Thermal Properties of Polymer Hole-Transport Layers Influence the Efficiency Roll-off and Stability of Perovskite Light-Emitting Diodes.

While the performance of metal halide perovskite light-emitting diodes (PeLEDs) has rapidly improved in recent years, their stability remains a bottleneck to commercial realization. Here, we show that the thermal stability of polymer hole-transport layers (HTLs) used in PeLEDs represents an important factor influencing the external quantum efficiency (EQE) roll-off and device lifetime. We demonstrate a reduced EQE roll-off, a higher breakdown current density of approximately 6 A cm-2, a maximum radiance of 760 W sr-1 m-2, and a longer device lifetime for PeLEDs using polymer HTLs with high glass-transition temperatures. Furthermore, for devices driven by nanosecond electrical pulses, a record high radiance of 1.23 MW sr-1 m-2 and an EQE of approximately 1.92% at 14.6 kA cm-2 are achieved. Thermally stable polymer HTLs enable stable operation of PeLEDs that can sustain more than 11.7 million electrical pulses at 1 kA cm-2 before device failure.

Origins of Photoluminescence Instabilities at Halide Perovskite/Organic Hole Transport Layer Interfaces.

Metal halide perovskites are promising for optoelectronic device applications; however, their poor stability under solar illumination remains a primary concern. While the intrinsic photostability of isolated neat perovskite samples has been widely discussed, it is important to explore how charge transport layers─employed in most devices─impact photostability. Herein, we study the effect of organic hole transport layers (HTLs) on light-induced halide segregation and photoluminescence (PL) quenching at perovskite/organic HTL interfaces. By employing a series of organic HTLs, we demonstrate that the HTL's highest occupied molecular orbital energy dictates behavior; furthermore, we reveal the key role of halogen loss from the perovskite and subsequent permeation into organic HTLs, where it acts as a PL quencher at the interface and introduces additional mass transport pathways to facilitate halide phase separation. In doing so, we both reveal the microscopic mechanism of non-radiative recombination at perovskite/organic HTL interfaces and detail the chemical rationale for closely matching the perovskite/organic HTL energetics to maximize solar cell efficiency and stability.

Hydrothermal Synthesis of Zinc-Doped Silica Nanospheres Simultaneously Featuring Stable Fluorescence and Long-Lived Room-Temperature Phosphorescence.

Fluorescence and phosphorescence are known as two kinds of fundamental optical signals, which have been used for myriad applications. To date, simultaneous activation of stable fluorescence and long-lived room-temperature phosphorescence (RTP) emission in the aqueous phase remains a big challenge. We prepare zinc-doped silica nanospheres (Zn@SiNSs) with fluorescence and RTP properties using a facile hydrothermal synthetic strategy. For the as-prepared Zn@SiNSs, the recombination of electrons and holes in defects and defect-stabilized excitons derived from oxygen vacancy/C=N bonds lead to the production of stable fluorescence and long-lived RTP (emission lasting for ≈9 s, quantum yield (QY): ≈33.6 %, RTP lifetime: ≈236 ms). The internal Si-O bonded networks and hydrophilic surface in Zn@SiNSs can reduce nonradiative decay to form self-protective RTP, and also provide high water solubility, excellent pH- and photostability.

Pinhole-Free Hybrid Perovskite Film with Arbitrarily-Shaped Micro-Patterns for Functional Optoelectronic Devices.

In many optoelectronic applications, patterning is required for functional and/or aesthetic purposes. However, established photolithographic technique cannot be applied directly to the hybrid perovskites, which are considered as promising candidates for optoelectronic applications. In this work, a wettability-assisted photolithography (WAP) process, which employs photolithography and one-step solution process to deposit hybrid perovskite, was developed for fabricating patterned hybrid perovskite films. Uniform pinhole-free hybrid perovskite films with sharp-edged micropatterns of any shapes can be constructed through the WAP process. Semitransparent solar cells with an adjustable active layer average visible transmittance of a wide range from 20.0% to 100% and regular solar cells based on patterned CH3NH3PbI3 perovskite films were fabricated to demonstrate that the WAP process was compatible with the manufacturing process of optoelectronic devices. With the widely equipped photolithographic facilities in the modern semiconductor industry, we believe the WAP process have a great potential in the industrial production of functionally or aesthetically patterned hybrid perovskite devices.

