Ligand Passivation Research Articles

Enabling white color tunability in complex 3D-printed composites by using lead-free self-trapped exciton 2D perovskite/carbon quantum dot inks.

The generation of stable white light emission using lead-free perovskites remains a huge challenge in the development of future display and lighting technologies, due to fast material deterioration and the decrease of the color quality. In this work, we report a combination of diverse types of 2D A2SnX4 (A = bulky cation, X = Br, I) perovskites exhibiting self-trapped exciton (STE) emission and blue luminescent carbon quantum dots (CQDs), with the purpose of generating A2SnX4/CQD inks with a broadband emission in the visible region and a tunable white light color. By varying the concentration of the 2D perovskite, the white emission of the mixtures is modulated to cool, neutral, and warm tonalities, with a PL quantum yield up to 45%. From the combinations, the PEA2SnI4/CQD-based ink shows the longest stability, due to suitable surface ligand passivation provided by the capping ligands covering the CQDs, compensating the defect sites in the perovskite. Then, by incorporating the PEA2SnI4/CQDs inks into an acrylate polymer matrix, the quenching of the PL component from the perovskite was restrained, being stable for >400 h under ambient conditions and at a relative humidity of ∼50%, and allowing the preparation of complex 3D-printed composites with stable white emission tonalities. This contribution offers an application of STE-based Sn-perovskites to facilitate the future fabrication of lead-free white-light optoelectronic devices.

Improving the Stability of Halide Perovskites for Photo‐, Electro‐, Photoelectro‐Chemical Applications

AbstractOwing to their remarkable and adjustable optoelectronic properties, halide perovskites (HPs) have been regarded as a class of promising materials for various optoelectronic applications based on different energy conversion reactions, including photovoltaic cell, photocatalysis, electrocatalysis, and photoelectrochemical (PEC) systems. However, the low stability of HPs upon exposure to ambient conditions (e.g., water, heat, light, electricity) greatly hinders the practical applications of HPs. In the past few years, significant efforts have been devoted to enhancing the eventual stability of the perovskite‐based optoelectronic systems, mainly focusing on delivering improvements in the stabilities of halide perovskite materials and the relevant operation conditions of optoelectronic systems, which deserve in‐depth and systematic summaries. In this comprehensive review, the in‐depth environment‐induced decomposition mechanisms of typical HPs are elucidated. Simultaneously, the strategies for addressing the instability issues of halide perovskite materials are critically reviewed, including dimension control, compositional engineering, ligand passivation, and encapsulation engineering. Furthermore, the photoelectric applications based on the modified HPs and operation conditions are discussed systematically. In the last part of this review, future perspectives and outlooks toward the stability of HPs and their photoelectric applications are envisaged respectively.

High‐Efficiency Infrared Sulfide Lead Quantum Dot Solar Cells via Mixed Halide Ions Ligand Engineering

Tandem solar cells are regarded as an effective way to break through the theoretical efficiency of the Shockley–Queisser limit, and large‐size lead sulfide quantum dots (PbS QDs) are considered ideal infrared (IR) photovoltaic materials for absorbing low‐energy IR photons in the bottom subcells of tandem solar cells due to their tunable bandgaps and multiexciton generation effects. However, the exposed (100) surface of large‐size PbS QDs leads to poor passivation during the ligand‐exchange process, resulting in degraded device performance. Herein, a mixed halide ions ligand passivation strategy is developed to synergistically passivate the (111) and (100) facets of large‐size QDs. Particularly, a gradual dropwise addition of lead chloride salts dissolved in dimethyl sulfoxide for achieving precisely proportional surface passivation of Cl ions in the ligand exchange is proposed, which enhances the quality of the QD solids and obtains excellent control of the surface trap states. Additionally, optical and electrical characterization results show that the passivated IR PbS QD solids have higher carrier mobility, longer carrier lifetime, and lower defect density, which increases the IR efficiency of IR PbS QD solar cells to 1.25%.

