Oligomeric Zinc Thiolates Tethering Multidentate Carboxylates for Nondestructive Aqueous Phase Transfer of Quantum Dots.

Functionalization of quantum dots (QDs) via ligand exchange is prone to debase their photoluminescence quantum yield (PL QY) owing to the unavoidable surface damage by excess reactants, and even worse in aqueous medium. Herein, the oligomeric zinc thiolate as the multidentate hydrophilic ligand featuring facile synthetic protocol is proposed. A simple reaction between ZnCl2 and 3-mercaptopropionic acid produces oligomeric ligands containing 3-6 zinc thiolate units, where the terminal moieties provide multidentate anchoring to the surface as well as hydrophilicity. 2D proton nuclear Overhauser effect spectroscopy (2D 1 H NOESY) and X-ray photoelectron spectroscopy (XPS) reveal that the oligomeric zinc thiolate ligands adsorb on the surface via multidentate metal carboxylate bindings without destruction of molecular structure, regardless of partial dissociation of thiolate branches in aqueous phase. Enhanced binding affinity granted by the multidentate nature allows for the effective exchange of original surface ligands without considerable surface deterioration. The zinc thiolate-capped Cd-free aqueous QDs exhibit a high photoluminescence quantum yield of ≈90% and extended stability against long-term storage and photochemical stress.

Interface polarization in heterovalent core-shell nanocrystals.

The potential profile and the energy level offset of core-shell heterostructured nanocrystals (h-NCs) determine the photophysical properties and the charge transport characteristics of h-NC solids. However, limited material choices for heavy metal-free III-V-II-VI h-NCs pose challenges in comprehensive control of the potential profile. Herein, we present an approach to such a control by steering dipole densities at the interface of III-V-II-VI h-NCs. The controllable heterovalency at the interface is responsible for interfacial dipole densities that result in the vacuum-level shift, providing an additional knob for the control of optical and electrical characteristics of h-NCs. The synthesis of h-NCs with atomic precision allows us to correlate interfacial dipole moments with the NCs' photochemical stability and optoelectronic performance.

Linearly polarized emission from CdSe/CdS core-in-rod nanostructures: Effects of core position.

Semiconductor nanocrystals with an anisotropic morphology exhibit unique properties, most notably their linear polarization. The colloidal growth of semiconductor nanorods with core dots inside, also referred to as dot-in-rod (DIR) structure, has enabled the synthesis of anisotropic nanocrystals with better stability and controllable fluorescence polarization. In this study, we synthesize CdSe/CdS DIR nanocrystals, in which the position of the CdSe core particle can be controlled by using different ligand compositions during the CdS growth. Varying the core position within the DIR structure, e.g., from the center to the end of the DIR particles, results in a change in the degree of linear polarization. When the core is positioned at the center of the nanorod, the linear polarization turns out to be higher compared with tip-core DIRs. Time-resolved photoluminescence analysis reveals that the center-core DIRs have higher electron-hole interaction than tip-core DIRs because of weak uniaxial strain in center-core DIR that arises from lattice dislocations at the interface to relieve accumulated strain.

Light-Driven Ammonia Production by Azotobacter vinelandii Cultured in Medium Containing Colloidal Quantum Dots.

There is an evergrowing demand for environment-friendly processes to synthesize ammonia (NH3) from atmospheric nitrogen (N2). Although diazotrophic N2 fixation represents an undeniably "green" process of NH3 synthesis, the slow reaction rate makes it less suitable for industrially meaningful large-scale production. Here, we report the photoinduced N2 fixation using a hybrid system composed of colloidal quantum dots (QDs) and aerobic N2-fixing bacteria, Azotobacter vinelandii. Compared to the case where A. vinelandii cells are simply mixed with QDs, NH3 production increases significantly when A. vinelandii cells are cultured in the presence of core/shell InP/ZnSe QDs. During the cell culture of A. vinelandii, the cellular uptake of QDs is facilitated in the exponential growth phase. Experimental results as well as theoretical calculations indicate that the photoexcited electrons in QDs within A. vinelandii cells are directly transferred to MoFe protein, the catalytic component of nitrogenase. We also observe that the excess amount of QDs left on the outer surface of A. vinelandii disrupts the cellular membrane, leading to the decrease in NH3 production due to the deactivation of nitrogenase. The successful uptake of QDs in QD-A. vinelandii hybrid with minimal amount of QDs on the outer surface of the bacteria is key to efficient photosensitized NH3 production. The comprehensive understanding of the QD-bacteria interface paves an avenue to novel and efficient nanobiohybrid systems for chemical production.

