Electroluminescence Quantum Efficiency Research Articles

Reducing Non-Radiative Energy Losses in Non-fullerene Organic Solar Cells.

With the rapid advancement of non-fullerene acceptors (NFAs), the power conversion efficiency (PCE) of organic solar cells (OSCs) has surpassed the 20% threshold, highlighting their considerable potential as next-generation energy conversion devices. In comparison to inorganic or perovskite solar cells, the open-circuit voltage (Voc) of OSCs is constrained by substantial non-radiative energy losses (ΔEnr), leading to values notably below those anticipated by the Shockley-Queisser limit. In OSCs, non-radiative energy losses are intimately associated with the electroluminescent quantum efficiency (EQEEL) of charge transfer states, which is in turn directly affected by the photoluminescence quantum yield (PLQY) of acceptor materials. Consequently, enhancing the PLQY of low-bandgap acceptor materials has emerged as a pivotal strategy to effectively mitigate ΔEnr. This review article delves into the intrinsic correlation between molecular structure and PLQY from the vantage point of acceptor material design. It further explores methodologies for designing acceptor materials exhibiting high PLQY, with the ultimate goal of realizing OSCs that combine high efficiency with minimal ΔEnr.

Understanding the Nonradiative Charge Recombination in Organic Photovoltaics: From Molecule to Device

AbstractOrganic photovoltaics (OPVs) have made significant strides with efficiencies now exceeding 20%, positioning them as potential competitors to inorganic solar technologies. One of the most critical challenges toward this goal is the severe open‐circuit voltage (Voc) loss caused by the nonradiative charge recombination (NRCR). Herein, this review comprehensively summarizes the NRCR mechanisms and suppression techniques of OPVs across various scales from molecule to device. Specifically, the origins of NRCR in a single molecule are first summarized, and molecular design principles toward high photoluminescence quantum yield are reviewed following the Marcus theory. Next, the effect of aggregation on NRCR is reviewed, as well as the molecular and processing strategies to modulate the film packing for NRCR suppression. Furthermore, the progresses in the avoidance of nonradiative loss pathways mediated by charge transfer states and triplet states in donor:acceptor bulk heterojunctions are tracked. Besides, the interfacial optimization and device structure design to maximize the electroluminescent quantum efficiency are presented. Finally, several potential pathways toward curtailing NRCR for high‐performance OPVs are outlined. Therefore, this review shows an insightful perspective to understand and mitigate the NRCR at multi‐scales, and is poised to provide a clear roadmap for the next breakthrough of OPVs.

To Maximize Luminescence for an Efficient Organic Solar Cell†

Comprehensive SummaryWith the continuous development of photovoltaic materials, organic solar cells (OSCs) have made remarkable advancements, surpassing a power conversion efficiency (PCE) of 20%. However, the PCEs of OSCs remain lower than that of inorganic solar cells due to significant energy losses, mainly stemming from the relatively large non‐radiative recombination losses (usually be expressed as ∆E3), resulting in low open‐circuit voltages. This can be achieved by reducing non‐radiative recombination, and hereby increasing the electroluminescence quantum efficiency (EQEEL) of the photo‐active layer. This review analyzes the significance of luminescence efficiency in achieving high‐performance OSCs by examining the reciprocal relationship between ∆E3 and EQEEL. High‐efficiency organic solar cells can also be used as effective organic light‐emitting diodes (OLEDs). The discussion provides insights into the influencing factors of EQEEL and the mechanisms for adjusting various parameters, which include enhancements in photoluminescence quantum yield and the proportion of radiative excitons. The objective is to offer insights into the crucial role of luminescence performance in OSC development, guiding researchers toward developing novel photovoltaic materials or optimization strategies to enhance the luminescence performance of the active layer in OSCs, fostering the simultaneous advancement of OSCs and OLEDs. Key Scientists

Room-temperature efficient and tunable interlayer exciton emissions in WS2/WSe2 heterobilayers at high generation rates.