Performance enhancement of PbS quantum dot solar cells employing a hybrid solid-state ligand exchange protocol

In this work, a hybrid (HB) solid-state ligand exchange strategy was developed for PbS quantum dots (QDs) films, incorporating a synergistic utilization of the popular inorganic ligand tetrabutylammonium iodide (TBAI) and the organic short bidentate linker 1, 2-Ethanedithiol (EDT) in a two-stage process. The two-stage process consisted of a primary solid-state ligand treatment with TBAI in a controlled manner followed by a second-stage ligand treatment with EDT. We could achieve an optimal iodine/EDT ligand passivation ratio for the QDs films by controlling the TBAI ligand treatment time. The method integrates the benefits of both the ligands and resolves the intrinsic incompleteness of the solid-state TBAI ligand exchange. The QDs films thus created have an optimal surface coverage and reduced inter-dot spacing due to an improved QDs close packing. This in turn led to lesser recombination routes due to reduced mid-bandgap trap states and an improved charge transport property through an enhanced electronic coupling between the QDs. A power conversion efficiency of 8.2 % has been achieved in the device with an optimized TBAI /EDT ligand passivation ratio for the QDs films with an EDT hole transport layer.

Trade‐Off Between Efficiency and Stability of CsPbBr3 Perovskite Quantum Dot‐Based Light‐Emitting Diodes by Optimized Passivation Ligands for Br/Pb

AbstractAlthough significant progress has been made in improving the external quantum efficiencies (EQEs) of perovskite quantum dot (QD) light‐emitting diodes (QLEDs), understanding the degradation mechanism and enhancing stability remain a challenge. Herein, increasing the content of Br‐based passivation ligands is shown to enhance the EQE up to 16.1% by reducing the defects of CsPbBr3 QDs in a Br‐rich environment. However, the operational lifetimes of perovskite QLEDs gradually decrease with the increase of halide content, owing to the intensified ion migration under continuous electric field confirmed by the current behavior of QLEDs and time‐of‐flight secondary‐ion mass spectrometry. Furthermore, a thorough analysis of the relationship between electricity and luminance of QLEDs suggests that a small amount of residue oleic acid ligands could weaken ion migration. Accordingly, a halide‐ and acid‐hybrid (HAH) co‐passivation strategy is proposed to optimize the content of Br‐ and acid‐based ligands, and achieve a maximum EQE of 18.6% and an operational lifetime (T50, extrapolated) of 213 h for CsPbBr3 QLEDs. This approach for passivating QDs combines the high efficiency of Br‐based ligands with the improved stability of acid‐based ligands. The study elucidates the correlation between ligands and device performance, highlighting the significance of two or even multiple ligands for efficient and stable perovskite QLEDs.

PbS Colloidal Quantum Dots Infrared Solar Cells: Defect Information and Passivation Strategies

Large‐sized lead sulfide quantum dots (PbS QDs) offer strong absorption in the infrared, making them suitable for bottom cells in tandem devices. However, current QD‐based tandem devices underperform compared to single junction devices. This review focuses on defect information and passivation strategies in large‐sized QD solar cells. Defects from oxidation, polydispersity, and nonbonding sites on the (001) facet during QD synthesis are examined. Ligand‐exchange‐related defects such as tangled atoms, incomplete passivation, and excess ligands are analyzed. Surface and interface defects resulting from solar cell fabrication are also discussed. Strategies including cation exchange, thermodynamic growth, kinetic growth, and mixed halide ligands are summarized. Post‐treatment approaches could also help to address surface and interface defects. Large‐sized PbS‐QDs show promise as infrared radiation absorbers. Overcoming defects and implementing effective passivation strategies are crucial for single junction and tandem solar cells.

In situ and General Multidentate Ligand Passivation Achieves Efficient and Ultra-Stable CsPbX3 Perovskite Quantum Dots for White Light-Emitting Diodes.

Inorganic CsPbX3 perovskite quantum dots (PeQDs) show great potential in white light-emitting diodes (WLEDs) due to excellent optoelectronic properties, but their practical application is hampered by low photoluminescence quantum yield (PLQY) and especially poor stability. Herein, we developed an in-situ and general multidentate ligand passivation strategy that allows for CsPbX3 PeQDs not only near-unit PLQY, but significantly improved stability against storage, heat, and polar solvent. The enhanced optical property arises from high effectiveness of the multidentate ligand, diethylenetriaminepentaacetic acid (DTPA) with five carboxyl groups, in passivating uncoordinated Pb2+ defects and suppressing nonradiative recombination. First-principles calculations reveal that the excellent stability is attributed to tridentate binding mode of DTPA that remarkably boosts the adsorption capacity to PeQD core. Finally, combining the green and red PeQDs with blue chip, we demonstrated highly luminous WLEDs with distinctly enhanced operation stability, a wide color gamut of 121.3% of national television system committee, standard white light of (0.33,0.33) in CIE 1931, and tunable color temperatures from warm to cold white light readily by emitters' ratio. This study provides an operando yet general approach to achieve efficient and stable PeQDs for WLEDs and accelerates their progress to commercialization.