Efficient, Selective CO2 Photoreduction Enabled by Facet-Resolved Redox-Active Sites on Colloidal CdS Nanosheets.

Advances in nanotechnology have enabled precise design of catalytic sites for CO2 photoreduction, pushing product selectivity to near unity. However, activity of most nanostructured photocatalysts remains underwhelming due to fast recombination of photogenerated electron-hole pairs and sluggish hole transfer. To address these issues, we construct colloidal CdS nanosheets (NSs) with the large basal planes terminated by S2- atomic layers as intrinsic photocatalysts (CdS-S2- NSs). Experimental investigation reveals that the S2- termination endows ultrathin CdS-S2- NSs with facet-resolved redox-catalytic sites: oxidation occurs on S2--terminated large basal facets and reduction happens on side facets. Such an allocation of redox sites not only promotes spatial separation of photoinduced electrons and holes but also facilitates balanced extraction of holes and electrons by shortening the hole diffusion distance along the (001) direction of the ultrathin NSs. Consequently, the CdS-S2- NSs exhibit superb performance for photocatalytic CO2-to-CO conversion, which was verified by the isotope-labeled experiments to be a record-breaking performance: a CO selectivity of 99%, a CO formation rate of 2.13 mol g-1 h-1, and an effective apparent quantum efficiency of 42.1% under the irradiation (340 to 450 nm) of a solar simulator (AM 1.5G). The breakthrough performance achieved in this work provides novel insights into the precise design of nanostructures for selective and efficient CO2 photoreduction.

Polarized Electroluminescence Emission in High-Performance Quantum Rod Light-Emitting Diodes via the Langmuir-Blodgett Technique.

Due to their anisotropic structure, quantum rods (QRs) feature unique properties that differ from quantum dots, such as suppression of non-radiative Auger recombination and linearly polarized light emission. Despite many potential advantages, the progress of QR-based light-emitting diodes (QR-LEDs) is left behind due to the difficulty in aligning QRs. In this study, polarized electroluminescence emission is reported in high-performance QR-LEDs by employing the Langmuir-Blodgett (LB) technique. The adoption of the LB technique successfully produces a highly dense and smooth QR film with a high degree of alignment. As a result, the aligned QR films exhibit polarized photoluminescence emission with a degree of linear polarization of 2.1. Advantageous features of the LB technique, such as nondestructiveness, precise thickness control, and the nonnecessity of an additional matrix material, allow to fabricate QR-LEDs with the same procedure as the standard spin coating-based scheme. The device is fabricated via the LB technique, which shows excellent device performance, such as the low turn-on voltage of 1.8 V, peak luminance of 56 287 cd m-2 , and peak external quantum efficiency (EQE) of 10.33%. Furthermore, these devices clearly exhibit an indication of polarized electroluminescence emission, which opens new opportunities for QRs in display technologies.

Fluorescence Switchable Block Copolymer Particles with Doubly Alternate-Layered Nanoparticle Arrays.

The precise self-assembly of block copolymers (BCPs) and inorganic nanoparticles (NPs) under 3D confinement offers microparticles with programmable nanostructures and functionalities. Here, fluorescence-switchable hybrid microspheres are developed by forming doubly alternating arrays of Au NPs and CdSe/ZnS quantum dots (QDs) within polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) BCP domains. These doubly alternating arrays afford controlled nonradiative energy transfer (NRET) between the QDs and Au NPs that is dependent on the layer-to-layer distance. Solvent-selective swelling of the hybrid particles tunes the distance between layers, modulating their NRET behavior and affording switchable fluorescence. The particle fluorescence is "OFF" in water through strong NRET from the QDs to Au NPs, but is "ON" in alcohols due to the increased distance between the Au NP and QD arrays in the swollen P4VP domains. The experimentally observed NRET intensity as a function of interparticle distance shows larger quenching efficiencies than those theoretically predicted due to the enhanced quenching within a 3D-confined system. Finally, the robust and reversible fluorescence switching of the hybrid particles in different solvents is demonstrated, highlighting their potentials for bioimaging, sensing, and diagnostic applications.

Recombinant Escherichia coli as a biofactory for various single- and multi-element nanomaterials.