Transition metal dichalcogenide (TMDC) heterobilayers (HBs) have been intensively investigated lately because they offer novel platforms for the exploration of interlayer excitons (IXs). However, the potentials of IXs in TMDC HBs have not been fully studied as efficient and tunable emitters for both photoluminescence (PL) and electroluminescence (EL) at room temperature (RT). Also, the efficiencies of the PL and EL of IXs have not been carefully quantified. In this work, we demonstrate that IX in WS2/WSe2 HBs could serve as promising emitters at high generation rates due to its immunity to efficiency roll-off. Furthermore, by applying gate voltages to balance the electron and hole concentrations and to reinforce the built-in electric fields, high PL quantum yield (QY) and EL external quantum efficiency (EQE) of ∼0.48% and ∼0.11% were achieved at RT, respectively, with generation rates exceeding 1021 cm-2·s-1, which confirms the capabilities of IXs as efficient NIR light emitters by surpassing most of the intralayer emissions from TMDCs.

Enhanced Photon Recycling Enables Efficient Perovskite Light‐Emitting Diodes

AbstractPerovskite light‐emitting diodes (PeLEDs) have recently experienced rapid growth in performance. While photon recycling, which involves the reemission of reabsorbed light, significantly boosts efficiency, PeLED structures are typically based on classical design principles, often overlooking photon recycling. Here, a practical strategy to maximize the benefit of the photon recycling effect in PeLEDs is demonstrated. Parasitic absorption in electrodes represents a significant loss that impedes the efficient recycling of photons in trapped modes. The design strategy is verified by improving the average electroluminescence quantum efficiencies from 19.5% to 22.0% in near‐infrared PeLEDs with thinner indium tin oxide (ITO) electrodes, ultimately achieving a champion efficiency of 23.9%. The effect of photon recycling is visualized by transient photoluminescence mapping. It is quantified computationally that the additional efficiency coming from photon recycling is doubled from 2.3% to 4.8% in the device by suppressing the relative loss in ITO from 39% to 13%. The strategies raise the theoretical upper bound efficiency of PeLEDs with a gold top electrode from 27% to 37% by boosting the photon recycling effect.

Tunable Ag Nanocavity Enhanced Green Electroluminescence from SiNx:O Light-Emitting Diode.

As the driving source, highly efficient silicon-based light emission is urgently needed for the realization of optoelectronic integrated chips. Here, we report that enhanced green electroluminescence (EL) can be obtained from oxygen-doped silicon nitride (SiNx:O) films based on an ordered and tunable Ag nanocavity array with a high density by nanosphere lithography and laser irradiation. Compared with that of a pure SiNxO device, the green electroluminescence (EL) from the SiNx:O/Ag nanocavity array device can be increased by 7.1-fold. Moreover, the external quantum efficiency of the green electroluminescence (EL) is enhanced 3-fold for SiNx:O/Ag nanocavity arrays with diameters of 300 nm. The analysis of absorption spectra and the FDTD calculation reveal that the localized surface plasmon (LSP) resonance of size-controllable Ag nanocavity arrays and SiNx:O films play a key role in the strong green EL. Our discovery demonstrates that SiNx:O films coupled with tunable Ag nanocavity arrays are promising for silicon-based light-emitting diode devices of the AI period in the future.

Impact of Spontaneous Orientational Polarization on Triplet-Triplet Upconversion-Based Blue Organic Light-Emitting Diodes.

The spontaneous orientation polarization (SOP) of a permanent dipole moment of the molecule induces a giant surface potential (GSP) in an organic semiconductor film, and GSP is expected to be a crucial parameter for understanding the operational mechanism of organic light-emitting diodes (OLEDs). This study demonstrates that the voltage-dependent migration of a carrier recombination zone induced by a polar electron transporting layer (ETL) having a positive SOP causes a decline in the overall performance of the OLED in triplet-triplet upconversion (TTU) based on OLEDs. Specifically, the TTU efficiency in an OLED with 2,2',2″-(1,3,5-benzinetriyl)-tris(1-phenyl-1-H-benzimidazole) (TPBi) as the ETL decreased by 20% due to the reduction of electrically generated triplet exciton density. This decrease resulted in a lower external electroluminescence (EL) quantum efficiency (EQE) of 5.4% at 1 mA cm-2, while the OLED with a nonpolar ETL resulted in an EQE of around 8.1% at 1 mA cm-2. We confirmed a shift in the recombination zone from the current density dependence of the EL spectra in the OLEDs. Our results indicate that the fixed carrier recombination zone near a hole transport layer and an emitting layer (HTL/EML) strongly enhanced the TTU process, while the polar EML/ETL interface induced the migration of the recombination zone depending on voltage, resulting in the decrease of triplet exciton density.