Effect of silica encapsulation on the stability and photoluminescence emission of FAxCs1-xPbX3 quantum dots for white mini light emitting diodes

Development of wide-color gamut white light-emitting diodes (WLEDs) for displays, with nitride-based phosphors and conventional core-shell quantum dots (QDs) such as InP, CdSe, and all-inorganic CsPbI3 perovskite quantum dots due to their excellent optoelectronic properties performance, is an excellent candidate for new optoelectronic applications.However, in backlight applications, the color gamut of perovskite quantum dots will be reduced due to the matching degree of color filter, which will limit its application in wide color gamut. To address these issues, in this paper, we propose a novel approach, namely, formamidine acetate (FA+) cationic doping, in CsPbI3 system synthesized at room temperature by organic-inorganic ligand passivation method which can effectively maintain structural stability. At the same time, the PL emission band of CsPbI3 is increased by doping FA + cations and the color gamut range is improved. We will discuss this change in detail, and quantum dot films using spin coating method can be maintained for a month in atmospheric conditions. For practical applications, the color gamut range can reach 133%. Therefore, our proposed perovskite quantum dots, FAxCs1-xPbI3, have great potential for application in wide color gamut displays.

Multidentate Ligand-Passivated CsPbI3 Perovskite Nanocrystals for Stable and Efficient Red-Light-Emitting Diodes.

CsPbI3 nanocrystals (NCs) have become a research hot spot in the field of light-emitting diodes (LEDs). Whereas, the long chain ligands with weak affinity to CsPbI3 NCs have prevented their further development and commercialization. Herein, a novel multidentate short ligand tetramethylthiuram disulfide (TMTD) was employed via a ligand exchange process to enhance hole mobility and decrease trap density of the CsPbI3 NCs film. Therefore, TMTD passivated CsPbI3 NCs LED exhibited 20.65% maximum external quantum efficiency and 3861 cd/m2 maximum luminance. Furthermore, TMTD passivated CsPbI3 NCs LED exhibited good operational stability with a 128 min half-lifetime. This strategy using multidentate short ligand passivation provides an effective way to promote perovskite LED development and commercialization.

Spectroscopic Insight into Customized Iodine Ligands Passivated Red‐Emitting CsPb(Br,I)3 Perovskite Nanocrystals via Time‐Resolved Photoluminescence

AbstractMolecular engineering toward the structure of a passivation ligand is essential to improve the photoluminescence (PL) efficiency of perovskite nanocrystals (PNCs). To establish the surface recovery mechanism of red‐emitting CsPb(Br,I)3 NCs with PbI2 additives in the presence of a tightly bound passivation layer, time‐resolved photoluminescence (TRPL) measurements and their chemometric analysis are employed. Two quaternary alkylammonium ligands, didodecyldimethylammonium iodide (DDAI) and tridodecylmethylammonium iodide (TDAI), are used to form a passivation layer, and then their role in the surface defects recovery is investigated by varying the amount of PbI2 additives. It is found that the structural difference between DDAI and TDAI can affect the accessibility of PbI2 additives to surface defects. The TRPL spectra analysis reveals that the ligand passivation with DDAI does not induce discernible lifetime enhancement with using PbI2 additives, but only a non‐radiative pathway is gradually accelerated with increasing the amount of them. The TDAI ligand, however, shows the opposite behavior to give the best PL performance with a distinct molar ratio of TDAI:PbI2, even though the passivation itself gives a lower PL performance. It is argued that the intrinsic structural properties of the TDAI ligand are responsible for the effective surface recovery with the additives.