Nanomaterials (NMs) are mostly synthesized by chemical and physical methods, but biological synthesis is also receiving great attention. However, the mechanisms for biological producibility of NMs, crystalline versus amorphous, are not yet understood. Here we report biosynthesis of 60 different NMs by employing a recombinant Escherichia coli strain coexpressing metallothionein, a metal-binding protein, and phytochelatin synthase that synthesizes a metal-binding peptide phytochelatin. Both an in vivo method employing live cells and an in vitro method employing the cell extract are used to synthesize NMs. The periodic table is scanned to select 35 suitable elements, followed by biosynthesis of their NMs. Nine crystalline single-elements of Mn3O4, Fe3O4, Cu2O, Mo, Ag, In(OH)3, SnO2, Te, and Au are synthesized, while the other 16 elements result in biosynthesis of amorphous NMs or no NM synthesis. Producibility and crystallinity of the NMs are analyzed using a Pourbaix diagram that predicts the stable chemical species of each element for NM biosynthesis by varying reduction potential and pH. Based on the analyses, the initial pH of reactions is changed from 6.5 to 7.5, resulting in biosynthesis of various crystalline NMs of those previously amorphous or not-synthesized ones. This strategy is extended to biosynthesize multi-element NMs including CoFe2O4, NiFe2O4, ZnMn2O4, ZnFe2O4, Ag2S, Ag2TeO3, Ag2WO4, Hg3TeO6, PbMoO4, PbWO4, and Pb5(VO4)3OH NMs. The strategy described here allows biosynthesis of NMs with various properties, providing a platform for manufacturing various NMs in an environmentally friendly manner.

Depletion-Mediated Interfacial Assembly of Semiconductor Nanorods.

Electronic devices comprised of nanocrystal (NC) thin film are projected to demonstrate enhanced figure of merit if NC building blocks self-assemble into highly uniform, 2-dimensional (2-D) superstructures with long-range order. Despite intensive research efforts and remarkable progress, long-range assembly of colloidal anisotropic NCs into thin films with orientational and positional order has remained to be addressed. One of the most promising approaches is to dissolve excess free molecules into NC solution, which has enabled the formation of NC monolayers with exceptional quality at air/solution interface. Nevertheless, the assembly mechanism and the role of free molecules have not been comprehensively elucidated, restricting the use of the approach. Here, we find that the interfacial assembly of CdSe/CdS core/shell nanorods (NRs) results in various ordered structures in the presence of free oleic acid molecules. The structures include a bundle of standing NRs, a belt of multilayered lying NRs, and a monolayer smectic phase, obtained by simple change in density of surface ligands on the NRs. Experimental observation and theoretical calculation reveal that the assembly is initiated at the air/solution interface due to the preferential depletion attraction of NRs to the interface. However, subsequent growth is significantly altered depending on the ligand density that determines the relative magnitude of interface-NR depletion attraction to inter-NR attraction. Highly ordered structures of NRs, especially for the monolayer smectic phase, are promising as a polarized light-emitting layer for thin-film optical devices. In addition, our findings on the depletion-mediated NR assembly provide important and universal design criteria for 2-D structuring of NCs with diverse geometries and compositions.

Threshold Voltage Control of Multilayered MoS2 Field-Effect Transistors via Octadecyltrichlorosilane and their Applications to Active Matrixed Quantum Dot Displays Driven by Enhancement-Mode Logic Gates.

In recent past, for next-generation device opportunities such as sub-10 nm channel field-effect transistors (FETs), tunneling FETs, and high-end display backplanes, tremendous research on multilayered molybdenum disulfide (MoS2 ) among transition metal dichalcogenides has been actively performed. However, nonavailability on a matured threshold voltage control scheme, like a substitutional doping in Si technology, has been plagued for the prosperity of 2D materials in electronics. Herein, an adjustment scheme for threshold voltage of MoS2 FETs by using self-assembled monolayer treatment via octadecyltrichlorosilane is proposed and demonstrated to show MoS2 FETs in an enhancement mode with preservation of electrical parameters such as field-effect mobility, subthreshold swing, and current on-off ratio. Furthermore, the mechanisms for threshold voltage adjustment are systematically studied by using atomic force microscopy, Raman, temperature-dependent electrical characterization, etc. For validation of effects of threshold voltage engineering on MoS2 FETs, full swing inverters, comprising enhancement mode drivers and depletion mode loads are perfectly demonstrated with a maximum gain of 18.2 and a noise margin of ≈45% of 1/2 VDD . More impressively, quantum dot light-emitting diodes, driven by enhancement mode MoS2 FETs, stably demonstrate 120 cd m-2 at the gate-to-source voltage of 5 V, exhibiting promising opportunities for future display application.

