A General Nucleation Model for Semiconductor Nanocrystals.

We introduce a nonclassical model for nanocrystal nucleation in solution which centers on the dynamic interplay of chemical bond breakage and formation coupled with the desolvation of precursor molecules, which we term the molecular chemistry (MC) model. Departing from classical theory, our model employs the bond count as the key variable rather than particle size, thereby redefining the role of supersaturation and its role in determining the so-called critical nucleus size. We apply the model to CdSe nanocrystal formation in nonpolar solvents and showcase its efficacy in predicting solvent dynamics, precursor characteristics, crystal phase, stoichiometry, "magic number" behavior, and transition states. While the coupled-cluster method is used to determine the bond energy, we show that it is possible to derive reaction pathways by reducing the calculations to algebraic approximations for the nucleation energy. This singular set of bond energy parameters allows nanocrystal nucleation and growth to be conceptualized as a straightforward chemical reaction.

The Multiple Roles of Na Ions in Highly Efficient CZTSSe Solar Cells.

Sodium (Na) doping is a well-established technique employed in chalcopyrite and kesterite solar cells. While various improvements can be achieved in crystalline quality, electrical properties, or defect passivation of the absorber materials by incorporating Na, a comprehensive demonstration of the desired Na distribution in CZTSSe is still lacking. Herein, a straightforward Na doping approach by dissolving NaCl into the CZTS precursor solution is proposed. It is demonstrated that a favorable Na ion distribution should comprise a precisely controlled Na+ concentration at the front surface and an enhanced distribution within the bottom region of the absorber layer. These findings demonstrated that Na ions play several positive roles within the device, leading to an overall power conversion efficiency of 12.51%.

Liquid Metal Doping Induced Asymmetry in Two-Dimensional Metal Oxides.

The emergence of ferroelectricity in two-dimensional (2D) metal oxides is a topic of significant technological interest; however, many 2D metal oxides lack intrinsic ferroelectric properties. Therefore, introducing asymmetry provides access to a broader range of 2D materials within the ferroelectric family. Here, the generation of asymmetry in 2D SnO by doping the material with Hf0.5Zr0.5O2 (HZO) is demonstrated. A liquid metal process as a doping strategy for the preparation of 2D HZO-doped SnO with robust ferroelectric characteristics is implemented. This technology takes advantage of the selective interface enrichment of molten Sn with HZO crystallites. Molecular dynamics simulations indicate a strong tendency of Hf and Zr atoms to migrate toward the surface of liquid metal and embed themselves within the growing oxide layer in the form of HZO. Thus, the liquid metal-based harvesting/doping technique is a feasible approach devised for producing novel 2D metal oxides with induced ferroelectric properties, represents a significant development for the prospects of random-access memories.

Temperature Dependence of the CdS Bandgap in the Extreme Confinement Regime.

A non-empirical equation describing the effect of size on the temperature dependence of the optical bandgap of CdS (dEg/dT) is obtained on the basis of the Brus equation. Intriguingly, we find that dEg/dT diverges strongly from bulk values only within the "extreme confinement" (EC) regime. We conducted both experimental and theoretical investigations of the absorption spectra of CdS clusters and quantum dots as a function of temperature above room temperature. Our results show that the value of dEg/dT obtained from absorption spectra in the EC regime is 2.5 times higher than in the strong confinement regime. Notable ligand sensitivities are also observed for dEg/dT in the case of CdS clusters. Ab initio molecular dynamics simulations and density functional theory calculations reveal that thermal fluctuations are the crucial factor influencing the bandgap temperature coefficient. Our results help resolve some long-standing debates regarding the dEg/dT behavior of semiconductor quantum dots.

Synthesis of Layered Lead-Free Perovskite Nanocrystals with Precise Size and Shape Control and Their Photocatalytic Activity.

Halide perovskites have attracted enormous attention due to their potential applications in optoelectronics and photocatalysis. However, concerns over their instability, toxicity, and unsatisfactory efficiency have necessitated the development of lead-free all-inorganic halide perovskites. A major challenge in designing efficient halide perovskites for practical applications is the lack of effective methods for producing nanocrystals with precise size and shape control. In this work, a layered perovskite, Cs4ZnSb2Cl12 (CZS), is found from calculations to exhibit size- and facet-dependent optoelectronic properties in the nanoscale, and thus, a colloidal method is used to synthesize the CZS nanoparticles with size-tunable morphologies: zero- (nanodots), one- (nanowires and nanorods), two- (nanoplates), and three-dimensional (nanopolyhedra). The growth kinetics of the CZS nanostructures, along with the effects of surface ligands, reaction temperature, and time were investigated. The optoelectronic properties of the nanocrystals varied with size due to quantum confinement effects and with shape due to anisotropy within the crystals and the exposure of specific facets. These properties could be modulated to enhance the visible-light photocatalytic performance for toluene oxidation. In particular, the 9.7 nm CZS nanoplates displayed a toluene to benzaldehyde conversion rate of 1893 µmol g-1 h-1 (95% selectivity), 500 times higher than the bulk synthesized CZS, and comparable with the reported photocatalysts. This study demonstrates the integration of theoretical calculations and synthesis, revealing an approach to the design and fabrication of novel, high-performance colloidal perovskite nanocrystals for optoelectronic and photocatalytic applications.

