Nickel Oxide Hole Injection Layers for Balanced Charge Injection in Quantum Dot Light-Emitting Diodes.

Quantum dot (QD) light-emitting diodes (QLEDs) are promising for next-generation displays, but suffer from carrier imbalance arising from lower hole injection compared to electron injection. A defect engineering strategy is reported to tackle transport limitations in nickel oxide-based inorganic hole-injection layers (HILs) and find that hole injection is able to enhance in high-performance InP QLEDs using the newly designed material. Through optoelectronic simulations, how the electronic properties of NiOx affect hole injection efficiency into an InP QD layer, finding that efficient hole injection depends on lowering the hole injection barrier and enhancing the acceptor density of NiOx is explored. Li doping and oxygen enriching are identified as effective strategies to control intrinsic and extrinsic defects in NiOx, thereby increasing acceptor density, as evidenced by density functional theory calculations and experimental validation. With fine-tuned inorganic HIL, InP QLEDs exhibit a luminance of 45 200 cd m-2 and an external quantum efficiency of 19.9%, surpassing previous inorganic HIL-based QLEDs. This study provides a path to designing inorganic materials for more efficient and sustainable lighting and display technologies.

The dynamic adsorption affinity of ligands is a surrogate for the passivation of surface defects.

Surface defects in semiconducting materials, though they have been widely studied, remain a prominent source of loss in optoelectronic devices; here we sought a new angle of approach, looking into the dynamic roles played by surface defects under atmospheric stressors and their chemical passivants in the lifetime of optoelectronic materials. We find that surface defects possess properties distinct from those of bulk defects. ab initio molecular dynamics simulations reveal a previously overlooked reversible degradation mechanism mediated by hydrogen vacancies. We find that dynamic surface adsorption affinity (DAA) relative to surface treatment ligands is a surrogate for passivation efficacy, a more strongly-correlated feature than is the static binding strength emphasized in prior reports. This guides us to design targeted passivator ligands with high molecular polarity: for example, 4-aminobutylphosphonic acid exhibits strong DAA and provides defect passivation applicable to a range of perovskite compositions, including suppressed hydrogen vacancy formation, enhanced photovoltaic performances and operational stability in perovskite solar cells.

Sub-Second Long Lifetime Triplet Exciton Reservoir for Highly Efficient and Stable Organic Light-Emitting Diode.

In organic light-emitting diode (OLED), achieving high efficiency requires effective triplet exciton confinement by carrier-transporting materials, which typically have higher triplet energy (ET ) than the emitter, leading to poor stability. Here, an electron-transporting material (ETM), whose ET is 0.32 eV lower than that of the emitter is reported. In devices, it surprisingly exhibits strong confinement effect and generates excellent efficiency. Additionally, the device operational lifetime is 4.9 times longer than the device with a standard ETM, 1,3,5-tri(1-phenyl-1H-benzo[d]imidazol-2-yl) phenyl (whose ET 0.36 eV is higher than the emitter). This anomalous finding is ascribed to the exceptionally long triplet state lifetime (≈0.2 s) of the ETM. It is named as long-lifetime triplet exciton reservoir effect. The systematic analysis reveals that the long triplet lifetime of ETM can compensate the requirement for high ET with the help of endothermic energy transfer. Such combination of low ET and long lifetime provides equivalent exciton confinement effect and high molecular stability simultaneously. It offers a novel molecular design paradigm for breaking the dilemma between high efficiency and prolonged operational lifetime in OLEDs.

Thickness-variation-insensitive near-infrared quantum dot LEDs.

In terms of tunable luminescence and high quantum efficiency, colloidal quantum dots (CQDs) are promising semiconductors for constructing near-infrared light-emitting diodes (NIR-LEDs). However, currently available NIR-LEDs are susceptible to variations in the emission layer thickness (EMLT), the highest external quantum efficiency (EQE) decreases to below 50% (relative to peak EQE) when the EMLT varies out of a narrow range of (±30 nm). This is due to the thickness-dependent carrier recombination rate and current density variation, resulting in batch-to-batch EQE fluctuations that limit LED reproducibility. Here we report efficient NIR-LEDs that exhibit EQE variations of less than 15% (relative to the champion EQE) over an EMLT range of 40-220 nm; the highest achievable EQE of ∼11.5% was obtained by encapsulating a 212 nm-thick CQD within a type-I inorganic shell to enhance the radiative recombination in the dots, resulting in a high photoluminescence quantum yield of 80%, and by post-treating the films with a bifunctional linking agent to improve and balance the hole and electron mobilities in the entire film (electron mobility: 8.23 × 10-3 cm2 V-1 s-1; hole mobility: 7.0 × 10-3 cm2 V-1 s-1). This work presents the first NIR-LEDs that exhibit EMLT-invariant EQE over an EMLT range of 40-220 nm, which represents the highest EQE among reported CQD NIR-LEDs with a QD thickness exceeding 100 nm.