Enhanced thermal stability of InP quantum dots coated with Al-doped ZnS shell.

Colloidal InP quantum dots (QDs) have attracted a surge of interest as environmentally friendly light-emitters in downconversion liquid crystal displays and light-emitting diodes (LEDs). A ZnS shell on InP-based core QDs has helped achieve high photoluminescence (PL) quantum yield (QY) and stability. Yet, due to the difficulty in the growth of a thick ZnS shell without crystalline defects, InP-based core/shell QDs show inferior stability against QY drop compared to Cd chalcogenide precedents, e.g., CdSe/CdS core/thick-shell QDs. In this work, we demonstrate the synthesis of InP-based core/shell QDs coated with an Al-doped ZnS outer shell. QDs with an Al-doped shell exhibit remarkable improvement in thermal and air stability even when the shell thickness is below 2 nm, while the absorption and PL spectra, size, and crystal structure are nearly the same as the case of QDs with a pristine ZnS shell. X-ray photoelectron spectroscopy reveals that Al3+ in Al-doped QDs forms an Al-oxide layer at elevated temperature under ambient atmosphere. The as-formed Al-oxide layer blocks the access of external oxidative species penetrating into QDs and prevents QDs from oxidative degradation. We also trace the chemical pathway of the incorporation of Al3+ into ZnS lattice during the shell growth. Furthermore, we fabricate QD-LEDs using Al-doped and undoped QDs and compare the optoelectronic characteristics and stability.

Performance Limits of Luminescent Solar Concentrators Tested with Seed/Quantum-Well Quantum Dots in a Selective-Reflector-Based Optical Cavity.

Luminescent solar concentrators (LSCs) can serve as large-area sunlight collectors for photovoltaic devices. An important LSC characteristic is a concentration factor (C), which is defined as the ratio of the output and the input photon flux densities. This parameter can be also thought of as an effective enlargement factor of a solar cell active area. On the basis of thermodynamic considerations, the C-factor can reach extremely high values that exceed those accessible with traditional concentrating optics. In reality, however, the best reported values of C are around 30. Here we demonstrate that using a new type of high-emissivity quantum dots (QDs) incorporated into a specially designed cavity, we are able to achieve the C of ∼62 for spectrally integrated emission and ∼120 for the red portion of the photoluminescence spectrum. The key feature of these QDs is a seed/quantum-well/thick-shell design, which allows for obtaining a high emission quantum yield (>95%) simultaneously with a large LSC quality factor (QLSC of ∼100) defined as the ratio of absorption coefficients at the wavelengths of incident and reemitted light. By incorporating the QDs into a specially designed cavity equipped with a top selective reflector (a Bragg mirror or a thin silver film), we are able to effectively recycle reemitted light achieving light trapping coefficients of ∼85%. The observed performance of these devices is in remarkable agreement with analytical modeling, which allows us to project that the applied approach should allow one to boost the spectrally integrated concentration factors to more than 100 by further improving light trapping and/or increasing QLSC.

Highly luminescent silica-coated CdS/CdSe/CdS nanoparticles with strong chemical robustness and excellent thermal stability.

We present facile synthesis of bright CdS/CdSe/CdS@SiO2 nanoparticles with 72% of quantum yields (QYs) retaining ca 80% of the original QYs. The main innovative point is the utilization of the highly luminescent CdS/CdSe/CdS seed/spherical quantum well/shell (SQW) as silica coating seeds. The significance of inorganic semiconductor shell passivation and structure design of quantum dots (QDs) for obtaining bright QD@SiO2 is demonstrated by applying silica encapsulation via reverse microemulsion method to three kinds of QDs with different structure: CdSe core and 2 nm CdS shell (CdSe/CdS-thin); CdSe core and 6 nm CdS shell (CdSe/CdS-thick); and CdS core, CdSe intermediate shell and 5 nm CdS outer shell (CdS/CdSe/CdS-SQW). Silica encapsulation inevitably results in lower photoluminescence quantum yield (PL QY) than pristine QDs due to formation of surface defects. However, the retaining ratio of pristine QY is different in the three silica coated samples; for example, CdSe/CdS-thin/SiO2 shows the lowest retaining ratio (36%) while the retaining ratio of pristine PL QY in CdSe/CdS-thick/SiO2 and SQW/SiO2 is over 80% and SQW/SiO2 shows the highest resulting PL QY. Thick outermost CdS shell isolates the excitons from the defects at surface, making PL QY relatively insensitive to silica encapsulation. The bright SiO2-coated SQW sample shows robustness against harsh conditions, such as acid etching and thermal annealing. The high luminescence and long-term stability highlights the potential of using the SQW/SiO2 nanoparticles in bio-labeling or display applications.

