Long-range order enabled stability in quantum dot light-emitting diodes.

Light-emitting diodes (LEDs) based on perovskite quantum dots (QDs) have produced external quantum efficiencies (EQEs) of more than 25% with narrowband emission1,2, but these LEDs have limited operating lifetimes. We posit that poor long-range ordering in perovskite QD films-variations in dot size, surface ligand density and dot-to-dot stacking-inhibits carrier injection, resulting in inferior operating stability because of the large bias required to produce emission in these LEDs. Here we report a chemical treatment to improve the long-range order of perovskite QD films: the diffraction intensity from the repeating QD units increases three-fold compared with that of controls. We achieve this using a synergistic dual-ligand approach: an iodide-rich agent (aniline hydroiodide) for anion exchange and a chemically reactive agent (bromotrimethylsilane) that produces a strong acid that in situ dissolves smaller QDs to regulate size and more effectively removes less conductive ligands to enable compact, uniform and defect-free films. These films exhibit high conductivity (4 × 10-4 S m-1), which is 2.5-fold higher than that of the control, and represents the highest conductivity recorded so far among perovskite QDs. The high conductivity ensures efficient charge transportation, enabling red perovskite QD-LEDs that generate a luminance of 1,000 cd m-2 at a record-low voltage of 2.8 V. The EQE at this luminance is more than 20%. Furthermore, the stability of the operating device is 100 times better than previous red perovskite LEDs at EQEs of more than 20%.

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.

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.

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.

Arresting Ion Migration from the ETL Increases Stability in Infrared Light Detectors Based on III-V Colloidal Quantum Dots.

III-V colloidal quantum dots (CQDs) are of interest in infrared photodetection, and recent developments in CQDs synthesis and surface engineering have improved performance. Here this work investigates photodetector stability, finding that the diffusion of zinc ions from charge transport layers (CTLs) into the CQDs active layer increases trap density therein, leading to rapid and irreversible performance loss during operation. In an effort to prevent this, this work introduces organic blocking layers between the CQDs and ZnO layers; but these negatively impact device performance. The device is then, allowing to use a C60:BCP as top electron-transport layer (ETL) for good morphology and process compatibility, and selecting NiOX as the bottom hole-transport layer (HTL). The first round of NiOX -based devices show efficient light response but suffer from high leakage current and a low open-circuit voltage (Voc) due to pinholes. This work introduces poly[bis(4-phenyl) (2,4,6-trimethylphenyl)amine] (PTAA) with NiOX NC to form a hybrid HTL, an addition that reduces pinhole formation, interfacial trap density, and bimolecular recombination, enhancing carrier harvesting. The photodetectors achieve 53% external quantum efficiency (EQE) at 970 nm at 1 V applied bias, and they maintain 95% of initial performance after 19 h of continuous illuminated operation. The photodetectors retain over 80% of performance after 80 days of shelf storage.

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.

Large piezoelectric response in a Jahn-Teller distorted molecular metal halide.

Piezoelectric materials convert between mechanical and electrical energy and are a basis for self-powered electronics. Current piezoelectrics exhibit either large charge (d33) or voltage (g33) coefficients but not both simultaneously, and yet the maximum energy density for energy harvesting is determined by the transduction coefficient: d33*g33. In prior piezoelectrics, an increase in polarization usually accompanies a dramatic rise in the dielectric constant, resulting in trade off between d33 and g33. This recognition led us to a design concept: increase polarization through Jahn-Teller lattice distortion and reduce the dielectric constant using a highly confined 0D molecular architecture. With this in mind, we sought to insert a quasi-spherical cation into a Jahn-Teller distorted lattice, increasing the mechanical response for a large piezoelectric coefficient. We implemented this concept by developing EDABCO-CuCl4 (EDABCO = N-ethyl-1,4-diazoniabicyclo[2.2.2]octonium), a molecular piezoelectric with a d33 of 165 pm/V and g33 of ~2110 × 10-3 V m N-1, one that achieved thusly a combined transduction coefficient of 348 × 10-12 m3 J-1. This enables piezoelectric energy harvesting in EDABCO-CuCl4@PVDF (polyvinylidene fluoride) composite film with a peak power density of 43 µW/cm2 (at 50 kPa), the highest value reported for mechanical energy harvesters based on heavy-metal-free molecular piezoelectric.

Self-assembled monolayer-based blue perovskite LEDs.

