Magic-sized Clusters Research Articles

Self-assembly of an organometallic Fe9O6 cluster from aerobic oxidation of (tmeda)Fe(CH2tBu)2.

Aerobic oxidation of (tmeda)Fe(CH2tBu)2 in toluene or THF solution leads to the self-assembly of a magic-sized all-ferrous oxide cluster containing the Fe9O6 subunit and bearing organometallic and diamine ligands. Mössbauer studies of the cluster are consistent with an all-ferrous assignment and magnetometry reveals complex intracluster and intercluster magnetic interactions.

Synthesis of InP branched nanostructures by controlling the intermediate nanoclusters

Herein, we present the syntheses of branched, hyper-branched and dendrimer-like InP nanostructures from InP magic-sized clusters and additives.

Transformation of ZnS Precursor Compounds to Magic-Size Clusters Exhibiting Optical Absorption Peaking at 269 nm.

We report our investigation on the transformation pathway from precursor compounds (PCs) to magic-size clusters (MSCs) for semiconductor ZnS. We show, for the first time, a synthetic approach to ZnS MSCs in a single-ensemble form exhibiting optical absorption peaking at 269 nm. We thus symbolize the MSCs as MSC-269. The synthesis was performed with zinc oleate (Zn(OA)2) and elemental sulfur (S) as the respective Zn and S sources and 1-octadecene (ODE) as the reaction medium. Prior to the addition of S, oleylamine (OLA) is mixed with Zn(OA)2. ZnS MSC-269 evolved at a relatively high temperature from a reaction mixture or at room temperature during a dispersion incubation of a reaction product in a solvent. Both optical absorption and NMR studies support that the evolution of colloidal semiconductor MSCs contains three different stages. The present study narrows our knowledge gap on PC-to-MSC transformations that involve a loss of ligands from the PC.

On-Demand Sonochemical Synthesis of Ultrasmall and Magic-Size CdSe Quantum Dots in Single-Phase and Emulsion Systems.

The sonochemical synthesis of CdSe quantum dots (QDs) in a single-liquid bulk phase and in an emulsion-based system is presented. Reactions utilized cadmium oleate and trioctylphosphine selenide precursors and were monitored as a function of sonication time under controlled temperature conditions to isolate the effects of cavitation from those of bulk temperature changes. QD synthesis was found to be slow in the single-phase liquid system (i.e., 1-octadecene) but greatly accelerated in the dispersed system (i.e., emulsions of 1-octadecene in ethylene glycol). It is hypothesized that the emulsion system increases the cavitation efficiency while also delivering acoustic energy in closer proximity to the precursor molecules. The capacity of CdSe production in the emulsion system was found to be 3.8 g/(L h), which is comparable to the typical hot-injection synthesis of CdSe QDs and can likely be further optimized. While the single-phase solvent system was found to produce ultrasmall QDs that exhibit broadband white-light emission, the emulsion system was found to produce well-defined magic-size clusters (MSCs) with photoluminescence quantum yield as high as 34%. Differences in synthesis rate and product properties from the emulsion and single-phase systems were probed by X-ray diffraction, electron microscopy, UV-visible (vis) and photoluminescence spectroscopy, and small-angle X-ray scattering (SAXS). Finally, precise temporal control of the QD synthesis was demonstrated via on-off cycling of the ultrasound waves.

The magic-sized carbon clusters on the transition metal surfaces with a four-fold symmetry

In order to understand the metal surface type dependent graphene chemical vapor deposition (CVD) growth, we have systematically explored the structural evolution of carbon clusters on Cu(100) substrate by using density functional theory (DFT) calculation. It is revealed that the most stable carbon clusters, Cn (n = 1–32), experience a structural transition from linear sp1 atom chain to sp2 2D network at a critical cluster size of n = 13. The highly stable sp2 network structures on a Cu(100) facet are mostly in a rectangular shape as the interplay between the C6v symmetry of graphene and the C4v symmetry of the Cu(100) surface leads to a C2v symmetry of the whole system. A few carbon clusters, C14, C20, C24 and C28, which all possesses the C2v symmetry are highly stable and possess the feature of magic sized clusters. Among them, C28 was found to have superior stability in a very large size range and are expected to be observed on various transition metal surfaces. Our study shows that graphene nucleation on a transition metal surface depends on surface type and symmetry dependent, which offers a theoretical guidance for the controllable CVD growth of graphene and graphene quantum dotes.