Anion optimization for bifunctional surface passivation in perovskite solar cells.

Pseudo-halide (PH) anion engineering has emerged as a surface passivation strategy of interest for perovskite-based optoelectronics; but until now, PH anions have led to insufficient defect passivation and thus to undesired deep impurity states. The size of the chemical space of PH anions (>106 molecules) has so far limited attempts to explore the full family of candidate molecules. We created a machine learning workflow to speed up the discovery process using full-density functional theory calculations for training the model. The physics-informed machine learning model allowed us to pinpoint promising molecules with a head group that prevents lattice distortion and anti-site defect formation, and a tail group optimized for strong attachment to the surface. We identified 15 potential bifunctional PH anions with the ability to passivate both donors and acceptors, and through experimentation, discovered that sodium thioglycolate was the most effective passivant. This strategy resulted in a power-conversion efficiency of 24.56% with a high open-circuit voltage of 1.19 volts (24.04% National Renewable Energy Lab-certified quasi-steady-state) in inverted perovskite solar cells. Encapsulated devices maintained 96% of their initial power-conversion energy during 900 hours of one-sun operation at the maximum power point.

Low-loss contacts on textured substrates for inverted perovskite solar cells.

Inverted perovskite solar cells (PSCs) promise enhanced operating stability compared to their normal-structure counterparts1-3. To improve efficiency further, it is crucial to combine effective light management with low interfacial losses4,5. Here we develop a conformal self-assembled monolayer (SAM) as the hole-selective contact on light-managing textured substrates. Molecular dynamics simulations indicate that cluster formation during phosphonic acid adsorption leads to incomplete SAM coverage. We devise a co-adsorbent strategy that disassembles high-order clusters, thus homogenizing the distribution of phosphonic acid molecules, and thereby minimizing interfacial recombination and improving electronic structures. We report a laboratory-measured power conversion efficiency (PCE) of 25.3% and a certified quasi-steady-state PCE of 24.8% for inverted PSCs, with a photocurrent approaching 95% of the Shockley-Queisser maximum. An encapsulated device having a PCE of 24.6% at room temperature retains 95% of its peak performance when stressed at 65 °C and 50% relative humidity following more than 1,000 h of maximum power point tracking under 1 sun illumination. This represents one of the most stable PSCs subjected to accelerated ageing: achieved with a PCE surpassing 24%. The engineering of phosphonic acid adsorption on textured substrates offers a promising avenue for efficient and stable PSCs. It is also anticipated to benefit other optoelectronic devices that require light management.

Engineering ligand reactivity enables high-temperature operation of stable perovskite solar cells.

Perovskite solar cells (PSCs) consisting of interfacial two- and three-dimensional heterostructures that incorporate ammonium ligand intercalation have enabled rapid progress toward the goal of uniting performance with stability. However, as the field continues to seek ever-higher durability, additional tools that avoid progressive ligand intercalation are needed to minimize degradation at high temperatures. We used ammonium ligands that are nonreactive with the bulk of perovskites and investigated a library that varies ligand molecular structure systematically. We found that fluorinated aniliniums offer interfacial passivation and simultaneously minimize reactivity with perovskites. Using this approach, we report a certified quasi-steady-state power-conversion efficiency of 24.09% for inverted-structure PSCs. In an encapsulated device operating at 85°C and 50% relative humidity, we document a 1560-hour T85 at maximum power point under 1-sun illumination.

Molecular-Additive-Assisted Tellurium Homogenization in ZnSeTe Quantum Dots.

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.

Sterically Suppressed Phase Segregation in 3D Hollow Mixed-Halide Wide Band Gap Perovskites.

