Dangling Bond Defects: The Critical Roadblock to Efficient Photoconversion in Hybrid Quantum Dot Solar Cells

Inorganic–organic hybrid materials based on silicon quantum dots (SiQDs) have been utilized for photovoltaic applications but suffer from rapid charge recombination and low carrier mobility. We present an ab initio investigation of charge dynamics to pinpoint the source of this severe problem, and our results indicate that such devices show great promise provided that dangling bond (DB) defects can be sufficiently removed. Without DBs, the predicted charge transfer (CT) rate is much higher than that of photoluminescence (PL), while the electron hopping (EH) proceeds more quickly than interfacial charge recombination (CR). In contrast, one DB in a SiQD leads to a dramatic enhancement, by 10 orders of magnitude, in the CR rate and a reduction of the EH rate by 4 orders of magnitude, so that the diffusion of carriers to electrodes becomes extremely difficult. Although other factors, such as dot size distribution and oxidation, also play a deleterious role in device performance, their effects are deemed much less important than the critical role played by dangling bonds

Tunable and Energetically Robust PbS Nanoplatelets for Optoelectronic Applications

PbS nanoplatelets (NPLs) are proposed as robust materials for novel optoelectronic devices. Compared to quantum dot assemblies, ab initio simulations are employed to show that such pseudo-two-dimensional systems may provide stronger absorption and higher carrier mobility due to the distinct wave function distributions, large electronic couplings, and small hopping barriers. More importantly, both energetic and spatial traps are absent in conditions far from charge balance, indicating an extraordinary robustness against off-stoichiometry as a result of surface homogeneity and sufficient cross-linking. Based on our findings, we present several types of optoelectronic device architectures spanning photovoltaics and photodetectors that could take advantage of the superior properties found in NPLs

Toward the Ultimate Limit of Connectivity in Quantum Dots with High Mobility and Clean Gaps

Colloidal quantum dots (CQDs) are highly versatile nanoscale optoelectronic building blocks, but despite their materials engineering flexibility, there is a considerable lack of fundamental understanding of their electronic structure as they couple within thin films. By employing a joint experimental–theoretical study, we reveal the impact of connectivity in CQD assemblies, going beyond the single CQD picture. High-resolution transmission electron microscopy (HR-TEM) demonstrates connectivity motifs across different CQD sizes and length scales and provides the necessary perspective to build robust computational models to systematically study the achievable degree of connectivity in these materials. We focused on state-of-the-art surface ligand treatments, taking into account both the degree of connectivity and nanocrystal orientation, and performed <i>ab initio</i> simulations within the phonon-assisted hopping regime. Importantly, both the TEM studies and our simulation results revealed morphological and electronic defects that could dramatically reduce optoelectronic performance, and yet would not have been captured within a single CQD model that neglects connectivity. We calculate carrier mobility in the presence of such defect states and conclude that the best-achievable CQD assemblies for optoelectronics will require a modest degree of fusing <i>via</i> the {001} facet, followed by atomic ligand passivation to generate a clean band gap and unprecedentedly high charge transport

Room Temperature Multiferroicity of Charge Transfer Crystals

Room temperature multiferroics has been a frontier research field by manipulating spin-driven ferroelectricity or charge-order-driven magnetism. Charge-transfer crystals based on electron donor and acceptor assembly, exhibiting simultaneous spin ordering, are drawing significant interests for the development of all-organic magnetoelectric multiferroics. Here, we report that a remarkable anisotropic magnetization and room temperature multiferroicity can be achieved through assembly of thiophene donor and fullerene acceptor. The crystal motif directs the dimensional and compositional control of charge-transfer networks that could switch magnetization under external stimuli, thereby opening up an attractive class of all-organic nanoferronics

Epitaxial Templating of Two-Dimensional Metal Chloride Nanocrystals on Monolayer Molybdenum Disulfide

We demonstrate the formation of ionic metal chloride (CuCl) two-dimensional (2D) nanocrystals epitaxially templated on the surface of monolayer molybdenum disulfide (MoS₂). These 2D CuCl nanocrystals are single atomic planes from a nonlayered bulk CuCl structure. They are stabilized as a 2D monolayer on the surface of the MoS₂ through interactions with the uniform periodic surface of the MoS₂. The heterostructure 2D system is studied at the atomic level using aberration-corrected transmission electron microscopy at 80 kV. Dynamics of discrete rotations of the CuCl nanocrystals are observed, maintaining two types of preferential alignments to the MoS₂ lattice, confirming that the strong interlayer interactions drive the stable CuCl structure. Strain maps are produced from displacement maps and used to track real-time variations of local atomic bonding and defect production. Density functional theory calculations interpret the formation of two types of energetically advantageous commensurate superlattices <i>via</i> strong chemical bonds at interfaces and predict their corresponding electronic structures. These results show how vertical heterostructured 2D nanoscale systems can be formed beyond the simple assembly of preformed layered materials and provide indications about how different 2D components and their interfacial coupling mode could influence the overall property of the heterostructures

