Colloidal semiconductor II–VI metal chalcogenide (ME) magic-size clusters (MSCs) exhibit either an optical absorption singlet or doublet. In the latter case, a sharp photoluminescence (PL) signal is observed. Whether the PL-inactive MSCs transform to the PL-active ones is unknown. We show that PL-inactive CdS MSC-322 transforms to PL-active CdS MSC-328 and MSC-373 in the presence of acetic acid (HOAc). MSC-322 displays a sharp absorption at ≈322 nm, whereas MSC-328 and MSC-373 both have broad absorptions respectively around 328 and 373 nm. In a reaction of cadmium myristate and S powder in 1-octadecene, MSC-322 develops; with HOAc, MSC-328 and MSC-373 are present. We propose that the MSCs evolve from their relatively transparent precursor compounds (PCs). The PC-322 to PC-328 quasi-isomerization involves monomer substitution, while monomer addition occurs for the PC-328 to PC-373 transformation. Our findings suggest that S dominates the precursor self-assembly quantitatively, and ligand-bonded Cd mainly controls MSC optical properties.

The field of isomerization reactions for colloidal semiconductor magic-size clusters (MSCs) remains largely unexplored. Here, we show that MSCs isomerize via two fundamental pathways that are regulated by the acidity and amount of an incoming ligand, with CdTeSe as the model system. When MSC-399 isomerizes to MSC-422 at room temperature, the peak red-shift from 399 to 422 nm is continuous (pathway 1) and/or stepwise (pathway 2) as monitored in situ and in real time by optical absorption spectroscopy. We propose that pathway 1 is direct, with intracluster configuration changes and a relatively large energy barrier. Pathway 2 is indirect, assisted by the MSC precursor compounds (PCs), from MSC-399 to PC-399 to PC-422 to MSC-422. Pathway 1 is activated when PC-422 to MSC-422 is suppressed. Our findings unambiguously suggest that when a change occurs directly on a nanospecies, its absorption peak continuously shifts. The present study provides an in-depth understanding of the transformative behavior of MSCs via ligand-induced isomerization upon external chemical stimuli.

Microplastic contamination of the environment and ecosystem has attracted much attention in recent years. Its presence has been detected in the most remote regions and its propagation through the food chain poses a serious health risk to humans and animals. To better understand their presence in the environment, their detection and identification plays a critical role in any remediation effort. FTIR and Raman imaging provide simultaneously size metrology and spectral information and have been gold standard tools for microplastic analysis. In this study, we will present state-of-the-art chemical imaging methods, Fourier transform infrared spectroscopy (FTIR) and Raman imaging as well as quantum cascade laser mapping, for the detection of microplastic particles. We will demonstrate enhanced detection through the use of reflective substrates and discuss the signal enhancement strategies of these chemical imaging techniques as well as their limitations.

The transformation of colloidal semiconductor magic-size clusters (MSCs) from zinc to cadmium chalcogenide (ZnE to CdE) at low temperatures has received scant attention. Here, we report the first room-temperature evolution of CdE MSCs from ZnE samples and our interpretation of the transformation pathway. We show that when prenucleation stage samples of ZnE are mixed with cadmium oleate (Cd(OA)2), CdE MSCs evolve; without this mixing, ZnE MSCs develop. When ZnE MSCs and Cd(OA)2 are mixed, CdE MSCs also form. We propose that Cd(OA)2 reacts with the precursor compounds (PCs) of the ZnE MSCs but not directly with the ZnE MSCs. The cation exchange reaction transforms the ZnE PCs into CdE PCs, from which CdE MSCs develop. Our findings suggest that in reactions that lead to the production of binary ME quantum dots, the E precursor dominates the formation of binary ME PCs (M = Zn or Cd) to have similar stoichiometry. The present study provides a much more profound view of the formation and transformation mechanisms of the ME PCs.