Band gap tuning in mixed-halide perovskites enables efficient multijunction solar cells and LEDs. However, these wide band gap perovskites, which contain a mixture of iodide and bromide ions, are known to phase segregate under illumination, introducing voltage losses that limit stability. Previous studies have employed inorganic perovskites, halide alloys, and grain/interface passivation to minimize halide segregation, yet photostability can be further advanced. By focusing on the role of halide vacancies in anion migration, one expects to be able to erect local barriers to ion migration. To achieve this, we employ a 3D "hollow" perovskite structure, wherein a molecule that is otherwise too large for the perovskite lattice is incorporated. The amount of hollowing agent, ethane-1,2-diammonium dihydroiodide (EDA), varies the density of the hollow sites. Photoluminescence measurements reveal that 1% EDA in the perovskite bulk can stabilize a 40% bromine mixed-halide perovskite at 1 sun illumination intensity. These, along with capacitance-frequency measurements, suggest that hollow sites limit the mobility of the halide vacancies.

Suppressed phase segregation for triple-junction perovskite solar cells.

The tunable bandgaps and facile fabrication of perovskites make them attractive for multi-junction photovoltaics1,2. However, light-induced phase segregation limits their efficiency and stability3-5: this occurs in wide-bandgap (>1.65 electron volts) iodide/bromide mixed perovskite absorbers, and becomes even more acute in the top cells of triple-junction solar photovoltaics that require a fully 2.0-electron-volt bandgap absorber2,6. Here we report that lattice distortion in iodide/bromide mixed perovskites is correlated with the suppression of phase segregation, generating an increased ion-migration energy barrier arising from the decreased average interatomic distance between the A-site cation and iodide. Using an approximately 2.0-electron-volt rubidium/caesium mixed-cation inorganic perovskite with large lattice distortion in the top subcell, we fabricated all-perovskite triple-junction solar cells and achieved an efficiency of 24.3 per cent (23.3 per cent certified quasi-steady-state efficiency) with an open-circuit voltage of 3.21 volts. This is, to our knowledge, the first reported certified efficiency for perovskite-based triple-junction solar cells. The triple-junction devices retain 80 per cent of their initial efficiency following 420 hours of operation at the maximum power point.

Bifunctional Electron-Transporting Agent for Red Colloidal Quantum Dot Light-Emitting Diodes.

Indium phosphide (InP) quantum dots have enabled light-emitting diodes (LEDs) that are heavy-metal-free, narrow in emission linewidth, and physically flexible. However, ZnO/ZnMgO, the electron-transporting layer (ETL) in high-performance red InP/ZnSe/ZnS LEDs, suffers from high defect densities, quenches luminescence when deposited on InP, and induces performance degradation that arises due to trap migration from the ETL to the InP emitting layer. We posited that the formation of Zn2+ traps on the outer ZnS shell, combined with sulfur and oxygen vacancy migration between ZnO/ZnMgO and InP, may account for this issue. We synthesized therefore a bifunctional ETL (CNT2T, 3',3'″,3'″″-(1,3,5-triazine-2,4,6-triyl)tris(([1,1'-biphenyl]-3-carbonitrile)) designed to passivate Zn2+ traps locally and in situ and to prevent vacancy migration between layers: the backbone of the small molecule ETL contains a triazine electron-withdrawing unit to ensure sufficient electron mobility (6 × 10-4 cm2 V-1 s-1), and the star-shaped structure with multiple cyano groups provides effective passivation of the ZnS surface. We report as a result red InP LEDs having an EQE of 15% and a luminance of over 12,000 cd m-2; this represents a record among organic-ETL-based red InP LEDs.

Rational design of Lewis base molecules for stable and efficient inverted perovskite solar cells.

Lewis base molecules that bind undercoordinated lead atoms at interfaces and grain boundaries (GBs) are known to enhance the durability of metal halide perovskite solar cells (PSCs). Using density functional theory calculations, we found that phosphine-containing molecules have the strongest binding energy among members of a library of Lewis base molecules studied herein. Experimentally, we found that the best inverted PSC treated with 1,3-bis(diphenylphosphino)propane (DPPP), a diphosphine Lewis base that passivates, binds, and bridges interfaces and GBs, retained a power conversion efficiency (PCE) slightly higher than its initial PCE of ~23% after continuous operation under simulated AM1.5 illumination at the maximum power point and at ~40°C for >3500 hours. DPPP-treated devices showed a similar increase in PCE after being kept under open-circuit conditions at 85°C for >1500 hours.

Regulating surface potential maximizes voltage in all-perovskite tandems.