Sublimed C60 for efficient and repeatable perovskite-based solar cells.

Thermally evaporated C60 is a near-ubiquitous electron transport layer in state-of-the-art p-i-n perovskite-based solar cells. As perovskite photovoltaic technologies are moving toward industrialization, batch-to-batch reproducibility of device performances becomes crucial. Here, we show that commercial as-received (99.75% pure) C60 source materials may coalesce during repeated thermal evaporation processes, jeopardizing such reproducibility. We find that the coalescence is due to oxygen present in the initial source powder and leads to the formation of deep states within the perovskite bandgap, resulting in a systematic decrease in solar cell performance. However, further purification (through sublimation) of the C60 to 99.95% before evaporation is found to hinder coalescence, with the associated solar cell performances being fully reproducible after repeated processing. We verify the universality of this behavior on perovskite/silicon tandem solar cells by demonstrating their open-circuit voltages and fill factors to remain at 1950 mV and 81% respectively, over eight repeated processes using the same sublimed C60 source material. Notably, one of these cells achieved a certified power conversion efficiency of 30.9%. These findings provide insights crucial for the advancement of perovskite photovoltaic technologies towards scaled production with high process yield.

Triiodide Attacks the Organic Cation in Hybrid Lead Halide Perovskites: Mechanism and Suppression.

Molecular I2 can be produced from iodide-based lead perovskites under thermal stress; triiodide, I3 - , is formed from this I2 and I- . Triiodide attacks protic cation MA+ - or FA+ -based lead halide perovskites (MA+ , methylammonium; FA+ , formamidinium) as explicated through solution-based nuclear magnetic resonance (NMR) studies: triiodide has strong hydrogen-bonding affinity for MA+ or FA+ , which leads to their deprotonation and perovskite decomposition. Triiodide is a catalyst for this decomposition that can be obviated through perovskite surface treatment with thiol reducing agents. In contrast to methods using thiol incorporation into perovskite precursor solutions, no penetration of the thiol into the bulk perovskite is observed, yet its surface application stabilizes the perovskite against triiodide-mediated thermal stress. Thiol applied to the interface between FAPbI3 and Spiro-OMeTAD ("Spiro") prevents oxidized iodine species penetration into Spiro and thus preserves its hole-transport efficacy. Surface-applied thiol affects the perovskite work function; it ameliorates hole injection into the Spiro overlayer, thus improving device performance. It helps to increase interfacial adhesion ("wetting"): fewer voids are observed at the Spiro/perovskite interface if thiols are applied. Perovskite solar cells (PSCs) incorporating interfacial thiol treatment maintain over 80% of their initial power conversion efficiency (PCE) after 300 h of 85 °C thermal stress.

Electrochemical Doping of Halide Perovskites by Noble Metal Interstitial Cations.

Metal halide perovskites are an attractive class of semiconductors, but it has proven difficult to control their electronic doping by conventional strategies due to screening and compensation by mobile ions or ionic defects. Noble-metal interstitials represent an under-studied class of extrinsic defects that plausibly influence many perovskite-based devices. In this work, doping of metal halide perovskites is studied by electrochemically formed Au+ interstitial ions, combining experimental data on devices with a computational analysis of Au+ interstitial defects based on density functional theory (DFT). Analysis suggests that Au+ cations can be easily formed and migrate through the perovskite bulk via the same sites as iodine interstitials (Ii + ). However, whereas Ii + compensates n-type doping by electron capture, the noble-metal interstitials act as quasi-stable n-dopants. Experimentally, voltage-dependent, dynamic doping by current density-time (J-t), electrochemical impedance, and photoluminescence measurements are characterized. These results provide deeper insight into the potential beneficial and detrimental impacts of metal electrode reactions on long-term performance of perovskite photovoltaic and light-emitting diodes, as well as offer an alternative doping explanation for the valence switching mechanism of halide-perovskite-based neuromorphic and memristive devices.

Improved Charge Balance in Green Perovskite Light-Emitting Diodes with Atomic-Layer-Deposited Al2O3.