(Invited) A “Cocktail” Approach to Effective Passivation of Metal Halide Perovskite Magic Sized Clusters and Quantum Dots Using Novel Planar Molecular Ligands Based on Trivalent Metal Nitrate Coordination Complex

Metal halide perovskites nanoparticles, including magic sized clusters (MSCs) and perovskite quantum dots (PQDs), exhibit interesting properties promising for emerging applications in energy and photonics. Their stabilization is critical for maintaining their properties and functionalities. One approach to stabilization is to use molecular ligands to passivate their surface. We have discovered a new class of molecular ligands based on trivalent metal nitrate coordination complex that is highly effective in passivating perovskite MSCs or PQDs. We can tune from PQDs to MSCs at will by adjusting the ligand concentration and/or using different ligands, with stronger binding ligands and higher ligand concentration favoring MSCs over PQDs. Both the MSCs and PQDs are highly stable and photoluminescent. Experimental evidence suggests that the planar geometry of the coordination ligands is critical for the outcomes observed. Such ligands should work for both nanoparticles and bulk films, and are likely more desired than linear or “cone-shaped” ligands. The results indicate that the size, shape, charge (including distribution), orientation, and inter-ligand interaction are critical characters affecting the effectiveness of passivation. Furthermore, due to the nature of multiple defects on the MSC or PQD surface, a combination of ligands is required for effective passivation, essentially a “cocktail” approach. We also found that the approach works well for both all inorganic perovskites such as CsPbBr3 as well as organo-metal halide perovskites such as CH3NH3PbBr3. We suggest that the passivation approach developed may be applicable to materials beyond perovskites.

Four Types of CdTe Magic-Size Clusters from One Prenucleation Stage Sample at Room Temperature.

Four types of colloidal semiconductor CdTe magic-size clusters (MSCs), each of which is in a single-ensemble form, have been obtained at room temperature from a single induction period (IP) sample in dispersion. The induction period is the prenucleation stage that occurs prior to nucleation and growth of colloidal quantum dots (QDs). Three types display sharp optical absorption peaking at either 371, 417, or 448 nm, and the fourth type exhibits a sharp absorption doublet with peaks at 350 and 371 nm. These MSCs are respectively denoted as sMSC-371, sMSC-417, sMSC-448, and dMSC-371. We show that the evolution of the various MSCs is affected by the nature of their dispersions. We hypothesize that the evolution of MSCs involves their precursor compounds (PCs), which are transparent in optical absorption. The present study explores new avenues for the exclusive synthesis of four types of CdTe MSCs (with each in a single-ensemble form) and provides an improved understanding for their formation.

Tuning from Quantum Dots to Magic Sized Clusters of CsPbBr3 Using Novel Planar Ligands Based on the Trivalent Nitrate Coordination Complex.

We report the first demonstration of using trivalent metal hydrated nitrate coordination complexes (TMHNCCs) as novel passivation ligands to control the synthesis of magic sized clusters (MSCs) and quantum dots (QDs) of CsPbBr3 perovskite at room temperature. We can easily tune from QDs to MSCs or produce a mixture of the two by changing the amount of TMHNCC ligands used, with more ligands favoring MSCs. The original TMHNCC introduced, aluminum nitrate nonahydrate [ANN, Al(NO3)3·9H2O], led to the production of aluminum dihydroxide nitrate tetrahydrate {ADNT, [Al(OH)2(NO3)]·4H2O}, with the assistance of oleic acid (OA) and oleylamine (OAm). Through several control experiments, we determined that ADNT is the primary ligand for effectively passivating the MSCs and QDs, with OAm being essential for deprotonating ANN and OA for adjusting the pH of the reaction system. We suggest that ADNT is planar on the surface of the MSCs or QDs with its NO3- and OH- groups binding to the Cs+ and Pb2+ defect sites and Al3+ binding to the Br- defect sites of the MSCs or QDs.