Ligand and solvent effects on the absorption spectra of CdS magic-sized clusters.

The absorption spectra of congenetic wurtzite (WZ) and zincblende (ZB) CdS magic-sized clusters are investigated. We demonstrate that the exciton peak positions can be tuned by up to 500 meV by varying the strong coupling between X-type ligands and the semiconductor cores, while the addition of L-type ligands primarily affects cluster midgap states. When Z-type ligands are displaced by L-type ligands, red shifts in the absorption spectra are observed, despite the fact there is a small decrease in cluster size. Density functional theory calculations are used to explain these findings and they reveal the importance of Cd and S dangling bonds on the midgap states during the Z- to L-type ligand exchange process. Overall, ZB CdS clusters show higher chemical stability than WZ clusters but their optical properties exhibit greater sensitivity to the solvent. Conversely, WZ CdS clusters are not stable in a Lewis base-rich environment, resulting in various changes in their spectra. Our findings enable researchers to select capping ligands that modulate the optical properties of semiconductor clusters while maintaining precise control over their solvent interactions.

Moisture-Assisted near-UV Emission Enhancement of Lead-Free Cs4CuIn2Cl12 Double Perovskite Nanocrystals.

Lead-based halide perovskite nanocrystals (NCs) are recognized as emerging emissive materials with superior photoluminescence (PL) properties. However, the toxicity of lead and the swift chemical decomposition under atmospheric moisture severely hinder their commercialization process. Herein, we report the first colloidal synthesis of lead-free Cs4CuIn2Cl12 layered double perovskite NCs via a facile moisture-assisted hot-injection method stemming from relatively nontoxic precursors. Although moisture is typically detrimental to NC synthesis, we demonstrate that the presence of water molecules in Cs4CuIn2Cl12 synthesis enhances the PL quantum yield (mainly in the near-UV range), induces a morphological transformation from 3D nanocubes to 2D nanoplatelets, and converts the dark transitions to radiative transitions for the observed self-trapped exciton relaxation. This work paves the way for further studies on the moisture-assisted synthesis of novel lead-free halide perovskite NCs for a wide range of applications.

Rational Atom Substitution to Obtain Efficient, Lead-Free Photocatalytic Perovskites Assisted by Machine Learning and DFT Calculations.

Inorganic lead-free halide perovskites, devoid of toxic or rare elements, have garnered considerable attention as photocatalysts for pollution control, CO2 reduction and hydrogen production. In the extensive perovskite design space, factors like substitution or doping level profoundly impact their performance. To address this complexity, a synergistic combination of machine learning models and theoretical calculations were used to efficiently screen substitution elements that enhanced the photoactivity of substituted Cs2 AgBiBr6 perovskites. Machine learning models determined the importance of d10 orbitals, highlighting how substituent electron configuration affects electronic structure of Cs2 AgBiBr6 . Conspicuously, d10 -configured Zn2+ boosted the photoactivity of Cs2 AgBiBr6 . Experimental verification validated these model results, revealing a 13-fold increase in photocatalytic toluene conversion compared to the unsubstituted counterpart. This enhancement resulted from the small charge carrier effective mass, as well as the creation of shallow trap states, shifting the conduction band minimum, introducing electron-deficient Br, and altering the distance between the B-site cations d band centre and the halide anions p band centre, a parameter tuneable through d10 configuration substituents. This study exemplifies the application of computational modelling in photocatalyst design and elucidating structure-property relationships. It underscores the potential of synergistic integration of calculations, modelling, and experimental analysis across various applications.

The quantum chemical solvation of indole: accounting for strong solute-solvent interactions using implicit/explicit models.