Highly Efficient Perovskite Solar Cells Enabled by Multiple Ligand Passivation

Highly Efficient Perovskite Solar Cells Enabled by Multiple Ligand Passivation

Surface Reconstruction of CsPbBr3 Nanocrystals by the Ligand Engineering Approach for Achieving High Quantum Yield and Improved Stability.

Oleylamine/oleic acid (OAm/OA) as the commonly used ligand is indispensable in the synthesis of perovskite nanocrystals (PNCs). Unfortunately, poor colloidal stability and unsatisfactory photoluminescence quantum yield (PLQY) are observed, resulting from a highly dynamic binding nature between ligands. Herein, we adopt a facile hybrid ligand (DDAB/ZnBr2) passivation strategy to reconstruct the surface chemistry of CsPbBr3 NCs. The hybrid ligand can detach the native surface ligand, in which the acid-base reactions between ligands are suppressed effectively. Also, they can substitute the loose capping ligand, anchor to the surface firmly, and supply sufficient halogens to passivate the surface trap, realizing an exceptional PLQY of 95% and an enhanced tolerance toward ambient storage, UV irradiation, anti-solvents, and thermal treatment. Besides, the as-fabricated white light-emitting diode (WLED) utilizing the PNCs as the green-emitting phosphor has a luminous efficiency around 73 lm/W; the color gamut covers 125% of the NTSC standard.

Hybrid Ligand Polymerization for Weakly Confined Lead Halide Perovskite Quantum Dots

Rational ligand passivation is essential to achieve a higher performance of weakly confined lead halide perovskite quantum dots (PQDs) via a mechanism of surface chemistry and/or microstrain. In situ passivation with 3-mercaptopropyltrimethoxysilane (MPTMS) produces CsPbBr3 PQDs with an enhanced photoluminescence quantum yield (PLQY, ΦPL) of up to 99%; meanwhile, charge transport of the PQD film can be enhanced by one order of magnitude. Herein, we examine the effect of the molecular structure of MPTMS as the ligand exchange agent in comparison to octanethiol. Both thiol ligands promote crystal growth of PQDs, inhibit nonradiative recombination, and cause blue-shifted PL, while the silane moiety of MPTMS manipulates surface chemistry and outperforms owing to its unique cross-linking chemistry characterized by FTIR vibrations at 908 and 1641 cm-1. Emergence of the diagnostic vibrations is ascribed to hybrid ligand polymerization arising from the silyl tail group that confers the advantages of narrower size dispersion, lower shell thickness, more static surface binding, and higher moisture resistance. In contrast, the superior electrical property of the thiol-passivated PQDs is mostly determined by the covalent S-Pb bonding on the interface.

Methoxy Functionalization of Phenethylammonium Ligand for Efficient Perovskite Light‐Emitting Diodes

AbstractAlthough the electroluminescent performances of perovskite light‐emitting diodes (PeLEDs) are continuously improved through defect management strategies, the complicated design of passivation ligands brings great challenges to the rational defect‐annihilation process. Herein, considering the bonding strength with uncoordinated Pb2+, the methoxy group with strong electron donating ability is introduced to commonly used phenethylammonium ligand as an efficient additive, namely 4‐methoxy‐phenethylammonium iodide (4‐MeO‐PEAI), to facilitate passivation process in perovskite light‐emitting materials. It is demonstrated that the 4‐MeO‐PEAI agent substantially increases the crystal orientation, enlarges the crystalline grain size, and mitigates the deep‐level trap centers through strong bonding between the methoxy group with unpaired Pb2+ ions. The external quantum efficiencyvalue of the PeLEDs with optimized passivation reaches a maximum of 21.6%, with an emission peak of 790 nm. In addition, a nearly threefold increase of the operational half‐lifetime T50 of the 4‐MeO‐PEAI‐mediated devices is observed as compared to the reference sample. Further theoretical calculation results suggest that the adhesion of the ligands on perovskite surface via vacancies leads to an increased dissociation barrier of perovskite; thus, ameliorating the degradation of the PeLEDs under electric field. The findings provide an effective design strategy of the passivation agents to produce high‐performance perovskite‐based optoelectronics devices.