Perovskite light-emitting diodes (LEDs) have experienced a rapid increase in efficiency over the last several years and are now regarded as promising low-cost devices for displays and communication systems. However, it is often challenging to employ ZnO, a well-studied electron transport material, in perovskite LEDs due to chemical instability at the ZnO/perovskite interface and charge injection imbalance caused by the relatively high conductivity of ZnO. In this work, we address these problems by depositing an ultrathin Al2O3 interlayer at the ZnO/perovskite interface, allowing the fabrication of green-emitting perovskite LEDs with a maximum luminance of 21 815 cd/m2. Using atomic layer deposition, we can precisely control the Al2O3 thickness and thus fine-tune the electron injection from ZnO, allowing us to enhance the efficiency and operational stability of our LEDs.

Hot-Casting-Assisted Liquid Additive Engineering for Efficient and Stable Perovskite Solar Cells.

High-performance inorganic-organic lead halide perovskite solar cells (PSCs) are often fabricated with a liquid additive such as dimethyl sulfoxide (DMSO), which retards crystallization and reduces roughness and pinholes in the perovskite layers. However, DMSO can be trapped during perovskite film formation and induce voids and undesired reaction byproducts upon later processing steps. Here, it is shown that the amount of residual DMSO can be reduced in as-spin-coated films significantly through use of preheated substrates, or a so-called hot-casting method. Hot casting increases the perovskite film thickness given the same concentration of solutions, which allows for reducing the perovskite solution concentration. By reducing the amount of DMSO in proportion to the concentration of perovskite precursors and using hot casting, it is possible to fabricate perovskite layers with improved perovskite-substrate interfaces by suppressing the formation of byproducts, which increase trap density and accelerate degradation of the perovskite layers. The best-performing PSCs exhibit a power conversion efficiency (PCE) of 23.4% (23.0% stabilized efficiency) under simulated solar illumination. Furthermore, encapsulated devices show considerably reduced post-burn-in decay, retaining 75% and 90% of their initial and post-burn-in efficiencies after 3000 h of operation with maximum power point tracking (MPPT) under high power of ultraviolet (UV)-containing continuous light exposure.

Targeted Noninvasive Treatment of Choroidal Neovascularization by Hybrid Cell-Membrane-Cloaked Biomimetic Nanoparticles.

Choroidal neovascularization (CNV) is the leading cause of vision loss in many blinding diseases, but current antiangiogenic therapies with invasively intravitreal injection suffer from poor patient compliance and a rate of devastating ocular complications. Here, we develop an alternative antiangiogenic agent based on hybrid cell-membrane-cloaked nanoparticles for noninvasively targeted treatment of CNV. The retinal endotheliocyte membrane coating provides as-fabricated nanoagents with homotypic targeting capability and binding ability to the vascular endothelial growth factor. The fusion of red blood cell membranes protects the hybrid membrane-coated nanoparticles from phagocytosis by macrophages. In a laser-induced wet age-related macular degeneration mouse model, a significantly enhanced accumulation is observed in CNV regions after intravenous delivery of the hybrid membrane-coated nanoparticles. Moreover, an excellent therapeutic efficacy is achieved in reducing the leakage and area of CNV. Overall, the biomimetic antiangiogenic nanoagents provide an effective approach for noninvasive treatment of CNV.

Nanoparticles as a Hedgehog signaling inhibitor for the suppression of cancer growth and metastasis.

Nanoparticles (NPs) have been intensively explored for the treatment of tumors during the past decade, yet little information has been provided on the NPs' inherent therapeutic activity against cancers. With this goal in mind, we reveal that biocompatible silicon (Si) NPs (SiNPs) feature excellent anti-growth and anti-metastasis activities against prostate cancer cells that show aberrant activation of the Hedgehog (HH) signaling pathway. Without activation by the Sonic hedgehog (Shh)-agonist, mouse embryonic fibroblast (NIH3T3) cells show no response to SiNP exposure. The distinct inhibitory effect of SiNPs on the HH signaling pathway leads to significant suppression of the proliferation, migration, and invasion of human prostate cancer cells. Crucially, in two mouse tumor models, the growth and metastasis of prostate cancer cells are also efficiently inhibited by SiNPs.

Dielectric screening in perovskite photovoltaics.

The performance of perovskite photovoltaics is fundamentally impeded by the presence of undesirable defects that contribute to non-radiative losses within the devices. Although mitigating these losses has been extensively reported by numerous passivation strategies, a detailed understanding of loss origins within the devices remains elusive. Here, we demonstrate that the defect capturing probability estimated by the capture cross-section is decreased by varying the dielectric response, producing the dielectric screening effect in the perovskite. The resulting perovskites also show reduced surface recombination and a weaker electron-phonon coupling. All of these boost the power conversion efficiency to 22.3% for an inverted perovskite photovoltaic device with a high open-circuit voltage of 1.25 V and a low voltage deficit of 0.37 V (a bandgap ~1.62 eV). Our results provide not only an in-depth understanding of the carrier capture processes in perovskites, but also a promising pathway for realizing highly efficient devices via dielectric regulation.