Blue perovskite light-emitting diodes (LEDs) have shown external quantum efficiencies (EQEs) of more than 10%; however, devices that emit in the true blue-those that accord with the emission wavelength required for Rec. 2100 primary blue-have so far been limited to EQEs of ~6%. We focused here on true blue emitting CsPbBr3 colloidal nanocrystals (c-NCs), finding in early studies that they suffer from a high charge injection barrier, a problem exacerbated in films containing multiple layers of nanocrystals. We introduce a self-assembled monolayer (SAM) active layer that improves charge injection. We identified a bifunctional capping ligand that simultaneously enables the self-assembly of CsPbBr3 c-NCs while passivating surface traps. We report, as a result, SAM-based LEDs exhibit a champion EQE of ~12% [CIE of (0.132, 0.069) at 4.0 V with a luminance of 11 cd/m2], and 10-fold-enhanced operating stability relative to the best previously reported Rec. 2100-blue perovskite LEDs.

Bimolecularly passivated interface enables efficient and stable inverted perovskite solar cells.

Compared with the n-i-p structure, inverted (p-i-n) perovskite solar cells (PSCs) promise increased operating stability, but these photovoltaic cells often exhibit lower power conversion efficiencies (PCEs) because of nonradiative recombination losses, particularly at the perovskite/C60 interface. We passivated surface defects and enabled reflection of minority carriers from the interface into the bulk using two types of functional molecules. We used sulfur-modified methylthio molecules to passivate surface defects and suppress recombination through strong coordination and hydrogen bonding, along with diammonium molecules to repel minority carriers and reduce contact-induced interface recombination achieved through field-effect passivation. This approach led to a fivefold longer carrier lifetime and one-third the photoluminescence quantum yield loss and enabled a certified quasi-steady-state PCE of 25.1% for inverted PSCs with stable operation at 65°C for >2000 hours in ambient air. We also fabricated monolithic all-perovskite tandem solar cells with 28.1% PCE.

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.

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.

Sequential Co-Passivation in InAs Colloidal Quantum Dot Solids Enables Efficient Near-Infrared Photodetectors.

III-V colloidal quantum dots (CQDs) are promising materials for optoelectronic applications, for they avoid heavy metals while achieving absorption spanning the visible to the infrared (IR). However, the covalent nature of III-V CQDs requires the development of new passivation strategies to fabricate conductive CQD solids for optoelectronics: this work shows herein that ligand exchanges, previously developed in II-VI and IV-VI quantum dots and employing a single ligand, do not fully passivate CQDs, and that this curtails device efficiency. Guided by density functional theory (DFT) simulations, this work develops a co-passivation strategy to fabricate indium arsenide CQD photodetectors, an approach that employs the combination of X-type methyl ammonium acetate (MaAc) and Z-type ligands InBr3 . This approach maintains charge carrier mobility and improves passivation, seen in a 25% decrease in Stokes shift, a fourfold reduction in the rate of first-exciton absorption linewidth broadening over time-under-stress, and leads to a doubling in photoluminescence (PL) lifetime. The resulting devices show 37% external quantum efficiency (EQE) at 950 nm, the highest value reported for InAs CQD photodetectors.

Multication perovskite 2D/3D interfaces form via progressive dimensional reduction.

Many of the best-performing perovskite photovoltaic devices make use of 2D/3D interfaces, which improve efficiency and stability - but it remains unclear how the conversion of 3D-to-2D perovskite occurs and how these interfaces are assembled. Here, we use in situ Grazing-Incidence Wide-Angle X-Ray Scattering to resolve 2D/3D interface formation during spin-coating. We observe progressive dimensional reduction from 3D to n = 3 → 2 → 1 when we expose (MAPbBr3)0.05(FAPbI3)0.95 perovskites to vinylbenzylammonium ligand cations. Density functional theory simulations suggest ligands incorporate sequentially into the 3D lattice, driven by phenyl ring stacking, progressively bisecting the 3D perovskite into lower-dimensional fragments to form stable interfaces. Slowing the 2D/3D transformation with higher concentrations of antisolvent yields thinner 2D layers formed conformally onto 3D grains, improving carrier extraction and device efficiency (20% 3D-only, 22% 2D/3D). Controlling this progressive dimensional reduction has potential to further improve the performance of 2D/3D perovskite photovoltaics.