Highly Stable CsPbBr3 Nanocrystals for Photocatalytic Reduction of CO2: Ionic Liquid as a Surface Passivation Ligand and Reaction Precursor

All inorganic metal halide perovskites (MHPs) have been regarded as a new type of promising photocatalyst for the reduction of CO2. However, due to their strong ionicity and the labile surface ligands, there is still much room for improvement of the stability and efficiency of MHP photocatalysts. Here, we propose a new strategy simultaneously using ionic liquid (IL) as a surface passivation ligand and a precursor to mediate the growth and then stabilize CsPbBr3 MHPs for the photocatalytic reduction of CO2. First, the TEM and XRD results show that the prepared CsPbBr3 has a cubic morphology with the monoclinic phase when the IL of 1-octyl-3-methylimidazolium bromide ([Omim]Br) is used as the surface ligand. When the molar ratio of [Omim]Br to Pb(CH3COO)2 is optimized to 2, the photoluminescence quantum yield of the prepared CsPbBr3 can reach as high as 90.93%, suggesting the effective reduction of surface defects by the IL ligand. Importantly, the CsPbBr3 nanocrystals show high stability under the ambient stimuli of light, heat, and humidity. The subsequent FT-IR and XPS characterizations indicate that the presence of [Omim]Br on the surface of CsPbBr3 increases the Br-rich state, which accounts for the excellent optical property and stability of the CsPbBr3 nanocrystals. Finally, with the assistance of IL as the activator of CO2, the CsPbBr3 photocatalysts provide a high evolution rate of 24.56 and 6.66 μmol g–1 h–1 for CO and CH4, respectively. Multifunctional ILs as passivation ligands, reaction precursors, and CO2 activators provide an efficient pathway to fabricate stable metal halide perovskites for photocatalytic CO2 conversion.

Influence of Capping Ligands, Solvent, and Thermal Effects on CdSe Quantum Dot Optical Properties by DFT Calculations.

Cadmium selenide nanomaterials are very important materials in photonics, catalysis, and biomedical applications due to their optical properties that can be tuned through size, shape, and surface passivation. In this report, static and ab initio molecular dynamics density functional theory (DFT) simulations are used to characterize the effect of ligand adsorption on the electronic properties of the (110) surface of zinc blende and wurtzite CdSe and a (CdSe)33 nanoparticle. Adsorption energies depend on ligand surface coverage and result from a balance between chemical affinity and ligand-surface and ligand-ligand dispersive interactions. In addition, while little structural reorganization occurs upon slab formation, Cd···Cd distances become shorter and the Se-Cd-Se angles become smaller in the bare nanoparticle model. This originates mid-gap states that strongly influence the absorption optical spectra of nonpassivated (CdSe)33. Ligand passivation on both zinc blende and wurtzite surfaces does not induce a surface reorganization, and thus, the band gap remains nonaffected with respect to bare surfaces. In contrast, structural reconstruction is more apparent for the nanoparticle, which significantly increases its highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gap upon passivation. Solvent effects decrease the band gap difference between the passivated and nonpassivated nanoparticles, the maximum of the absorption spectra being blue-shifted around 20 nm by the effect of the ligands. Overall, calculations show that flexible surface cadmium sites are responsible for the appearance of mid-gap states that are partially localized on the most reconstructed regions of the nanoparticle that can be controlled through appropriate ligand adsorption.

Mixed Ligand Passivation as the Origin of Near-Unity Emission Quantum Yields in CsPbBr3 Nanocrystals

Key features of syntheses, involving the quaternary ammonium passivation of CsPbBr3 nanocrystals (NCs), include stable, reproducible, and large (often near-unity) emission quantum yields (QYs). The archetypical example involves didodecyl dimethyl ammonium (DDDMA+)-passivated CsPbBr3 NCs where robust QYs stem from interactions between DDDMA+ and NC surfaces. Despite widespread adoption of this synthesis, specific ligand-NC surface interactions responsible for large DDDMA+-passivated NC QYs have not been fully established. Multidimensional nuclear magnetic resonance experiments now reveal a new DDDMA+-NC surface interaction, beyond established "tightly bound" DDDMA+ interactions, which strongly affects observed emission QYs. Depending upon the existence of this new DDDMA+ coordination, NC QYs vary broadly between 60 and 85%. More importantly, these measurements reveal surface passivation through unexpected didodecyl ammonium (DDA+) that works in concert with DDDMA+ to produce near-unity (i.e., >90%) QYs.