Perovskite solar cell towards lower toxicity: a theoretical study of physical lead reduction strategy.

The huge performance enhancements of the organometal halide perovskite solar cells (OHPSCs) have appealed enormous attention within recent ten years. Although the rapid growth of the device power conversion efficiency (PCE) has attained over 25%, the contamination of health-hazardous components still holds back its sustainable applications. To reduce the lead usage, many groups have tried chemical lead reduction solutions: substituting the lead by other group 14 metal elements to realize the low-lead OHPSCs. Unfortunately, neither the PCE nor the stability, low-lead OHPSCs all lag far behind the state-of-the-art conventional lead-based OHPSCs. In this work, we present a physical lead reduction (PLR) concept by reducing the perovskite film thickness to restrict the perovskite hazard risk with minor scarification in device performances. Through the simulation of transfer matrix model, we theoretically demonstrated that by introducing the optical space layer, the device PCE could maintain 96% of the original maximum value while attenuating the perovskite film thickness to one-third. This means that the usage of lead can be reduced by ∼70% with PLR concept, which could have broad appeal as a new lead reduction strategy towards high performance OHPSCs.

Diboron-Assisted Interfacial Defect Control Strategy for Highly Efficient Planar Perovskite Solar Cells.

Metal halide perovskite films are endowed with the nature of ions and polycrystallinity. Formamidinium iodide (FAI)-based perovskite films, which include large cations (FA) incorporated into the crystal lattice, are most likely to induce local defects due to the presence of the unreacted FAI species. Here, a diboron-assisted strategy is demonstrated to control the defects induced by the unreacted FAI both inside the grain boundaries and at the surface regions. The diboron compound (C12 H10 B2 O4 ) can selectively react with unreacted FAI, leading to reduced defect densities. Nonradiative recombination between a perovskite film and a hole-extraction layer is mitigated considerably after the introduction of the proposed approach and charge-carrier extraction is improved as well. A champion power conversion efficiency of 21.11% is therefore obtained with a stabilized power output of 20.83% at the maximum power point for planar perovskite solar cells. The optimized device also delivers negligible hysteresis effect under various scanning conditions. This approach paves a new way for mitigating defects and improving device performance.

Enhanced photovoltage for inverted planar heterojunction perovskite solar cells.

The highest power conversion efficiencies (PCEs) reported for perovskite solar cells (PSCs) with inverted planar structures are still inferior to those of PSCs with regular structures, mainly because of lower open-circuit voltages (Voc). Here we report a strategy to reduce nonradiative recombination for the inverted devices, based on a simple solution-processed secondary growth technique. This approach produces a wider bandgap top layer and a more n-type perovskite film, which mitigates nonradiative recombination, leading to an increase in Voc by up to 100 millivolts. We achieved a high Voc of 1.21 volts without sacrificing photocurrent, corresponding to a voltage deficit of 0.41 volts at a bandgap of 1.62 electron volts. This improvement led to a stabilized power output approaching 21% at the maximum power point.

Dual-Source Precursor Approach for Highly Efficient Inverted Planar Heterojunction Perovskite Solar Cells.

The highest efficiencies reported for perovskite solar cells so far have been obtained mainly with methylammonium and formamidinium mixed cations. Currently, high-quality mixed-cation perovskite thin films are normally made by use of antisolvent protocols. However, the widely used "antisolvent"-assisted fabrication route suffers from challenges such as poor device reproducibility, toxic and hazardous organic solvent, and incompatibility with scalable fabrication process. Here, a simple dual-source precursor approach is developed to fabricate high-quality and mirror-like mixed-cation perovskite thin films without involving additional antisolvent process. By integrating the perovskite films into the planar heterojunction solar cells, a power conversion efficiency of 20.15% is achieved with negligible current density-voltage hysteresis. A stabilized power output approaching 20% is obtained at the maximum power point. These results shed light on fabricating highly efficient perovskite solar cells via a simple process, and pave the way for solar cell fabrication via scalable methods in the near future.