Dual Optoelectronic Organic Field-Effect Device: Combination of Electroluminescence and Photosensitivity.

Merging the functionality of an organic field-effect transistor (OFET) with either a light emission or a photoelectric effect can increase the efficiency of displays or photosensing devices. In this work, we show that an organic semiconductor enables a multifunctional OFET combining electroluminescence (EL) and a photoelectric effect. Specifically, our computational and experimental investigations of a six-ring thiophene-phenylene co-oligomer (TPCO) revealed that this material is promising for OFETs, light-emitting, and photoelectric devices because of the large oscillator strength of the lowest-energy singlet transition, efficient luminescence, pronounced delocalization of the excited state, and balanced charge transport. The fabricated OFETs showed a photoelectric response for wavelengths shorter than 530 nm and simultaneously EL in the transistor channel, with a maximum at ~570 nm. The devices demonstrated an EL external quantum efficiency (EQE) of ~1.4% and a photoelectric responsivity of ~0.7 A W-1, which are among the best values reported for state-of-the-art organic light-emitting transistors and phototransistors, respectively. We anticipate that our results will stimulate the design of efficient materials for multifunctional organic optoelectronic devices and expand the potential applications of organic (opto)electronics.

Quantum barriers engineering toward radiative and stable perovskite photovoltaic devices

Efficient photovoltaic devices must be efficient light emitters to reach the thermodynamic efficiency limit. Here, we present a promising prospect of perovskite photovoltaics as bright emitters by harnessing the significant benefits of photon recycling, which can be practically achieved by suppressing interfacial quenching. We have achieved radiative and stable perovskite photovoltaic devices by the design of a multiple quantum well structure with long (∼3 nm) organic spacers with oleylammonium molecules at perovskite top interfaces. Our L-site exchange process (L: barrier molecule cation) enables the formation of stable interfacial structures with moderate conductivity despite the thick barriers. Compared to popular short (∼1 nm) Ls, our approach results in enhanced radiation efficiency through the recursive process of photon recycling. This leads to the realization of radiative perovskite photovoltaics with both high photovoltaic efficiency (in-lab 26.0%, certified to 25.2%) and electroluminescence quantum efficiency (19.7 % at peak, 17.8% at 1-sun equivalent condition). Furthermore, the stable crystallinity of oleylammonium-based quantum wells enables our devices to maintain high efficiencies for over 1000 h of operation and >2 years of storage.

Multi‐Selenophene Strategy Enables Dimeric Acceptors‐Based Organic Solar Cells with over 18.5% Efficiency

AbstractDimeric acceptor (DMA) becomes a promising alternative to small‐molecular and polymeric acceptor‐based organic solar cells (OSCs) due to its well‐defined chemical structure, high batch‐to‐batch reproducibility, and low molecular diffusion properties. However, DMAs usually exhibit blueshifted absorptions, limiting their photon utilization abilities. Herein, multi‐selenophene strategies are adopted to develop redshifted DMAs. From monomer (YSe) to dimers (DYSe‐1 and DYSe‐2), reduced electron reorganization energies and exciton binding energies enable the efficient charge dynamics in the DMAs‐based OSCs. Together with their effective absorption extending to ≈920 nm, DYSe‐1‐ and DYSe‐2‐ based OSCs exhibit outstanding short‐circuit current densities (JSCs) over 27 mA cm−2, which are the best among DMAs. Besides, compared with the YSe‐based device, both DMA‐based devices have higher electroluminescence quantum efficiencies and thus reduce nonradiative recombination loss (ΔE3), contributing to their reduced energy losses. The resultant open‐circuit voltages (VOCs) of DYSe‐1‐ and DYSe‐2‐ based OSCs are ≈0.88 V, which, combining their super JSC values, lead to the promising power conversion efficiencies of 18.56% and 18.22%, respectively. These results are among the best in DMAs‐based OSCs and highlight the great potential of the multi‐selenophene strategy for the development of redshifted DMAs with high performance.