Air-Stable PbSe Nanocrystals Passivated by Phosphonic Acids.

We developed a new chemical strategy to enhance the stability of lead selenide nanocrystals (PbSe NCs) against oxidation through the surface passivation by P-O- moieties. In the synthesis of PbSe NCs, tris(diethylamino)phosphine (TDP) selenide (Se) was used as a Se precursor, and the resulting PbSe NCs withstood long-term air exposure while showing nearly no sign of oxidation. Nuclear magnetic resonance (NMR) spectroscopy reveals that TDP derivatives passivate the surface of PbSe NC. Through a series of ligand cleavage reactions, we found that the TDP derivatives are bound on NC surface through the P-O- moiety. Based on such understanding, it turned out that direct addition of various PAs during the synthesis of PbSe NCs also results in the NCs whose absorption spectrum remains nearly intact after air exposure for weeks. The P-O- moieties render the NCs stable in the operation of field effect transistors, suggesting that our findings can enable the use of air stable PbSe NCs in wider array of optoelectronic applications.

Quantum Dot/Siloxane Composite Film Exceptionally Stable against Oxidation under Heat and Moisture.

We report on the fabrication of a siloxane-encapsulated quantum dot (QD) film (QD-silox film), which exhibits stable emission intensity for over 1 month even at elevated temperature and humidity. QD-silox films are solidified via free radical addition reaction between oligosiloxane resin and ligand molecules on QDs. We prepare the QD-oligosiloxane resin by sol-gel condensation reaction of silane precursors with QDs blended in the precursor solution, forgoing ligand-exchange of QDs. The resulting QD-oligosiloxane resin remains optically clear after 40 days of storage, in contrast to other QD-containing resins which turn turbid and ultimately form sediments. QDs also disperse uniformly in the QD-silox film, whose photoluminescence (PL) quantum yield (QY) remains nearly unaltered under harsh conditions; for example, 85 °C/5% relative humidity (RH), 85 °C/85% RH, strongly acidic, and strongly basic environments for 40 days. The QD-silox film appears to remain equally emissive even after being immersed into boiling water (100 °C). Interestingly, the PL QY of the QD-silox film noticeably increases when the film is exposed to a moist environment, which opens a new, facile avenue to curing dimmed QD-containing films. Given its excellent stability, we envision that the QD-silox film is best suited in display applications, particularly as a PL-type down-conversion layer.

Quantum efficiency of colloidal suspensions containing quantum dot/silica hybrid particles.

We have investigated the fluorescence properties of colloidal suspensions conntaining quantum dot (QD)/silica hybrid particles. First, we synthesized QD/silica hybrid particles with silica-QD-silica (SQS) core-shell-shell geometry, and monitored the quantum efficiencies of their suspensions at various particle concentrations. We found that the quantum efficiency (QE) of SQS particles in deionized (DI) water was much lower than that of the QDs even at low particle concentration, mainly due to the light scattering of emitted photons at the silica/water interface, followed by reabsorption by QDs. As the concentration of SQS particles was increased, both light scattering and reabsorption by QDs became more important, which further reduced the QE. Refractive index-matched solvent, however, reduced light scattering, yielding greater QE than DI water. Next, we induced aggregation of SQS particles, and found that QE increased as particles aggregated in DI water because of reduced light scattering and reabsorption, whereas it remained almost constant in the refractive index-matched solvent. Finally, we studied aggregation of highly concentrated silica particle suspensions containing a low concentration of SQS particles, and found that QE increased with aggregation because light scattering and reabsorption were reduced.

Self-organization of nanorods into ultra-long range two-dimensional monolayer end-to-end network.