In this paper, we investigate the efficacy of different quantum chemical solvent modelling methods of indole in both water and methylcyclohexane solutions. The goal is to show that one can yield good photophysical properties in strongly coupled solute-solvent systems using standard DFT methods. We use standard and linearly-corrected Polarisable Continuum Models (PCM), as well as explicit solvation models, and compare the different model parameters, including the choice of density functional, basis set, and number of explicit solvent molecules. We demonstrate that implicit models overestimate energies and oscillator strengths. In particular, for indole-water, no level inversion is observed, suggesting a dielectric medium on its own is insufficient. In contrast, energies are seen to converge fairly rapidly with respect to cluster size towards experimentally measured properties in the explicit models. We find that the use of B3LYP with a diffuse basis set can adequately represent the photophysics of the system with a cluster size of between 9-12 explicit water molecules. Sampling of configurations from a molecular dynamics simulation suggests that the single point results are suitably representative of the solvated ensemble. For indole-water, we show that solvent reorganisation plays a significant role in stabilisation of the excited state energies. It is hoped that the findings and observations of this study will aid in the choice of solvation model parameters in future studies.

Efficient enumeration of bosonic configurations with applications to the calculation of non-radiative rates.

This work presents algorithms for the efficient enumeration of configuration spaces following Boltzmann-like statistics, with example applications to the calculation of non-radiative rates, and an open-source implementation. Configuration spaces are found in several areas of physics, particularly wherever there are energy levels that possess variable occupations. In bosonic systems, where there are no upper limits on the occupation of each level, enumeration of all possible configurations is an exceptionally hard problem. We look at the case where the levels need to be filled to satisfy an energy criterion, for example, a target excitation energy, which is a type of knapsack problem as found in combinatorics. We present analyses of the density of configuration spaces in arbitrary dimensions and how particular forms of kernel can be used to envelope the important regions. In this way, we arrive at three new algorithms for enumeration of such spaces that are several orders of magnitude more efficient than the naive brute force approach. Finally, we show how these can be applied to the particular case of internal conversion rates in a selection of molecules and discuss how a stochastic approach can, in principle, reduce the computational complexity to polynomial time.

Bilirubin analogues as model compounds for exciton coupling.

A series of phycobilin analogues have been investigated in terms of coupled excitonic systems. These compounds consist of a monomer, a tetrapyrrole structurally similar to bilirubin (bR), and two conjugated bR analogues. Spectroscopic and computational methods have been used to investigate the degree of interchromophore coupling. We find the synthesised bR analogue shows stronger excitonic coupling than bR, owing to a different molecular geometry. The excitonic coupling in the conjugated molecules can be controlled by modifying the bridge side-group. New computed energy levels for bR using the DFT/MRCI method are also presented, which improve on published values and re-assign the character of excited singlet states.

Computational Investigations of Dispersion Interactions between Small Molecules and Graphene-like Flakes.

We investigate dispersion interactions in a selection of atomic, molecular, and molecule-surface systems, comparing high-level correlated methods with empirically corrected density functional theory (DFT). We assess the efficacy of functionals commonly used for surface-based calculations, with and without the D3 correction of Grimme. We find that the inclusion of the correction is essential to get meaningful results, but there is otherwise little to distinguish between the functionals. We also present coupled-cluster quality interaction curves for H2, NO2, H2O, and Ar interacting with large carbon flakes, acting as models for graphene surfaces, using novel absolutely localized molecular orbital based methods. These calculations demonstrate that the problems with empirically corrected DFT when investigating dispersion appear to compound as the system size increases, with important implications for future computational studies of molecule-surface interactions.

Energetic degeneracy and electronic structures of germanium trimers doped with titanium.

Geometries and electronic structures of germanium trimer clusters doped with titanium TiGe3 -/0 were studied making use of the complete active space self-consistent field followed by second-order perturbation theory explicitly correlated coupled cluster singles and doubles method with perturbative triples corrections CCSD(T)-F12 and Tao-Perdew-Staroverov-Scuseria methods. Two electronic states (2A' and 2A″) of the anion (pyramid shape) were determined to be nearly degenerate and energetically competing for the anionic ground state of TiGe3 -. These two anionic states are believed to be concurrently populated in the experiment and induce six observed anion photoelectron bands. Total 14 electronic transitions starting from the 2A' and 2A″ states were assigned to five out of six visible bands in the experimental anion photoelectron spectrum of TiGe3 -. Each band was proven to be caused by multiple one-electron detachments from two populated anionic states. The last experimental band with the highest detachment energy is believed to be the result of various inner one-electron removals.

A computational exploration of aggregation-induced excitonic quenching mechanisms for perylene diimide chromophores.