Efficient Near‐Infrared Fluorescence in Deuterated Host–Guest System for Near‐Infrared Organic Light‐Emitting Diodes

AbstractNear‐infrared organic light‐emitting diodes (NIR‐OLEDs) possess substantial potential for future valuable applications, such as a light source for sensing applications. However, the low photoluminescence quantum yield (PLQY) of NIR‐emitting molecules represents a significant impediment to these applications. In this study, the impact of the deuteration of both of host (mCP‐d20: 1,3‐Dicarbazole‐benzene‐d20) and guest (BBT‐TPA‐d28: 4,8‐bis[4‐(N,N‐diphenylamino)phenyl]benzo[1,2‐c:4,5‐c']bis[1,2,5]thiadiazole‐d28) on NIR PL properties in the host–guest codeposited film is reported. The 1 wt%‐BBT‐TPA‐d28:mCP‐d20 codeposited film exhibited PLQY of 15 ± 2% with an emission peak wavelength at ≈900 nm, which is about three times higher than that of the film composed of undeuterated molecules. Importantly, the deuteration of only the host or guest does not yield the PLQY up to 15%, underlining the importance of the deuteration of both host and guest molecules in suppressing nonradiative decay processes. The NIR‐OLED with the deuterated codeposited film as an emissive layer demonstrates a maximum external electroluminescence quantum efficiency of 2.3 ± 0.2%.

Efficiency enhancement of organic light-emitting diodes with multifunctional magnetic composite nanoparticles of Fe3O4@Au@SiO2

Multifunctional nanomaterials have been widely utilized to optimize the performances of optoelectronic devices. In this work, magnetic composite nanoparticles (NPs) of Fe3O4@Au@SiO2 are used as dopants to improve the quantum efficiency of electroluminescence of the tris-(8-hydroxyquinoline) aluminum-based organic light emitting devices (OLEDs). As a result, the performances of doped OLED (Von = 2.8 V, L = 23,400 cd/m2, EQE = 1.55) are obviously boosted as compared to the control device (Von = 2.9 V, L = 19,780 cd/m2, EQE = 1.27). Especially, the current efficiency of fluorescent green OLEDs can be 22.5 % enhanced by simply mixing the magnetic Fe3O4@Au@SiO2 (0.5 wt‰) NPs into poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS), yielding the maximum value of 4.62 cd/A. The efficiency enhancement could be attributed to the collective effects of light-scattering, localized surface plasmon resonance (LSPR) and magnetic effect induced by magnetic composite NPs.

Decreasing exciton dissociation rates for reduced voltage losses in organic solar cells

Enhancing the device electroluminescence quantum efficiency (EQEEL) is a critical factor in mitigating non-radiative voltage losses (VNR) and further improving the performance of organic solar cells (OSCs). While the common understanding attributes EQEEL in OSCs to the dynamics of charge transfer (CT) states, persistent efforts to manipulate these decay dynamics have yielded limited results, with the EQEEL of high-efficiency OSCs typically remaining below 10−2%. This value is considerably lower than that observed in high efficiency inorganic photovoltaic devices. Here, we report that EQEEL is also influenced by the dissociation rate constant of singlet states (kDS). Importantly, in contrast to the traditional belief that advocates maximizing kDS for superior photovoltaic quantum efficiency (EQEPV), a controlled reduction in kDS is shown to enhance EQEEL without compromising EQEPV. Consequently, a promising experimental approach to address the VNR challenge is proposed, resulting in a significant improvement in the performance of OSCs.

