied. In this work we study the effect of changing the electron (e)/hole (h) supply ratio in the QDs emissive layer (EML) in CdSe-based R-, G-, and B-QLEDs with inverted structure in order to identify the type of excess carriers and investigate their effect on the electroluminescence performance of QLEDs of each color. Results show that in R-QLEDs, the e/h ratio in the EML is >1, whereas in G- and B-QLEDs, the e/h ratio is <1 with charge balance conditions being significantly worse in the case of B-QLEDs. Transient photoluminescence (PL) and steady state PL measurements show that, compared to electrons, holes lead to a stronger Auger quenching effect. Transient electroluminescence (TrEL) results indicate that Auger quenching leads to a gradual decline in the EL performance of the QLEDs after a few microseconds, with a stronger effect observed for positive charging versus negative charging. The results provide insights into the differences in the efficiency behavior of R-, G-, and B-QLEDs and uncover the role of excess holes and poor charge balance in the lower efficiency and EL stability of B-QLEDs.
RESUMEN
Blue quantum dot light-emitting devices (QLEDs) suffer from fast electroluminescence (EL) loss when under electrical bias. Here, it is identified that the fast EL loss in blue QLEDs is not due to a deterioration in the photoluminescence quantum yield of the quantum dots (QDs), contrary to what is commonly believed, but rather arises primarily from changes in charge injection overtime under the bias that leads to a deterioration in charge balance. Measurements on hole-only and electron-only devices show that hole injection into blue QDs increases over time whereas electron injection decreases. Results also show that the changes are associated with changes in hole and electron trap densities. The results are further verified using QLEDs with blue and red QDs combinations, capacitance versus voltage, and versus time characteristics of the blue QLEDs. The changes in charge injection are also observed to be partially reversible, and therefore using pulsed current instead of constant current bias for driving the blue QLEDs leads to an almost 2.5× longer lifetime at the same initial luminance. This work systematically investigates the origin of blue QLEDs EL loss and provides insights for designing improved blue QDs paving the way for QLEDs technology commercialization.
RESUMEN
Addition of aqueous hydrohalic acids during the synthesis of colloidal quantum dots (QDs) is widely employed to achieve high-quality QDs. However, this reliance on the use of aqueous solutions is incompatible with oxygen- and water-sensitive precursors such as those used in the synthesis of Te-alloyed ZnSe QDs. Herein, it is shown that this incompatibility leads to phase segregation into Te-rich and Te-poor regions, causing spectral broadening and luminescence peak shifting under high laser irradiation and applied electrical bias. Here, a synthetic strategy to produce anhydrous-HF in situ by using benzenecarbonyl fluoride (BF) as a chemical additive is reported. Through in situ 19 F NMR spectroscopy, it is found that BF reacts with surfactants in tandem, ultimately producing intermediary F···H···trioctylamine adducts. These act as a pseudo-HF source that releases anhydrous HF. The controlled release of HF during nucleation and growth steps homogenizes Te distribution in ZnSeTe lattice, leading to spectrally stable blue-emitting QDs under increasing laser flux from ≈3 µW to ≈12 mW and applied bias from 2.6 to 10 V. Single-dot photoluminescence (PL) spectroscopy and analyses of the absorption, PL and transient absorption spectra together with density functional theory point to the role of anhydrous HF as a Te homogenizer.