A fundamental understanding of formation pathways is critical to the controlled synthesis of colloidal semiconductor nanocrystals. As ultrasmall-size quantum dots (QDs) sometimes emerge in reactions along with magic-size clusters (MSCs), distinguishing their individual pathway of evolution is important, but has proven difficult. To decouple the evolution of QDs and MSCs, an unconventional, selective approach has been developed, along with a two-pathway model that provides a fundamental understanding of production selectivity. For on-demand production of either ultrasmall QDs or MSCs, the key enabler is in how to allow a reaction to proceed in the time prior to nucleation and growth of QDs. In this prenucleation stage, an intermediate compound forms, which is the precursor compound (PC) to the MSC. Here, the two-pathway model and the manipulation of such PCs to synthesize either ultrasmall QDs or binary and ternary MSCs are highlighted. The two-pathway model will assist the development of nucleation theory as well as provide a basis for a mechanism-enabled design and predictive synthesis of functional nanomaterials.

Little is known about how to precisely promote the selective production of either colloidal semiconductor metal chalcogenide (ME), magic-size clusters (MSCs), or quantum dots (QDs). Recently, a two-pathway model has been proposed to comprehend their evolution; here, we reveal for the first time that the size of precursors plays a decisive role in the selected evolution pathway of MSCs and QDs. With the reaction of cadmium myristate (Cd(MA)2) and tri-n-octylphosphine selenide (SeTOP) in 1-octadecene (ODE) as a model system, the size of Cd precursors was manipulated by the steric hindrance of carboxylic acid (RCOOH) additive. Without RCOOH, the reaction produced both CdSe MSCs and QDs (from 100 to 240 °C). With RCOOH, the reaction produced MSCs or QDs when R was small (such as CH3−) or large (such as C6H5−), respectively. According to the two-pathway model, the selective evolution is attributed to the promotion and suppression of the self-assembly of Cd and Se precursors, respectively. We propose that the addition of carboxylic acid may occur ligand exchange with Cd(MA)2, causing the different sizes of Cd precursor. The results suggest that the size of Cd precursors regulates the self-assemble behavior of the precursors, which dictates the directed evolution of either MSCs or QDs. The present findings bring insights into the two-pathway model, as the size of M and E precursors determine the evolution pathways of MSCs or QDs, the understanding of which is of great fundamental significance toward mechanism-enabled design and predictive synthesis of functional nanomaterials.

The transformations of colloidal semiconductor magic-size clusters (MSCs) are expected to occur with only discrete, step-wise redshifts in optical absorption. Here, we challenge this assumption presenting a novel, conceptually different transformation, for which the redshift is continuous. In the room-temperature transformation from CdTe MSC-448 to MSC-488 (designated by the peak wavelengths in nanometer), the redshift of absorption monitored in situ displays distinctly continuous and/or step-wise behavior. Based on conclusive evidence provided by real-time experiments, the former transformation is apparently direct and intra-cluster with a relatively large energy barrier. The latter transformation is indirect and assisted by MSC precursor compounds (PCs). The former transformation follows the latter often, being predominant at a relatively high temperature. The present findings encourage a reconsideration of the absorption redshift reported previously for transformations of binary II-VI MSCs, together with the pathway associated without the increase of cluster mass.

It is not resolved which model describes better the aqueous-phase nucleation and growth of semiconductor quantum dots (QDs), the classical one-step one or the nonclassical multi-step one. Here, we design a room-temperature reaction to trap reaction intermediates in the prenucleation stage of ZnSe QDs (as a model system). We show that the trapped intermediate can transform to magic-size clusters (MSCs) via intra-molecular reorganization and can fragment to enable the growth of QDs. The MSCs exhibit a sharp optical absorption peaking at 299 nm, labelled MSC-299. The intermediate, the precursor compound (PC-299) of MSC-299, is optically transparent at 299 nm and to longer wavelengths. This intermediate forms in various Zn and Se reaction systems. The present study provides unambiguous evidence that the nonclassical and classical pathways are both necessary to explain the nucleation and growth of aqueous-phase QDs, with the former pathway favored more by high reaction concentrations.

The transformation pathway for magic-size clusters (MSCs) with absorption doublets has remained unknown so far. Meng Zhang, Jianrong Zeng, Kui Yu et al. propose in their Research Article on page 20358 that the transformation from the MSCs with characteristic optical absorption at 373/393 nm (dMSC-393) to those at 433/460 nm (dMSC-460) occurs via the addition reaction of the CdSe monomers to the precursor compound of dMSC-393.