Monolayer WS2 electro- and photo-luminescence enhancement by TFSI treatment

Layered material heterostructures (LMHs) can be used to fabricate electroluminescent devices operating in the visible spectral region. A major advantage of LMH-based light emitting diodes (LEDs) is that electroluminescence (EL) emission can be tuned across that of different exciton complexes (e.g. biexcitons, trions, quintons) by controlling the charge density. However, these devices have an EL quantum efficiency as low as ∼10−4%. Here, we show that the superacid bis-(triuoromethane)sulfonimide (TFSI) treatment of monolayer WS2-LEDs boosts EL quantum efficiency by over one order of magnitude at room temperature. Non-treated devices emit light mainly from negatively charged excitons, while the emission in treated ones predominantly involves radiative recombination of neutral excitons. This paves the way to tunable and efficient LMH-based LEDs.

Extended theoretical modeling of reverse intersystem crossing for thermally activated delayed fluorescence materials.

Thermally activated delayed fluorescence (TADF) materials and multi-resonant (MR) variants are promising organic emitters that can achieve an internal electroluminescence quantum efficiency of ~100%. The reverse intersystem crossing (RISC) is key for harnessing triplet energies for fluorescence. Theoretical modeling is thus crucial to estimate its rate constant (kRISC) for material development. Here, we present a comprehensive assessment of the theory for simulating the RISC of MR-TADF molecules within a perturbative excited-state dynamics framework. Our extended rate formula reveals the importance of the concerted effects of nonadiabatic spin-vibronic coupling and vibrationally induced spin-orbital couplings in reliably determining kRISC of MR-TADF molecules. The excited singlet-triplet energy gap is another factor influencing kRISC. We present a scheme for gap estimation using experimental Arrhenius plots of kRISC. Erroneous behavior caused by approximations in Marcus theory is elucidated by testing 121 MR-TADF molecules. Our extended modeling offers in-depth descriptions of kRISC.

Three-dimensional sensing of surfaces by projection of invisible electroluminescence from organic light-emitting diodes.

Organic light-emitting diodes (OLEDs) that efficiently emit near-infrared (NIR) light and consume little power will create valuable applications for OLEDs beyond just displays. Here, we report such a NIR-OLED with high operational stability that can be used as a light source for three-dimensional sensing of object's surfaces. Using a narrow-energy-gap material as a host for producing NIR hyperfluorescence system, we fabricated a NIR-OLED exhibiting intense emission at 930 nm with a high external electroluminescence quantum efficiency of more than 1% at a current density of 100 milliamperes per square meter without any degradation even after more than 300 hours of operation. The NIR-OLEDs were integrated with dense complementary metal-oxide semiconductor circuits to make a micro-NIR-OLED projector (0.21 inch, 230,400 pixels). By actively driving the projector on a pixel by pixel and projecting their emission onto objects, we successfully scanned and sensed the surfaces in three dimensions with invisible NIR.

Evolution of interfacial defects and energy losses during aging of organic photovoltaics

As the power conversion efficiencies of Organic Solar Cells (OSCs) approach 20 %, the stability of the device becomes an increasingly urgent issue. To enhance device stability, it is crucial to identify potential loss mechanisms. In this study, we investigated the trap-state-dependent degradation mechanism of OSCs by directly comparing devices with different hole transport layers (HTLs) that introduce distinct interfacial defect distributions. Employing electrochemical impedance spectroscopy (EIS), Fourier transform photocurrent spectroscopy (FTPS), electroluminescence quantum efficiency (EQEEL), and temperature-dependent J-V techniques, we unraveled the relationship between device degradation and interfacial trap states and energy loss in PM6:Y6 devices. A lower density of interfacial deep traps is evidently correlated with smaller non-radiative recombination losses during the aging of devices based on PEDOT:PSS. Conversely, a higher density of deep traps in aged devices with WS2 interlayers and HTL-free configurations is presumed to be responsible for a significant increase in non-radiative recombination losses. The escalating deep-trap-state density in aged devices is observed to elevate carrier recombination, consequently deteriorating device performance. Beyond the scope of the energy balance theory, an additional factor, probably attributed to the change in the work function of ITO, was found to contribute significantly to energy loss in aged cells, particularly in HTL-free devices. These results highlight the potential for improving device stability via interface engineering.

