Polycyclic Aromatic Hydrocarbons (PAHs) in Interstellar Ices: A Computational Study into How the Ice Matrix Influences the Ionic State of PAH Photoproducts.

It has been experimentally observed that water-ice-embedded polycyclic aromatic hydrocarbons (PAHs) form radical cations when exposed to vacuum UV irradiation, whereas ammonia-embedded PAHs lead to the formation of radical anions. In this study, we explain this phenomenon by investigating the fundamental electronic differences between water and ammonia, the implications of these differences on the PAH-water and PAH-ammonia interaction, and the possible ionization pathways in these complexes using density functional theory (DFT) computations. In the framework of the Kohn-Sham molecular orbital (MO) theory, we show that the ionic state of the PAH photoproducts results from the degree of occupied-occupied MO mixing between the PAHs and the matrix molecules. When interacting with the PAH, the lone pair-type highest occupied molecular orbital (HOMO) of water has poor orbital overlap and is too low in energy to mix with the filled π-orbitals of the PAH. As the lone-pair HOMO of ammonia is significantly higher in energy and has better overlap with filled π-orbitals of the PAH, the subsequent Pauli repulsion leads to mixed MOs with both PAH and ammonia character. By time-dependent DFT calculations, we demonstrate that the formation of mixed PAH-ammonia MOs opens alternative charge-transfer excitation pathways as now electronic density from ammonia can be transferred to unoccupied PAH levels, yielding anionic PAHs. As this pathway is much less available for water-embedded PAHs, charge transfer mainly occurs from localized PAH MOs to mixed PAH-water virtual levels, leading to cationic PAHs.

Near-Edge Ligand Stripping and Robust Radiative Exciton Recombination in CdSe/CdS Core/Crown Nanoplatelets.

We address the relation between surface chemistry and optoelectronic properties in semiconductor nanocrystals using core/crown CdSe/CdS nanoplatelets passivated by cadmium oleate (Cd(Ol)2) as model systems. We show that addition of butylamine to a nanoplatelet (NPL) dispersion maximally displaces ∼40% of the original Cd(Ol)2 capping. On the basis of density functional theory simulations, we argue that this behavior reflects the preferential displacement of Cd(Ol)2 from (near)-edge surface sites. Opposite from CdSe core NPLs, core/crown NPL dispersions can retain 45% of their initial photoluminescence efficiency after ligand displacement, while radiative exciton recombination keeps dominating the luminescent decay. Using electron microscopy observations, we assign this robust photoluminescence to NPLs with a complete CdS crown, which prevents charge carrier trapping in the near-edge surface sites created by ligand displacement. We conclude that Z-type ligands such as cadmium carboxylates can provide full electronic passivation of (100) facets yet are prone to displacement from (near)-edge surface sites.

Role of Surface Reduction in the Formation of Traps in n-Doped II-VI Semiconductor Nanocrystals: How to Charge without Reducing the Surface.

The efficiency of nanocrystal (NC)-based devices is often limited by the presence of surface states that lead to localized energy levels in the bandgap. Yet, a complete understanding of the nature of these traps remains challenging. Although theoretical modeling has greatly improved our comprehension of the NC surface, several experimental studies suggest the existence of metal-based traps that have not yet been found with theoretical methods. Since there are indications that these metal-based traps form in the presence of excess electrons, the present work uses density functional theory (DFT) calculations to study the effects of charging II-VI semiconductor NCs with either full or imperfect surface passivation. It is found that charge injection can lead to trap-formation via two pathways: metal atom ejection from perfectly passivated NCs or metal-metal dimer-formation in imperfectly passivated NCs. Fully passivated CdTe NCs are observed to be stable up to a charge of two electrons. Further reduction leads to charge localization on a surface Cd atom and the formation of in-gap states. The effects of suboptimal passivation are probed by charging NCs where an X-type ligand is removed from the (100) plane. In this case, injection of even one electron leads to Cd-dimerization and trap-formation. Addition of an L-type amine ligand prevents this dimer-formation and is suggested to also prevent trapping of photoexcited electrons in charge neutral NCs. The results presented in this work are generalized to NCs of different sizes and other II-VI semiconductors. This has clear implications for n-doping II-VI semiconductor NCs without introducing surface traps due to metal ion reduction. The possible effect of these metal ion localized traps on the photoluminescence efficiency of neutral NCs is also discussed.