A rarely studied transformation in colloidal ternary magic-size clusters (MSCs) is addressed. We report the first observation of the transformation from ternary CdTeSe MSC-399 to MSC-422, which occurs at room temperature. These two MSC types display sharp optical absorption resonances at 399 and 422 nm, respectively, and are related in that they are quasi isomers, together with their counterpart precursor compounds (PCs). Binary CdTe and CdSe samples were prepared in the prenucleation stage also called the induction period (IP). After they were mixed and placed in a mixture of toluene and octylamine, the transformation was found to take place and to be assisted by the addition of the CdSe IP sample. A binary IP sample contains corresponding binary PCs and monomers (Mo) and fragments (Fr). We argue that the transformation pathway is enabled by the corresponding ternary PCs, involving the substitution reaction, namely CdTeSe PC-399 + CdSe (Mo/Fr)-1 ⇒ CdTeSe PC-422 + CdSe (Mo/Fr)-2. The present study provides an in-depth understanding of the formation characteristics of the MSCs.

Der Transformationsmechanismus für Magic-Size-Cluster (MSCs) mit Absorptionsdubletts war bisher unbekannt. Meng Zhang, Jianrong Zeng, Kui Yu et al. postulieren in ihrem Forschungsartikel auf S. 20521, dass die Transformation der MSCs mit charakteristischer optischer Absorption bei 373/393 nm (dMSC-393) zu solchen bei 433/460 nm (dMSC-460) über die Additionsreaktion der CdSe-Monomere an die Vorläuferverbindung von dMSC-393 erfolgt.

Divergent interpretations have appeared in the literature regarding the structural nature and evolutionary behavior for photoluminescent CdSe nanospecies with sharp doublets in optical absorption. We report a comprehensive description of the transformation pathway from one CdSe nanospecies displaying an absorption doublet at 373/393 nm to another species with a doublet at 433/460 nm. These two nanospecies are zero-dimensional (0D) magic-size clusters (MSCs) with 3D quantum confinement, and are labeled dMSC-393 and dMSC-460, respectively. Synchrotron-based small-angle X-ray scattering (SAXS) returns a radius of gyration of 0.92 nm for dMSC-393 and 1.14 nm for dMSC-460, and indicates that both types are disc shaped with the exponent of the SAXS form factor equal to 2.1. The MSCs develop from their unique counterpart precursor compounds (PCs), which are labeled PC-393 and PC-460, respectively. For the dMSC-393 to dMSC-460 transformation, the proposed PC-enabled pathway is comprised of three key steps, dMSC-393 to PC-393 (Step 1), PC-393 to PC-460 (Step 2 involving monomer addition), and PC-460 to dMSC-460 (Step 3). The present study provides a framework for understanding the PC-based evolution of MSCs and how PCs enable transformations between MSCs.

A knowledge of colloidal semiconductor magic-size clusters (MSCs) is essential for understanding how fundamental properties evolve during transformations from individual molecules to semiconductor quantum dots (QDs). Compared to QDs, MSCs display much narrower optical absorption bands; the higher cluster stability gives rise to a narrower size distribution. During the production of binary QDs such as II-VI metal (M) chalcogenide (E) ones, binary ME MSCs observed were interpreted as side products and/or the nuclei of QDs. Prior to the current development of our two-step approach followed by our two-pathway model, it had been extremely challenging to synthesize MSCs as a unique product without the nucleation and growth of QDs. With the two-step approach, we have demonstrated that MSCs can be readily engineered as a sole product at room temperature from a prenucleation stage sample, also called an induction period (IP) sample. It is important that we were able to discover that the evolution of the MSCs follows first-order reaction kinetics behavior. Accordingly, we proposed that a new type of compound, termed as "precursor compounds" (PCs) of MSCs, was produced in an IP sample. Such PCs are optically transparent at the absorption peak positions of their MSC counterparts as well as to longer wavelengths. It is thought that quasi isomerization of a single PC results in the development of one MSC.In this Account, we provide an overview of our latest advances regarding the transformations among binary CdE MSCs as well as from binary CdTe to ternary CdTeSe MSCs. Optical absorption spectroscopy has been employed to study these transformations, all of which display well-defined isosbestic points. We have proposed that these MSC to MSC transformations occur via their corresponding PCs, also called immediate PCs. It is reasonable that the as-synthesized PC (in an IP sample) and the immediate PC (in an incubated and/or diluted sample) probably have different configurations. A transformation between two PCs may involve an intermolecular reaction, with either first-order reaction kinetics or a more complicated time profile. A transformation between one immediate PC and its counterpart MSC may contain an intramolecular reaction. The present Account, which addresses the PC-enabled MSC transformations with isosbestic points probed by optical absorption spectroscopy, calls for more experimental and theoretical attention to understand these magic species and their transformation processes more precisely.