Improving Electroluminescence of Two‐Coordinate Au(I) Complexes: Insights into Steric and Electronic Control

AbstractThis research elucidates the effects of structural modulations on electroluminescent Au(I) complexes, shedding light on factors governing radiative and nonradiative processes. A series of Au(I) complexes, fortified with ortho‐substituents in carbene and amido ligands, are subjected to rigorous structural, photophysical, and quantum chemical investigations, which unveil distinct structural and electronic effects exerted by the ligands. The investigations reveal that nonradiative processes are governed primarily by the energy‐gap law. Radiative processes are observed to have a weak correlation with the mutual interactions of the molecular orbitals of carbene and amido ligands. Rather, it is discovered that an accumulation of the negative charge in the Au 5d orbital in the excited state decelerates radiative processes. The effectiveness of these findings is substantiated through the larger external quantum efficiency of electroluminescence devices employing the Au(I) complex, in comparison to those based on the archetypical Au(I) complex and the organic thermally activated delayed fluorescent molecule. These compelling revelations underscore the untapped potential of Au(I) complexes in the advancement of electroluminescence technology and advocate for continued investigations into the intriguing domain of ligand structural control.

Asymmetric Ternary Spiro Phosphine Oxide Hosts for Yellow Thermally Activated Delayed Fluorescence Diodes with External Quantum Efficiency Beyond 30%

AbstractYellow thermally activated delayed fluorescence (TADF) organic light‐emitting diodes (OLEDs) are indispensable for lighting, navigation, caution, and so on; however, their development is far behind those of three‐elementary‐color and white analogs, partially because of the lack of host specificity. In this contribution, spiro[bithoxanthene] (ST) and spiro[thioxanthene‐xanthene] (STX) are used as spiro skeletons to form asymmetric ternary structures through introducing two electron‐donating tert‐butyl carbazole (tBCz) and one electron‐withdrawing diphenyl phosphine oxide (DPPO) groups on different rings. The resulting hosts named STSPOtBCz2 and STXSPOtBCz2 not only inherit the steric hindrance of their spiro skeletons, but also achieve the ambipolar characteristics. Their suitable triplet energy levels (T1) of ≈2.5 eV support efficient energy transfer to a conventional yellow TADF emitter 4CzTPNBu with the T1 of ≈2.2 eV. It is shown that compared to STSPOtBCz2 with a symmetric core, the accumulated asymmetry of the spiro skeleton and the kind, number, and position of substitution groups in STXSPOtBCz2 further suppresses the emission quenching, resulting in the state‐of‐the‐art photoluminescent and electroluminescent quantum efficiencies of 93% and 30.6%, respectively. The maximum power efficiency beyond 90 lm W−1 further demonstrates the great potential of multi‐asymmetric host systems for energy‐saving practical application.

The Potential Game‐Changer: A Concept‐to‐Proof Study on D:A Heterojunction‐Free Organic Photovoltaics†

Comprehensive SummarySince 1986, the donor‐acceptor (D:A) heterojunction has been regarded a necessity for high‐efficiency organic photovoltaics (OPVs), due to its unique advantage in compensating the intrinsic limitations of organic semiconductors, such as high exciton binding energy and poor ambipolar charge mobility. While this adversely causes tremendous non‐radiative charge recombination and instability issues, which currently become the most critical limits for commercialization of OPVs. Here, we present a concept‐to‐proof study on the potential of D:A heterojunction free OPV by taking advantage of recent progress of non‐fullerene acceptors. First, we demonstrate that the “free carriers” can be spontaneously generated upon illumination in an NFA, i.e., the 6TIC‐4F single layer. Second, the 6TIC‐4F layer also exhibits good ambipolar charge transporting property. These exceptional characteristics distinguish it from the traditional organic semiconductors, and relieve it from the reliance of D:A heterojunction to independently work as active layer. As a result, the subsequent OPV by simply sandwiching the 6TIC‐4F layer between the cathode and anode yields a considerably high power conversion efficiency ~1%. Moreover, we find the D:A heterojunction free device exhibits two order of magnitude higher electroluminescence quantum efficiency and significantly reduced VOC loss by 0.16 eV compared to those of the D:A BHJ structure, validating its promise for higher efficiency in the future. Therefore, our work demonstrates the possibility of using D:A heterojunction‐free device structure for high performance, that can potentially become the next game changer of OPV.