Freestanding Organic Charge-Transfer Conformal Electronics

Wearable conformal electronics are essential components for next-generation humanlike sensing devices that can accurately respond to external stimuli in nonplanar and dynamic surfaces. However, to explore this potential, it is indispensable to achieve the desired level of deformability and charge-transport mobility in strain-accommodating soft semiconductors. Here, we show pseudo-two-dimensional freestanding conjugated polymer heterojunction nanosheets integrated into substrate-free conformal electronics owing to their exceptional crystalline controlled charge transport and high level of mechanical strength. These freestanding and mechanical robust polymer nanosheets can be adapted into a variety of artificial structured surfaces such as fibers, squares, circles, etc., which produce large-area stretchable conformal charge-transfer sensors for real-time static and dynamic monitoring

Atomic Structure and Dynamics of Defects in 2D MoS₂ Bilayers

We present a detailed atomic-level study of defects in bilayer MoS₂ using aberration-corrected transmission electron microscopy at an 80 kV accelerating voltage. Sulfur vacancies are found in both the top and bottom layers in 2H- and 3R-stacked MoS₂ bilayers. In 3R-stacked bilayers, sulfur vacancies can migrate between layers but more preferably reside in the (Mo–2S) column rather than the (2S) column, indicating more complex vacancy production and migration in the bilayer system. As the point vacancy number increases, aggregation into larger defect structures occurs, and this impacts the interlayer stacking. Competition between compression in one layer from the loss of S atoms and the van der Waals interlayer force causes much less structural deformations than those in the monolayer system. Sulfur vacancy lines neighboring in top and bottom layers introduce less strain compared to those staggered in the same layer. These results show how defect structures in multilayered two-dimensional materials differ from their monolayer form

Atomically Flat Zigzag Edges in Monolayer MoS₂ by Thermal Annealing

The edges of 2D materials show novel electronic, magnetic, and optical properties, especially when reduced to nanoribbon widths. Therefore, methods to create atomically flat edges in 2D materials are essential for future exploitation. Atomically flat edges in 2D materials are found after brittle fracture or when electrically biasing, but a simple scalable approach for creating atomically flat periodic edges in monolayer 2D transition metal dichalcogenides has yet to be realized. Here, we show how heating monolayer MoS₂ to 800 °C in vacuum produces atomically flat Mo terminated zigzag edges in nanoribbons. We study this at the atomic level using an ultrastable in situ heating holder in an aberration-corrected transmission electron microscope and discriminating Mo from S at the edge, revealing unique Mo terminations for all zigzag orientations that remain stable and atomically flat when cooling back to room temperature. Highly faceted MoS₂ nanoribbon constrictions are produced with Mo rich edge structures that have theoretically predicted spin separated transport channels, which are promising for spin logic applications

Molecular Assembly-Induced Charge Transfer for Programmable Functionalities

The donor–acceptor interface within molecular charge transfer (CT) solids plays a vital role in the hybridization of molecular orbitals to determine their carrier transport and electronic delocalization. In this study, we demonstrate molecular assembly-driven bilayer and crystalline solids, consisting of electron donor dibenzotetrathiafulvalene (DBTTF) and acceptor C₆₀, in which interfacial engineering-induced CT degree control is a key parameter for tuning its optical, electronic, and magnetic performance. Compared to the DBTTF/C₆₀ bilayer structure, the DBTTFC₆₀ cocrystalline solids show a stronger degree of charge transfer for broad CT absorption and a large dielectric constant. In addition, the DBTTFC₆₀ cocrystals exhibit distinct CT arrangement-driven anisotropic electron mobility and spin characteristics, which further enables the development of high-penetration and high-energy γ-ray photodetectors. The results presented in this paper provide a basis for the design and control of molecular charge transfer solids, which facilitates the integration of such materials into molecular electronics

Bandgap Tuning of Silicon Quantum Dots by Surface Functionalization with Conjugated Organic Groups

The quantum confinement and enhanced optical properties of silicon quantum dots (SiQDs) make them attractive as an inexpensive and nontoxic material for a variety of applications such as light emitting technologies (lighting, displays, sensors) and photovoltaics. However, experimental demonstration of these properties and practical application into optoelectronic devices have been limited as SiQDs are generally passivated with covalently bound insulating alkyl chains that limit charge transport. In this work, we show that strategically designed triphenylamine-based surface ligands covalently bonded to the SiQD surface using conjugated vinyl connectivity results in a 70 nm red-shifted photoluminescence relative to their decyl-capped control counterparts. This suggests that electron density from the SiQD is delocalized into the surface ligands to effectively create a larger hybrid QD with possible macroscopic charge transport properties