Morphological information has been obtained using the strong near-infrared photoluminescence emitted by germanium (Ge) nanocrystals (NCs) coherently imbedded in SiGe alloy layers, grown by molecular beam epitaxy on Si substrates. The emission spectra are analyzed for the effects of strain, carrier confinement, and disorder over a wide range of Ge concentrations in the surrounding SiGe medium. This analysis provided significant insight into the properties of the Ge nanocrystals, including their size and shape. We also discuss the mechanisms leading to the high quantum efficiency observed for emission from the Ge nanocrystals at low temperatures. We indicate how direct gap behavior might be achieved for Ge NCs lattice matched within dilute Ge1-ySny alloys, where tensile strain would be present in the NCs in all three directions.

This Chapter discusses the phenomena associated with germanium (Ge) nanocrystals emitting near infrared radiation under optical excitation. We describe how the emission properties are influenced by various effects, including those of strain and particle confinement, as well as excitation mechanisms. Two example systems are discussed, namely one of isolated Ge quantum dots and another of Ge nanocrystals coherently imbedded in SiGe alloy layers, where both systems were grown by molecular beam epitaxy (MBE) on Si substrates. For the Ge dot ensembles, we show how particle size information can be derived from the emission spectrum. For the Ge nanocrystals, the emission spectra are analyzed for the effects of strain and particle confinement over a wide range of Ge fractions in the surrounding SiGe medium. This analysis provided significant insight into the properties of the Ge nanocrystals, including their size and shape, which were a 1.4 nm thickness in the MBE growth direction and a 7 nm lateral dimension. We also discuss the mechanisms leading to the high quantum efficiency observed for emission from the Ge nanocrystals at low temperatures.

We report the first observation of the reversible transformations that occur among three types of CdTe magic-size clusters (MSCs) in dispersion at room temperature and discuss our understanding of the transformation pathway. The reversible transformations were achieved with CdTe prenucleation stage samples, which were prepared with reactions of cadmium oleate [Cd(OA)2] and tri-n-octylphosphine telluride in 1-octadecene and were then dispersed in mixtures of toluene and a primary amine at room temperature. Three types of OA-passivated CdTe MSCs evolved, exhibiting sharp optical absorption singlets peaking at 371, 417, and 448 nm. The MSCs and their immediate precursor compounds (PCs; with no sharp optical absorption) are labeled by the MSC absorption peak wavelengths. The transformation between MSC-371 and MSC-417 has a distinct isosbestic point at ∼385 nm and that between MSC-417 and MSC-448 at ∼430 nm. Our findings suggest that these PC-enabled reversible transformations occur through a process of quasi-isomerization, transforming between PCs and their counterpart MSCs, combined with substitution reactions that cause transformation between the two involved PCs.

CdTeSe alloy magic-size clusters have been synthesized, but the formation mechanism of their precursor compounds (which can transform into CdTeSe magic-size clusters) was unknown. As reported by X. Chen, K. Yu, and co-workers in their Research Article on page 16943, CdTeSe precursor compounds were formed through a substitution reaction: CdTe precursor compound + CdSe monomer/fragment → CdTeSe precursor compound + CdTe monomer/fragment.