The open-circuit voltage (VOC) deficit in perovskite solar cells is greater in wide-bandgap (over 1.7 eV) cells than in perovskites of roughly 1.5 eV (refs. 1,2). Quasi-Fermi-level-splitting measurements show VOC-limiting recombination at the electron-transport-layer contact3-5. This, we find, stems from inhomogeneous surface potential and poor perovskite-electron transport layer energetic alignment. Common monoammonium surface treatments fail to address this; as an alternative, we introduce diammonium molecules to modify perovskite surface states and achieve a more uniform spatial distribution of surface potential. Using 1,3-propane diammonium, quasi-Fermi-level splitting increases by 90 meV, enabling 1.79 eV perovskite solar cells with a certified 1.33 V VOC and over 19% power conversion efficiency (PCE). Incorporating this layer into a monolithic all-perovskite tandem, we report a record VOC of 2.19 V (89% of the detailed balance VOC limit) and over 27% PCE (26.3% certified quasi-steady state). These tandems retained more than 86% of their initial PCE after 500 h of operation.

Dipole Engineering through the Orientation of Interface Molecules for Efficient InP Quantum Dot Light-Emitting Diodes.

InP-based quantum dot (QD) light-emitting diodes (QLEDs) provide a heavy-metal-free route to size-tuned LEDs having high efficiency. The stability of QLEDs may be enhanced by replacing organic hole-injection layers (HILs) with inorganic layers. However, inorganic HILs reported to date suffer from inefficient hole injection, the result of their shallow work functions. Here, we investigate the tuning of the work function of nickel oxide (NiOx) HILs using self-assembled molecules (SAMs). Density functional theory simulations and near-edge X-ray absorption fine structure put a particular focus onto the molecular orientation of the SAMs in tuning the work function of the NiOx HIL. We find that orientation plays an even stronger role than does the underlying molecular dipole itself: SAMs having the strongest electron-withdrawing nitro group (NO2), despite having a high intrinsic dipole, show limited work function tuning, something we assign to their orientation parallel to the NiOx surface. We further find that the NO2 group─which delocalizes electrons over the molecule by resonance─induces a deep lowest unoccupied molecular orbital level that accepts electrons from QDs, producing luminescence quenching. In contrast, SAMs containing a trifluoromethyl group exhibit an angled orientation relative to the NiOx surface, better activating hole injection into the active layer without inducing luminescence quenching. We report an external quantum efficiency (EQE) of 18.8%─the highest EQE among inorganic HIL-based QLEDs (including Cd-based QDs)─in InP QLEDs employing inorganic HILs.

Wide-Bandgap Perovskite Quantum Dots in Perovskite Matrix for Sky-Blue Light-Emitting Diodes.

The epitaxial growth of a perovskite matrix on quantum dots (QDs) has enabled the emergence of efficient red light-emitting diodes (LEDs) because it unites efficient charge transport with strong surface passivation. However, the synthesis of wide-band gap (Eg) QD-in-matrix heterostructures has so far remained elusive in the case of sky-blue LEDs. Here, we developed CsPbBr3 QD-in-perovskite matrix solids that enable high luminescent efficiency and spectral stability with an optical Eg of over 2.6 eV. We screened alloy candidates that modulate the perovskite Eg and allow heteroepitaxy, seeking to implement lattice-matched type-I band alignment. Specifically, we introduced a CsPb1-xSrxBr3 matrix, in which alloying with Sr2+ increased the Eg of the perovskite and minimized lattice mismatch. We then developed an approach to passivation that would overcome the hygroscopic nature of Sr2+. We found that bis(4-fluorophenyl)phenylphosphine oxide strongly coordinates with Sr2+ and provides steric hindrance to block H2O, a finding obtained by combining molecular dynamics simulations with experimental results. The resulting QD-in-matrix solids exhibit enhanced air- and photo-stability with efficient charge transport from the matrix to the QDs. LEDs made from this material exhibit an external quantum efficiency of 13.8% and a brightness exceeding 6000 cd m-2.

All-perovskite tandem solar cells with improved grain surface passivation.

All-perovskite tandem solar cells hold the promise of surpassing the efficiency limits of single-junction solar cells1-3; however, until now, the best-performing all-perovskite tandem solar cells have exhibited lower certified efficiency than have single-junction perovskite solar cells4,5. A thick mixed Pb-Sn narrow-bandgap subcell is needed to achieve high photocurrent density in tandem solar cells6, yet this is challenging owing to the short carrier diffusion length within Pb-Sn perovskites. Here we develop ammonium-cation-passivated Pb-Sn perovskites with long diffusion lengths, enabling subcells that have an absorber thickness of approximately 1.2 µm. Molecular dynamics simulations indicate that widely used phenethylammonium cations are only partially adsorbed on the surface defective sites at perovskite crystallization temperatures. The passivator adsorption is predicted to be enhanced using 4-trifluoromethyl-phenylammonium (CF3-PA), which exhibits a stronger perovskite surface-passivator interaction than does phenethylammonium. By adding a small amount of CF3-PA into the precursor solution, we increase the carrier diffusion length within Pb-Sn perovskites twofold, to over 5 µm, and increase the efficiency of Pb-Sn perovskite solar cells to over 22%. We report a certified efficiency of 26.4% in all-perovskite tandem solar cells, which exceeds that of the best-performing single-junction perovskite solar cells. Encapsulated tandem devices retain more than 90% of their initial performance after 600 h of operation at the maximum power point under 1 Sun illumination in ambient conditions.