Ligand Dependent Growth and Optical Properties of Hybrid Organo-metal Halide Perovskite Magic Sized Clusters

Magic sized clusters (MSCs), small nanoparticles with a single size or narrow size distribution, possess unique chemical and physical properties. CH3NH3PbBr3 perovskite MSCs (PMSCs) were synthesize...

CdS magic-size clusters exhibiting one sharp ultraviolet absorption singlet peaking at 361 nm

We report, for the first time, the synthesis of CdS magic-size clusters (MSCs) which exhibit a single sharp absorption peaking at ∼ 361 nm, along with sharp band edge photoemission at ∼ 377 nm and broad trap emission peaking at ∼ 490 nm. These MSCs are produced in a single-ensemble form without the contamination of conventional quantum dots (QDs) and/or other-bandgap clusters. They are denoted as MSC-361. We present the details of several controlled syntheses done in oleylamine (OLA), using Cd(NO3)2 or Cd(OAc)2 as a Cd source and thioacetamide (TAA) or elementary sulfur (S) as a S source. A high synthetic reproducibility of the reaction of Cd(NO3)2 and TAA to single-ensemble MSC-361 is achieved, the product of which is not contaminated by other bandgap clusters and/or QDs. In some cases, the reaction product exhibits an additional absorption peak at ∼ 322 nm. We demonstrate that the two peaks, at 361 and 322 nm, do not evolve synchronously. Therefore, the 322 nm peak is not a higher order electronic transition of MSC-361, but due to the presence of another ensemble, namely MSC-322. The present study suggests that there is an outstanding need for the development of a physical model to narrow the knowledge gap regarding the electronic structure in these colloidal semiconductor CdS MSCs.

Photoluminescent Colloidal Nanohelices Self-Assembled from CdSe Magic-Size Clusters via Nanoplatelets.

Reports on photoluminescent colloidal semiconductor two-dimensional (2D) helical nanostructures with one-dimensional quantum confinement are relatively rare. Here, we discuss the formation of such photoluminescent nanostructures for CdSe. We show that when as-synthesized unpurified zero-dimensional (0D) CdSe magic-size clusters (MSCs) (passivated by carboxylate ligands with three-dimensional quantum confinement) are dispersed in a solvent (such as toluene or chloroform) containing hexadecylamine and then subjected to sonication, helical nanostructures are obtained, as observed by transmission electron microscopy. We demonstrate that the formation involves the self-assembly of 0D MSCs into 2D nanoplatelets, which act as intermediates. The CdSe MSCs and their self-assembled 2D nanostructures display almost identical static optical properties, namely, a sharp absorption doublet with peaks at 433 and 460 nm and a narrow emission peak at 465 nm; this is a subject for further study. This study introduces new methods for fabricating photoluminescent helical nanostructures via the self-assembly of photoluminescent MSCs.

One-Step Approach to Single-Ensemble CdS Magic-Size Clusters with Enhanced Production Yields.

We report on the development of a single-step method for synthesizing colloidal semiconductor magic-size clusters (MSCs) with an enhanced production yield in a single-ensemble form and free of the coproduction of conventional quantum dots (QDs). This process eliminates the need for the second step of a lower-temperature incubation used in a two-step approach reported recently for the fabrication of single-ensemble MSCs without QD contamination. We demonstrate that the combined use of a secondary phosphine (HPR2) and an α-methyl carboxylic acid [RCH(CH3)-COOH, MA] promotes the yield of MSCs and suppresses the nucleation and growth of QDs. With CdO and elemental S powder as Cd and S sources, respectively, a single ensemble of CdS MSC-311 (displaying a sharp absorption peak at 311 nm) evolves directly in a reaction in 1-octadecene with an enhanced production yield. This study introduces a one-step avenue for synthesizing effectively and selectively single-ensemble MSCs and improves our understanding of the two-pathway model proposed for the prenucleation stage of QDs.