Silicon-Germanium strain engineering has been used for more than two decades in silicon based devices and has contributed to the scaling down of a transistor’s size and to significant improvements in device performance. However, while conventional silicon-germanium based electronics has experienced rapid and steady growth, thanks to this continuous miniaturization of transistors, this trend cannot continue indefinitely. Industry has already moved to alternate methods such as FinFET devices, in which a thin silicon channel is placed vertically, and the FD-SOI (FD-SGOI) design consisting of a thin film Si(SiGe) channel placed horizontally. For nodes scaled down below 28 nm, low power operation will be inherently hindered by both the imperfect interface, non-uniformity of ultra-thin films and quantum confinement effects, which increase the effective bandgap. In these devices, despite the intense research activity on the strained SiGe ultra-thin body, which accounts for a large portion of such microelectronic devices (below the 45 nm node), we still fail to properly understand the mechanisms that limit hole and electron mobilities in SGOI layers. In addition, one of the main challenges for Si based devices remains the fabrication of efficient group-IV photon sources / photon detectors compatible with the microelectronic industry, which would usefully replace the integration of III-V heterostructures on Si. The major bottleneck is that group-IV semiconductor elements have indirect bandgaps, but with possibilities of being transformed to direct bandgaps using strain engineering strategies. In this presentation, we will review the formation mechanism of Ge-rich layers on SOI by condensation at different temperatures. TEM cross-section and GPA analysis of the heterostructures will be presented. We will also report the physical and optical properties of these heterostructures. Special attention is devoted to the influence of the SiGe thickness reduction (up to few MLs), where quantum confinement is prominent in the optical properties of the layers. Raman and PL results will be presented to better explain such confinement behavior. We show that novel SGOI substrates could represent a key strategy for the fabrication of future photonic devices.

Aqueous-phase approaches to semiconductor CdS magic-size clusters (MSCs) and the formation pathway have remained relatively unexplored. Here, we report the demonstration of an aqueous-phase, room-temperature approach to CdS MSCs, together with an exploration of their evolution pathway. The resulting CdS MSCs display a sharp optical absorption peak at about 360 nm and are labeled MSC-360. With CdCl 2 and thiourea as the respective Cd and S sources, and 3-mercarpotopropionic acid as the ligand, CdS MSC-360 develops in a mixture of a primary amine and water. We argue that the primary amine facilitates room-temperature decomposition of thiourea when CdCl 2 is present, and the formation pathway of MSCs is similar to that in organic-phase approaches. Our findings show there is a viable avenue to room-temperature aqueous-phase formation of CdS MSCs. Providing explanations of the procedure developed including the formation of large aggregates, the present study represents an important advance towards a mechanistic understanding of nanocrystal synthesis.

There is a continuing, urgent need for an ophthalmic (eye) drop for the clinical therapy of age-related macular degeneration (AMD), a leading cause of blindness. Here, we report the first formulation of an eye drop that is effective via autophagy for AMD treatment. This eye drop is based on a single natural product derivative (ACD), which is an amphiphilic molecule containing a 6-aminohexanoate group (H2N(CH2)5COO-). We demonstrate that this eye drop reverses the abnormal angiogenesis induced in a primate model of AMD that has the pathological characteristics close to that of human AMD. The ACD molecule was self-assembled in an aqueous environment leading to nanoparticles (NPs) about 9.0 nm in diameter. These NPs were encapsulated in calcium alginate hydrogel. The resulting eye drop effectively slowed the release of ACD and displayed extended release periods in both simulated blood (pH 7.4) and inflammatory (pH 5.2) environments. We show that the eye drop penetrated both the corneal and blood-eye barriers and reached the fundus. With low cellular toxicity, the drop targeted S1,25D3-membrane-associated rapid response steroid-binding protein (1,25D3-MARRS) promoting autophagy in a dose-dependent manner. In addition, the drop inhibited cell migration and tubular formation. On the other hand, when protein 1,25D3-MARRS was knocked down, the eye drop did not exhibit such inhibition functionalities. Our study indicates that the 6-aminohexanoate group on self-assembled NPs encapsulated in hydrogel leads to the positive in vivo outcomes. The present formulation offers a promising approach for clinical treatment of human AMD.