Multifunctional Conjugated Ligand Engineering for Stable and Efficient Perovskite Solar Cells.

Surface passivation is an effective way to boost the efficiency and stability of perovskite solar cells (PSCs). However, a key challenge faced by most of the passivation strategies is reducing the interface charge recombination without imposing energy barriers to charge extraction. Here, a novel multifunctional semiconducting organic ammonium cationic interface modifier inserted between the light-harvesting perovskite film and the hole-transporting layer is reported. It is shown that the conjugated cations can directly extract holes from perovskite efficiently, and simultaneously reduce interface non-radiative recombination. Together with improved energy level alignment and the stabilized interface in the device, a triple-cation mixed-halide medium-bandgap PSC with an excellent power conversion efficiency of 22.06% (improved from 19.94%) and suppressed ion migration and halide phase segregation, which lead to a long-term operational stability, is demonstrated. This strategy provides a new practical method of interface engineering in PSCs toward improved efficiency and stability.

Differentially Expressed Gene Profile of Acanthamoeba castellanii Induced by an Endosymbiont Legionella pneumophila.

Legionella pneumophila is an opportunistic pathogen that survives and proliferates within protists such as Acanthamoeba spp. in environment. However, intracellular pathogenic endosymbiosis and its implications within Acanthamoeba spp. remain poorly understood. In this study, RNA sequencing analysis was used to investigate transcriptional changes in A. castellanii in response to L. pneumophila infection. Based on RNA sequencing data, we identified 1,211 upregulated genes and 1,131 downregulated genes in A. castellanii infected with L. pneumophila for 12 hr. After 24 hr, 1,321 upregulated genes and 1,379 downregulated genes were identified. Gene ontology (GO) analysis revealed that L. pneumophila endosymbiosis enhanced hydrolase activity, catalytic activity, and DNA binding while reducing oxidoreductase activity in the molecular function (MF) domain. In particular, multiple genes associated with the GO term 'integral component of membrane' were downregulated during endosymbiosis. The endosymbiont also induced differential expression of various methyltransferases and acetyltransferases in A. castellanii. Findings herein are may significantly contribute to understanding endosymbiosis of L. pneumophila within A. castellanii.

Production of a polyclonal antibody against inosine-uridine preferring nucleoside hydrolase of Acanthamoeba castellanii and its access to diagnosis of Acanthamoeba keratitis.

Acanthamoeba keratitis (AK) is a rare disease but its prevalence throughout the globe continues to grow, primarily due to increased contact lens usage. Since early-stage symptoms associated with AK closely resemble those from other corneal infections, accurate diagnosis is difficult and this often results in delayed treatment and exacerbation of the disease, which can lead to permanent visual impairment. Accordingly, developing a rapid Acanthamoeba-specific diagnostic method is highly desired. In the present study, a rapid and differential method for AK diagnosis was developed using the secretory proteins derived from the pathogenic Acanthamoeba. Among the vast quantities of proteins secreted by the pathogenic Acanthamoeba, an open reading frame of the inosine-uridine preferring nucleoside hydrolase (IPNH) gene was obtained. After expressing and purifying the IPNH protein using the pGEX 4T-3 vector system, mice were immunized with the purified proteins for polyclonal antibody generation. Western blot was performed using protein lysates of the human corneal cell, non-pathogenic amoeba, pathogenic amoeba, and clinical amoeba isolate along with lysates from other causes of keratitis such as Staphylococcus aureus, Pseudomonas aeruginosa, and Fusarium solani to confirm Acanthamoeba-specificity. Western blot using the polyclonal IPNH antibody revealed that IPNH was Acanthamoeba-specific since these proteins were only observed in lysates of Acanthamoeba origin or its culture media. Our findings indicate that the IPNH antibody of Acanthamoeba may serve as a potential agent for rapid and differential AK diagnosis.