Highly uniform large-scale assembly of nanoscale building blocks can enable unique collective properties for practical electronic and photonic devices. We present a two-dimensional (2-D), millimeter-scale network of colloidal CdSe nanorods (NRs) in monolayer thickness through end-to-end linking. The colloidal CdSe NRs are sterically stabilized with tetradecylphosphonic acid (TDPA), and their tips are partially etched in the presence of gold chloride (AuCl3) and didecyldimethylammonium bromide (DDAB), which make them unwetted in toluene. This change in surface wetting property leads to spontaneous adsorption at the 2-D air/toluene interface. Anisotropy in both the geometry and the surface property of the CdSe NRs causes deformation of the NR/toluene/air interface, which derives capillary attraction between tips of neighboring NRs inward. As a result, the NRs confined at the interface spontaneously form a 2-D network composed of end-to-end linkages. We employ a vertical-deposition approach to maintain a consistent rate of NR supply to the interface during the assembly. The rate control turns out to be pivotal in the preparation of a highly uniform large scale 2-D network without aggregation. In addition, unprecedented control of the NR density in the network was possible by adjusting either the lift-up speed of the immersed substrate or the relative concentration of AuCl3 to DDAB. Our findings provide important design criteria for 2-D assembly of anisotropic nanobuilding blocks.

Temperature and magnetic-field dependence of radiative decay in colloidal germanium quantum dots.

We conduct spectroscopic and theoretical studies of photoluminescence (PL) from Ge quantum dots (QDs) fabricated via colloidal synthesis. The dynamics of late-time PL exhibit a pronounced dependence on temperature and applied magnetic field, which can be explained by radiative decay involving two closely spaced, slowly emitting exciton states. In 3.5 nm QDs, these states are separated by ∼1 meV and are characterized by ∼82 µs and ∼18 µs lifetimes. By using a four-band formalism, we calculate the fine structure of the indirect band-edge exciton arising from the electron-hole exchange interaction and the Coulomb interaction of the Γ-point hole with the anisotropic charge density of the L-point electron. The calculations suggest that the observed PL dynamics can be explained by phonon-assisted recombination of excitons thermally distributed between the lower-energy "dark" state with the momentum projection J = ± 2 and a higher energy "bright" state with J = ± 1. A fairly small difference between lifetimes of these states is due to their mixing induced by the exchange term unique to crystals with a highly symmetric cubic lattice such as Ge.

Anisotropic microparticles created by phase separation of polymer blends confined in monodisperse emulsion drops.

Anisotropic microparticles are promising as a new class of colloidal or granular materials due to their advanced functionalities which are difficult to achieve with isotropic particles. However, synthesis of the anisotropic microparticles with a highly controlled size and shape still remains challenging, despite their intense demands. Here, we report a microfluidic approach to create uniform anisotropic microparticles using phase separation of polymer blends confined in emulsion drops. Two different polymers are homogeneously dissolved in organic solvent at low concentration, which is microfluidically emulsified to produce oil-in-water emulsion drops. As the organic solvent diffuses out, small domains are formed in the emulsion drops, which are then merged, forming only two distinct domains. After the drops are fully consolidated, uniform anisotropic microparticles with two compartments are created. The shape of the resulting microparticles is determined by combination of a pair of polymers and type of surfactant. Spherical microparticles with eccentric core and incomplete shell are prepared by consolidation of polystyrene (PS) and poly(lactic acid) (PLA), and microparticles with single crater are formed by consolidation of PS and poly(methyl methacrylate) (PMMA); both emulsions are stabilized with poly(vinyl alcohol) (PVA). With surfactants of triblock copolymer, acorn-shaped Janus microparticles are obtained by consolidating emulsion drops containing PS and PLA. This microfluidic production of anisotropic particles can be further extended to any combination of polymers and colloids to provide a variety of structural and chemical anisotropy.

Ultrastable PbSe nanocrystal quantum dots via in situ formation of atomically thin halide adlayers on PbSe(100).

The fast degradation of lead selenide (PbSe) nanocrystal quantum dots (NQDs) in ambient conditions impedes widespread deployment of the highly excitonic, thus versatile, colloidal NQDs. Here we report a simple in situ post-synthetic halide salt treatment that results in size-independent air stability of PbSe NQDs without significantly altering their optoelectronic characteristics. From TEM, NMR, and XPS results and DFT calculations, we propose that the unprecedented size-independent air stability of the PbSe NQDs can be attributed to the successful passivation of under-coordinated PbSe(100) facets with atomically thin PbX2 (X = Cl, Br, I) adlayers. Conductive films made of halide-treated ultrastable PbSe NQDs exhibit markedly improved air stability and behave as an n-type channel in a field-effect transistor. Our simple in situ wet-chemical passivation scheme will enable broader utilization of PbSe NQDs in ambient conditions in many optoelectronic applications.