Double helical conformation and extreme rigidity in a rodlike polyelectrolyte.

The ubiquitous biomacromolecule DNA has an axial rigidity persistence length of ~50 nm, driven by its elegant double helical structure. While double and multiple helix structures appear widely in nature, only rarely are these found in synthetic non-chiral macromolecules. Here we report a double helical conformation in the densely charged aromatic polyamide poly(2,2'-disulfonyl-4,4'-benzidine terephthalamide) or PBDT. This double helix macromolecule represents one of the most rigid simple molecular structures known, exhibiting an extremely high axial persistence length (~1 micrometer). We present X-ray diffraction, NMR spectroscopy, and molecular dynamics (MD) simulations that reveal and confirm the double helical conformation. The discovery of this extreme rigidity in combination with high charge density gives insight into the self-assembly of molecular ionic composites with high mechanical modulus (~ 1 GPa) yet with liquid-like ion motions inside, and provides fodder for formation of other 1D-reinforced composites.

Rationalizing and Controlling the Surface Structure and Electronic Passivation of Cesium Lead Halide Nanocrystals.

Colloidal lead halide perovskite nanocrystals (NCs) have recently emerged as versatile photonic sources. Their processing and luminescent properties are challenged by the lability of their surfaces, i.e., the interface of the NC core and the ligand shell. On the example of CsPbBr3 NCs, we model the nanocrystal surface structure and its effect on the emergence of trap states using density functional theory. We rationalize the typical observation of a degraded luminescence upon aging or the luminescence recovery upon postsynthesis surface treatments. The conclusions are corroborated by the elemental analysis. We then propose a strategy for healing the surface trap states and for improving the colloidal stability by the combined treatment with didodecyldimethylammonium bromide and lead bromide and validate this approach experimentally. This simple procedure results in robust colloids, which are highly pure and exhibit high photoluminescence quantum yields of up to 95-98%, retained even after three to four rounds of washing.

Colloidal CdSe Nanoplatelets, A Model for Surface Chemistry/Optoelectronic Property Relations in Semiconductor Nanocrystals.

While the surface termination of quasi-spherical metal chalcogenide nanocrystals or quantum dots has been widely investigated, it remains unclear whether the ensuing surface chemistry models apply to similar nanocrystals with anisotropic shapes. In this work, we report on the surface-chemistry of 2D CdSe nanoplatelets, where we make use of an improved synthesis strategy that yields stable and aggregation free nanoplatelet suspensions with a photoluminescence quantum yield as high as 55%. We confirm that such nanoplatelets are enriched in Cd and, by means of 1H nuclear magnetic resonance spectroscopy, we show that the Cd-rich surface is terminated by X-type carboxylate ligands. Not unlike CdSe quantum dots (QDs), entire cadmium carboxylate entities can be displaced by the addition of amines, and the desorption isotherm points toward a considerable binding site heterogeneity. Moreover, we find that even the slightest displacement of cadmium carboxylate ligands quenches the nanoplatelet photoluminescence. These experimental findings are further confirmed by density functional theory (DFT) calculations on a 5 monolayer model CdSe nanoplatelet. These simulations show that the most labile ligands are located in the vicinity of facet edges, and that the displacement of ligands from such edge sites creates midgap states that can account for the observed photoluminescence quenching. Next to extending surface chemistry insights from colloidal QDs to nanoplatelets, this work indicates that CdSe nanoplatelets constitute a unique nanocrystal model system to establish a comprehensive description of midgap trap states, which includes their structural, chemical, and electronic properties.

Hot-electron transfer in quantum-dot heterojunction films.

Thermalization losses limit the photon-to-power conversion of solar cells at the high-energy side of the solar spectrum, as electrons quickly lose their energy relaxing to the band edge. Hot-electron transfer could reduce these losses. Here, we demonstrate fast and efficient hot-electron transfer between lead selenide and cadmium selenide quantum dots assembled in a quantum-dot heterojunction solid. In this system, the energy structure of the absorber material and of the electron extracting material can be easily tuned via a variation of quantum-dot size, allowing us to tailor the energetics of the transfer process for device applications. The efficiency of the transfer process increases with excitation energy as a result of the more favorable competition between hot-electron transfer and electron cooling. The experimental picture is supported by time-domain density functional theory calculations, showing that electron density is transferred from lead selenide to cadmium selenide quantum dots on the sub-picosecond timescale.