Formation of colloidal alloy semiconductor CdTeSe magic-size clusters at room temperature

Alloy semiconductor magic-size clusters (MSCs) have received scant attention and little is known about their formation pathway. Here, we report the synthesis of alloy CdTeSe MSC-399 (exhibiting sharp absorption peaking at 399 nm) at room temperature, together with an explanation of its formation pathway. The evolution of MSC-399 at room temperature is detected when two prenucleation-stage samples of binary CdTe and CdSe are mixed, which are transparent in optical absorption. For a reaction consisting of Cd, Te, and Se precursors, no MSC-399 is observed. Synchrotron-based in-situ small angle X-ray scattering (SAXS) suggests that the sizes of the two samples and their mixture are similar. We argue that substitution reactions take place after the two binary samples are mixed, which result in the formation of MSC-399 from its precursor compound (PC-399). The present study provides a room-temperature avenue to engineering alloy MSCs and an in-depth understanding of their probable formation pathway.

Capping Structure of Ligand-Cysteine on CdSe Magic-Sized Clusters.

Ligand molecules capping on clusters largely affect the formation and stabilization mechanism and the property of clusters. In semiconductor CdSe clusters, cysteine is used as one of the ligands and allows the formation of ultrastable (CdSe)34 magic-sized clusters. Cysteine has sulfhydryl, amine, and carboxylate groups, all of which have coordination ability to the CdSe surface, and the bonding states of the three functional groups of ligand–cysteine on the CdSe core have not been determined. In this work, the capping structure of ligand–cysteine is examined by performing Fourier transform infrared (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and multinuclear solid-state nuclear magnetic resonance (NMR) spectroscopy. FT-IR, XPS, and 1H, 13C, and 23Na magic-angle spinning NMR show that the sulfhydryl group of ligand–cysteine forms a sulfur–cadmium bond with a cadmium atom at the CdSe surface, while the carboxylate group does not contribute to the protection of the CdSe core and binds to a sodium ion contained as a counterion. 15N–{77Se} through-bond J-single quantum filtered NMR experiment reveals that the amine group of ligand–cysteine has no coordination to selenium atoms. By considering the N–Cd bond forming ratio (∼43%) revealed in our previous work, which is confirmed in this work by analyzing 13Cα signal intensity (∼42%), we concluded that cysteine capping on (CdSe)34 occurs in two ways: one involves both the sulfur–cadmium and nitrogen–cadmium bonds, and the other bears only the sulfur–cadmium bond.

X-ray total scattering study of magic-size clusters and quantum dots of cadmium sulphide.

Four types of magic-size CdS clusters and three different CdS quantum dots have been studied using the technique of X-ray total scattering and pair distribution function analysis. We found that the CdS quantum dots could be modelled as a mixed phase of atomic structures based on the two bulk crystalline phases, which is interpreted as representing the effects of random stacking of layers. However, the results for the magic-size clusters are significantly different. On one hand, the short-range features in the pair distribution function reflect the bulk, indicating that these structures are based on the same tetrahedral coordination found in the bulk phases (and therefore excluding new types of structures such as cage-like arrangements of atoms). But on the other hand, the longer-range atomic structure clearly does not reflect the layer structures found in the bulk and the quantum dots. We compare the effect of two ligands, phenylacetic acid and oleic acid, showing that in one case the ligand has little effect on the atomic structure of the magic-size nanocluster, and in another it has a significant effect.

Precursor Self-Assembly Identified as a General Pathway for Colloidal Semiconductor Magic-Size Clusters.