RESUMEN
Encapsulating blue quantum dot light-emitting devices (QLEDs) using an ultraviolet curable resin is known to lead to a significant increase in their efficiency. Some of this efficiency increase occurs immediately, whereas some of it proceeds over a period of time, typically over several tens of hours following the encapsulation, a behavior commonly referred to as positive aging. The root causes of this positive aging, especially in blue QLEDs, remain not well understood. Here, it is revealed that contrary to the expectation, the significant improvement in device efficiency during positive aging arises primarily from an improvement in electron injection across the QD/ZnMgO interface and not due to the inhibition of interface exciton quenching as is widely believed. The underlying changes are investigated by XPS measurements. Results show that the enhancement in device performance arises primarily from the reduction in O-related defects in both the QDs and ZnMgO at the QD/ZnMgO interface. After 51.5 h, the blue QLEDs reach the optimal performance, exhibiting an EQEmax of 12.58%, which is more than sevenfold higher than that in the control device without encapsulation. This work provides design principles for realizing high efficiency in blue QLEDs with oxide electron-transporting layers (ETLs) and provides a new understanding of the mechanisms underlying positive aging in these devices and thus offers a new starting point for both fundamental investigations and practical applications.
RESUMEN
Despite its benefits for facilitating device fabrication, utilization of a polymeric hole transport layer (HTL) in inverted quantum dots (QDs) light-emitting devices (IQLEDs) often leads to poor device performance. In this work, we find that the poor performance arises primarily from electron leakage, inefficient charge injection, and significant exciton quenching at the HTL interface in the inverted architecture and not due to solvent damage effects as is widely believed. We also find that using a layer of wider band gap QDs as an interlayer (IL) in between the HTL and the main QDs' emission material layer (EML) can facilitate hole injection, suppress electron leakage, and reduce exciton quenching, effectively mitigating the poor interface effects and resulting in high electroluminescence performance. Using an IL in IQLEDs with a solution-processed poly(9,9-dioctylfluorene-alt-N-(4-sec-butylphenyl)-diphenylamine) (TFB), HTL improves the efficiency by 2.85× (from 3 to 8.56%) and prolongs the lifetime by 9.4× (from 1266 to 11,950 h at 100 cd/m2), which, to the best of our knowledge, is the longest lifetime for an R-IQLED with a solution-coated HTL. Measurements on single-carrier devices reveal that while electron injection becomes easier as the band gap of the QDs decreases, hole injection surprisingly becomes more difficult, indicating that EMLs of QLEDs are more electron-rich in the case of red devices and more hole-rich in the case of blue devices. Ultraviolet photoelectron spectroscopy measurements verify that blue QDs have a shallower valence band energy than their red counterparts, corroborating these conclusions. The findings in this work, therefore, provide not only a simple approach for achieving high performance in IQLEDs with solution-coated HTLs but also novel insights into charge injection and its dependence on QDs' band gap as well as into different HTL interface properties of the inverted versus upright architecture.
RESUMEN
ZnO nanoparticles are widely used for the electron transport layers (ETLs) of quantum dots light emitting devices (QLEDs). In this work we show that incorporating fluorine (F) into the ZnO ETL results in significant enhancement in device electroluminescence stability, leading to LT50 at 100 cd m-2 of 2,370,000 h in red QLED, 47X longer than the control devices. X-ray photo-electron spectroscopy, time-of-flight secondary ion mass spectroscopy, photoluminescence and electrical measurements show that the F passivates oxygen vacancies and reduces electron traps in ZnO. Transient photoluminescence versus bias measurements and capacitance-voltage-luminance measurements reveal that the CF4 plasma-treated ETLs lead to increased electron concentration in the QD and the QD/hole transport layer interface, subsequently decreasing hole accumulation, and hence the higher stability. The findings provide new insights into the critical roles that optimizing charge distribution across the layers play in influencing stability and present a novel and simple approach for extending QLED lifetimes.
RESUMEN
The effect of adding polyethylenimine (PEI) into the ZnO electron transport layer (ETL) of inverted quantum dot (QD) light emitting devices (QDLEDs) to form a blended ZnO:PEI ETL instead of using it in a separate layer in a bilayer ZnO/PEI ETL is investigated. Results show that while both ZnO/PEI bilayer ETL and ZnO:PEI blended ETL can improve device efficiency by more than 50% compared to QDLEDs with only ZnO, the ZnO:PEI ETL significantly improves device stability, leading to more than 10 times longer device lifetime. Investigations using devices with marking luminescent layers, electron-only devices and delayed electroluminescence measurements show that the ZnO:PEI ETL leads to a deeper penetration of electrons into the hole transport layer (HTL) of the QDLEDs. The results suggest that the stability enhancement may be due to a consequent reduction in hole accumulation at the QD/HTL interface. The findings show that ZnO:PEI ETLs can be used for enhancing both the efficiency and stability of QDLEDs. They also provide new insights into the importance of managing charge distribution in the charge transport layers for realizing high stability QDLEDs and new approaches to achieve that.