Colloidal CsPbX3 (X = Cl, Br, I) Nanocrystals 2.0: Zwitterionic Capping Ligands for Improved Durability and Stability.

Colloidal lead halide perovskite nanocrystals (NCs) have recently emerged as versatile photonic sources. Their processing and optoelectronic applications are hampered by the loss of colloidal stability and structural integrity due to the facile desorption of surface capping molecules during isolation and purification. To address this issue, herein, we propose a new ligand capping strategy utilizing common and inexpensive long-chain zwitterionic molecules such as 3-(N,N-dimethyloctadecylammonio)propanesulfonate, resulting in much improved chemical durability. In particular, this class of ligands allows for the isolation of clean NCs with high photoluminescence quantum yields (PL QYs) of above 90% after four rounds of precipitation/redispersion along with much higher overall reaction yields of uniform and colloidal dispersible NCs. Densely packed films of these NCs exhibit high PL QY values and effective charge transport. Consequently, they exhibit photoconductivity and low thresholds for amplified spontaneous emission of 2 µJ cm-2 under femtosecond optical excitation and are suited for efficient light-emitting diodes.

Quantum-Confined and Enhanced Optical Absorption of Colloidal PbS Quantum Dots at Wavelengths with Expected Bulk Behavior.

Nowadays it is well-accepted to attribute bulk-like optical absorption properties to colloidal PbS quantum dots (QDs) at wavelengths above 400 nm. This assumption permits to describe PbS QD light absorption by using bulk optical constants and to determine QD concentration in colloidal solutions from simple spectrophotometric measurements. Here we demonstrate that PbS QDs experience the quantum confinement regime across the entire near UV-vis-NIR spectral range, therefore also between 350 and 400 nm already proposed to be sufficiently far above the band gap to suppress quantum confinement. This effect is particularly relevant for small PbS QDs (with diameter of ≤4 nm) leading to absorption coefficients that largely differ from bulk values (up to ∼40% less). As a result of the broadband quantum confinement and of the high surface-to-volume ratio peculiar of nanocrystals, suitable surface chemical modification of PbS QDs is exploited to achieve a marked, size-dependent enhancement of the absorption coefficients compared to bulk values (up to ∼250%). We provide empirical relations to determine the absorption coefficients at 400 nm of as-synthesized and ligand-exchanged PbS QDs, accounting for the broadband quantum confinement and suggesting a heuristic approach to qualitatively predict the ligand effects on the optical absorption properties of PbS QDs. Our findings go beyond formalisms derived from Maxwell Garnett effective medium theory to describe QD optical properties and permit to spectrophotometrically calculate the concentration of PbS QD solutions avoiding underestimation due to deviations from the bulk. In perspective, we envisage the use of extended π-conjugated ligands bearing electronically active substituents to enhance light-harvesting in QD solids and suggest the inadequacy of the representation of ligands at the QD surface as mere electric dipoles.

Chemically Triggered Formation of Two-Dimensional Epitaxial Quantum Dot Superlattices.

Two dimensional superlattices of epitaxially connected quantum dots enable size-quantization effects to be combined with high charge carrier mobilities, an essential prerequisite for highly performing QD devices based on charge transport. Here, we demonstrate that surface active additives known to restore nanocrystal stoichiometry can trigger the formation of epitaxial superlattices of PbSe and PbS quantum dots. More specifically, we show that both chalcogen-adding (sodium sulfide) and lead oleate displacing (amines) additives induce small area epitaxial superlattices of PbSe quantum dots. In the latter case, the amine basicity is a sensitive handle to tune the superlattice symmetry, with strong and weak bases yielding pseudohexagonal or quasi-square lattices, respectively. Through density functional theory calculations and in situ titrations monitored by nuclear magnetic resonance spectroscopy, we link this observation to the concomitantly different coordination enthalpy and ligand displacement potency of the amine. Next to that, an initial ∼10% reduction of the initial ligand density prior to monolayer formation and addition of a mild, lead oleate displacing chemical trigger such as aniline proved key to induce square superlattices with long-range, square micrometer order; an effect that is the more pronounced the larger the quantum dots. Because the approach applies to PbS quantum dots as well, we conclude that it offers a reproducible and rational method for the formation of highly ordered epitaxial quantum dot superlattices.