Ligand-Ligand-Interaction-Dominated Self-Assembly of Gold Nanoparticles at the Oil/Water Interface: An Atomic-Scale Simulation.

The self-assembly of nanoparticles (NPs) into ordered superlattices is a powerful strategy to fabricate functional nanomaterials. Subtle variations in the interactions between NPs will influence the self-assembled superlattices. Using all-atom molecular dynamics simulations, we explore the self-assembly of 16 gold NPs, 4 nm in diameter, capped with ligands at the oil-water interface, and quantify the interactions between NPs at the atomic scale. We demonstrate that the interaction between capping ligands rather than that between NPs is dominant during the assembly process. For dodecanethiol (DDT)-capped Au NPs, the assembled superlattice is highly ordered in a close-packed configuration at a slow evaporation rate, while it is disordered at a fast evaporation rate. When replacing the capping ligands with stronger polarization than DDT molecules, the NPs form a robust ordered configuration at different evaporation rates due to the stronger electrostatic attraction between capping ligands from different NPs. Moreover, Au-Ag binary clusters exhibit similar assembly behavior with Au NPs. Our work uncovers the nonequilibrium nature of NP assembly at the atomic scale and would be helpful in rationally controlling NPs superlattice by changing passivating ligands, solvent evaporation rate, or both.

Multi‐Bandgap Quantum Dots Ensemble for Near‐Infrared Photovoltaics

Narrow bandgap quantum dots (QDs) are an important class of materials for near‐infrared (NIR) optoelectronic devices owing to their size‐tunable bandgap and chemical root processing. In photovoltaic applications, NIR QDs could be particularly useful to complement the sub‐bandgap transmission loss of NIR solar radiation from perovskite and c‐Si solar cells. However, insufficient carrier extraction thickness associated with the narrow NIR excitonic bandwidth of QDs limits the conversion efficacy of the broad NIR solar spectrum. Here, we utilize a multi‐bandgap QD ensemble which widens the NIR absorption bandwidth to mimic the broad solar spectrum. A solution‐phase ligand passivation strategy is used to control doping properties and energy level alignment of multi‐bandgap QDs. We successfully developed bulk‐heterojunction solar cells using the multi‐bandgap QD ensemble, which yields higher carrier extraction thickness and broader NIR absorption. The gain from NIR absorption and carrier transport resulted in higher short‐circuit current generation and power conversion efficiency (PCE) in solar cell devices. The champion device shows 8.73% PCE under 1.5 AM solar illumination and 7.44% and 5.05% PCE for the NIR photons transmitted from perovskite and c‐Si layers.

Passivation of Surface Defects by X-type Short-Chain Ligands for High Quantum Yield and Stable CsPbX3 Quantum Dots Synthesis and Application in WLEDs

All-inorganic CsPbX3 perovskite quantum dots have excellent optoelectronic properties and are excellent candidates for optoelectronic applications. However, the surface ligands (oleyl ammonium, oleic acid) commonly used in traditional inorganic perovskite quantum dots easily fall off from the quantum dots and their protective power is relatively weak, resulting in poor quantum yield and stability of the quantum dots, limiting their application. In this paper, we introduce an X-type short-chain ligand (DDEAB) passivation strategy to enhance the optoelectronic properties of CsPbX3 quantum dots through a facile room-temperature synthesis method and the strong affinity of X-type ligands for surface atoms. The results of TRPL and X-ray photoelectron spectroscopy showed longer lifetime and stronger surface affinity. This result confirms that didecyldimethylammonium bromide (DDEAB) has better binding to CsPbBr3 QDs and can effectively reduce surface defects and improve quantum yield. As a result, the introduction of short-chain ligands can more effectively passivate the surface halogen defects of CsPbX3 QDs, achieving high quantum yield (>90%) and long-term storage environmental stability. In addition, DDEAB-passivated CsPbBr3 QDs have been successfully applied in white light emitting diodes (WLEDs) with wider color gamut (123%), and good EL stability compared to NTSC TV color standard. Our proposed short-chain ligand DDEAB passivation strategy may provide a reference guideline for the preparation of quantum dots and photovoltaic devices with high photoluminescence and environmental stability.