Perylene diimide (PDI) derivatives are widely used materials for luminescent solar concentrator (LSC) applications due to their attractive optical and electronic properties. In this work, we study aggregation-induced exciton quenching pathways in four PDI derivatives with increasing steric bulk, which were previously synthesized. We combine molecular dynamics and quantum chemical methods to simulate the aggregation behavior of chromophores at low concentration and compute their excited state properties. We found that PDIs with small steric bulk are prone to aggregate in a solid state matrix, while those with large steric volume displayed greater tendencies to isolate themselves. We find that for the aggregation class of PDI dimers, the optically accessible excitations are in close energetic proximity to triplet charge transfer (CT) states, thus facilitating inter-system crossing and reducing overall LSC performance. While direct singlet fission pathways appear endothermic, evidence is found for the facilitation of a singlet fission pathway via intermediate CT states. Conversely, the insulation class of PDI does not suffer from aggregation-induced photoluminescence quenching at the concentrations studied here and therefore display high photon output. These findings should aid in the choice of PDI derivatives for various solar applications and suggest further avenues for functionalization and study.

Soft X-Ray and Cathodoluminescence Examination of a Tanzanian Graphite Deposit.

Hyperspectral soft X-ray emission (SXE) and cathodoluminescence (CL) spectrometry have been used to investigate a carbonaceous-rich geological deposit to understand the crystallinity and morphology of the carbon and the associated quartz. Panchromatic CL maps show both the growth of the quartz and the evidence of recrystallization. A fitted CL map reveals the distribution of Ti4+ within the grains and shows subtle growth zoning, together with radiation halos from 238U decay. The sensitivity of the SXE spectrometer to carbon, together with the anisotropic X-ray emission from highly orientated pyrolytic graphite, has enabled the C Kα peak shape to be used to measure the crystal orientation of individual graphite regions. Mapping has revealed that most grains are predominantly of a single orientation, and a number of graphite grains have been investigated to demonstrate the application of this new SXE technique. A peak fitting approach to analyzing the SXE spectra was developed to project the C Kα 2pz and 2p(x+y) orbital components of the graphite. The shape of these two end-member components is comparable to those produced by electron density of states calculations. The angular sensitivity of the SXE spectrometer has been shown to be comparable to that of electron backscatter diffraction.

Wafer-Sized Ultrathin Gallium and Indium Nitride Nanosheets through the Ammonolysis of Liquid Metal Derived Oxides.

We report the synthesis of centimeter sized ultrathin GaN and InN. The synthesis relies on the ammonolysis of liquid metal derived two-dimensional (2D) oxide sheets that were squeeze-transferred onto desired substrates. Wurtzite GaN nanosheets featured typical thicknesses of 1.3 nm, an optical bandgap of 3.5 eV and a carrier mobility of 21.5 cm2 V-1 s-1, while the InN featured a thickness of 2.0 nm. The deposited nanosheets were highly crystalline, grew along the (001) direction and featured a thickness of only three unit cells. The method provides a scalable approach for the integration of 2D morphologies of industrially important semiconductors into emerging electronics and optical devices.

On reverse Monte Carlo constraints and model reproduction.

Reverse Monte Carlo (RMC) simulations were performed to investigate the effectiveness of any combination of five experimentally motivated constraints on the reproduction of a test case, a ternary ab initio model. It was found that low energy structures fitting a variety of constraints commonly used in the RMC methodology could still provide an incorrect description of the chemical structural unit populations in multi-elemental systems. It is shown that the use of an elemental bond type constraint is an effective way to avoid this. © 2017 Wiley Periodicals, Inc.

Surface-gate-defined single-electron transistor in a MoS2 bilayer.

We report the multi-scale modeling and design of a gate-defined single-electron transistor in a MoS2 bilayer. By combining density-functional theory and finite-element analysis, we design a surface gate structure to electrostatically define and tune a quantum dot and its associated tunnel barriers in the MoS2 bilayer. Our approach suggests new pathways for the creation of novel quantum electronic devices in two-dimensional materials.

2D MoS2 PDMS Nanocomposites for NO2 Separation.

At a relatively low loading concentration (≈0.02 wt%) of 2D MoS 2 flakes in PDMS, the composite membrane is able to almost completely block the permeation of NO2 gas molecules at ppm levels. This major reduction is ascribed to the strong physisorption of NO2 gas molecules onto the 2D MoS2 flake basal planes.

Ab Initio Comparison of Bonding Environments and Threshold Behavior in Ge(x)As10Se(90-x) and Ge(x)Sb10Se(90-x) Glass Models.

Ab initio models of Ge(x)As10Se(90-x), and Ge(x)Sb10Se(90-x) glasses are constructed, and their bonding environments are characterized and compared against each other and to recent experimental studies of equivalent glasses at the same stoichiometry and density. A minimum in the linear refractive index is found to correlate with a maximum in the number of length-one, predominantly Se, atomic chains for both glass types. The threshold behavior difference between GeAsSe and GeSbSe is shown to be due to the appearance of As-As-Se2 structural units beyond the MCN = 2.67 threshold in the GeAsSe glasses.