RESUMEN
Self-assembled monolayers (SAMs) deposited on bottom electrodes are commonly used to tune charge carrier injection or blocking in optoelectronic devices. Beside the enhancement of device performance, the fabrication of multifunctional devices in which the output can be modulated by multiple external stimuli remains a challenging target. In this work, we report the functionalization of an indium tin oxide (ITO) electrode with a SAM of a diarylethene derivative designed for optically control the electronic properties. Following the demonstration of dense SAM formation and its photochromic activity, as a proof-of-principle, an organic light-emitting diode (OLED) embedding the light-responsive SAM-covered electrode was fabricated and characterized. Optically addressing the two-terminal device by irradiation with ultraviolet light doubles the electroluminescence. The original value can be restored reversibly by irradiation with visible light. This expanded functionality is based on the photoinduced modulation of the electronic structure of the diarylethene isomers, which impact the charge carriers' confinement within the emissive layer. This approach could be successfully exploited in the field of opto-communication technology, for example to fabricate opto-electronic logic circuits.
RESUMEN
Organic light-emitting transistors are pivotal components for emerging opto- and nanoelectronics applications, such as logic circuitries and smart displays. Within this technology sector, the integration of multiple functionalities in a single electronic device remains the key challenge. Here we show optically switchable organic light-emitting transistors fabricated through a judicious combination of light-emitting semiconductors and photochromic molecules. Irradiation of the solution-processed films at selected wavelengths enables the efficient and reversible tuning of charge transport and electroluminescence simultaneously, with a high degree of modulation (on/off ratios up to 500) in the three primary colours. Different emitting patterns can be written and erased through a non-invasive and mask-free process, on a length scale of a few micrometres in a single device, thereby rendering this technology potentially promising for optically gated highly integrated full-colour displays and active optical memory.
RESUMEN
Ultrasound-induced liquid-phase exfoliation (UILPE) is an established method to produce single- (SLG) and few-layer (FLG) graphene nanosheets starting from graphite as a precursor. In this paper we investigate the effect of the ultrasonication power in the UILPE process carried out in either N-methyl-2-pyrrolidone (NMP) or ortho-dichlorobenzene (o-DCB). Our experimental results reveal that while the SLGs/FLGs concentration of the NMP dispersions is independent of the power of the ultrasonic bath during the UILPE process, in o-DCB it decreases as the ultrasonication power increases. Moreover, the ultrasonication power has a strong influence on the lateral size of the exfoliated SLGs/FLGs nanosheets in o-DCB. In particular, when UILPE is carried out at â¼600 W, we obtain dispersions composed of graphene nanosheets with a lateral size of 180 nm, whereas at higher power (â¼1000 W) we produce graphene nanodots (GNDs) with an average diameter of â¼17 nm. The latter nanostructures exhibit a strong and almost excitation-independent photoluminescence emission in the UV/deep-blue region of the electromagnetic spectrum arising from the GNDs' intrinsic states and a less intense (and strongly excitation wavelength dependent) emission in the green/red region attributed to defect states. Notably, we also observe visible emission with near-infrared excitation at 850 and 900 nm, a fingerprint of the presence of up-conversion processes. Overall, our results highlight the crucial importance of the solvent choice for the UILPE process, which under controlled experimental conditions allows the fine-tuning of the morphological properties, such as lateral size and thickness, of the graphene nanosheets toward the realization of luminescent GNDs.