Little is known about the formation pathway of colloidal semiconductor magic‐size clusters (MSCs). Here, the synthesis of the first single‐ensemble ZnSe MSCs, which exhibit a sharp optical absorption singlet peaking at 299 nm, is reported; their formation is independent of Zn and Se precursors used. It is proposed that the formation of MSCs starts with precursor self‐assembly followed by Zn and Se covalent bond formation to result in immediate precursors (IPs) which can transform into the MSCs. It is demonstrated that the IPs in cyclohexane appear transparent in optical absorption, and become visible as MSCs exhibiting one sharp optical absorption peak when a primary amine is added at room temperature. It is shown that when the preparation of the IP is controlled to be within the induction period, which occurs prior to nucleation and growth of conventional quantum dots (QDs), the resulting MSCs can be produced without the complication of the simultaneous coproduction of conventional QDs. The present study reveals the existence of precursor self‐assembly which leads to the formation of colloidal semiconductor MSCs and provides insights into a multistep nucleation process in cluster science.

Effect of Small Molecule Additives in the Prenucleation Stage of Semiconductor CdSe Quantum Dots.

For the addition of small molecules in the prenucleation stage of colloidal CdSe conventional quantum dots (QDs), there is insufficient knowledge regarding what are advantageous circumstances. Here, we present a study about such addition. When CH3COOH or Zn(OOCCH3)2 is added in the prenucleation stage (at 120 °C) of a reaction consisting of cadmium myristate (Cd(OOC(CH2)12CH3)2, Cd(MA)2 made from CdO) and Se powder in 1-octadecene (ODE), CdSe magic-size clusters (MSCs) exhibiting a single sharp absorption doublet at 433/460 nm are synthesized in a single-ensemble form (around 220 °C). We demonstrate that such small molecule addition suppresses the nucleation and growth of QDs and thus directs a competitive process to the formation of MSCs. The present study provides insight into the individual but linked pathways to forming CdSe QDs and MSCs and introduces new avenues to improve the production of MSCs through the addition of small molecules in the prenucleation stage.

Synthesis and Degradation of Cadmium-Free InP and InPZn/ZnS Quantum Dots in Solution.

This study advances the chemical research community toward the goal of replacing toxic cadmium-containing quantum dots (QDs) with environmentally benign InP QDs. The InP QD synthesis uniquely combines the previously reported use of InP magic-sized clusters (MSCs) as a single-source precursor for indium and phosphorus to form InP QDs, with zinc incorporation and subsequent ZnS shelling, to form InPZn/ZnS QDs with luminescence properties comparable to those of commonly used cadmium-containing luminescent QDs. The resulting InPZn/ZnS QDs have an emission quantum yield of about 50% across a broad range of emission peak wavelengths and emission peaks averaging 50 nm fwhm. The emission peak wavelength can be easily tuned by varying the Zn/In ratio in the reaction mixture. The strategy of using zinc stearate to tune the emission properties is advantageous as it does not lead to a loss of emission quantum yield or emission peak broadening. Although the initial optical properties of InP and InPZn/ZnS QDs are promising, thermal stability measurements of InPZn QDs show significant degradation in the absence of a shell compared to the CdSe QDs particularly at increased temperature in the presence of oxygen, which is indicative of thermal oxidation. There is no significant difference in the degradation rate of InP QDs made from molecular precursors and from MSCs. Additionally, the emission intensity and quantum yield of InPZn/ZnS QDs when purified and diluted in organic solvents under ambient conditions decrease significantly compared to those of CdSe/ZnS QDs. This indicates instability of the ZnS shell when prepared by common literature methods. This must be improved to realize high-quality, robust Cd-free QDs with the capability of replacing CdSe QDs in QD technologies.

Co2+-Doping of Magic-Sized CdSe Clusters: Structural Insights via Ligand Field Transitions

Magic-sized clusters represent materials with unique properties at the border between molecules and solids and provide important insights into the nanocrystal formation process. However, synthesis, doping, and especially structural characterization become more and more challenging with decreasing cluster size. Herein, we report the successful introduction of Co2+ ions into extremely small-sized CdSe clusters with the intention of using internal ligand field transitions to obtain structural insights. Despite the huge mismatch between the radii of Cd2+ and Co2+ ions (>21%), CdSe clusters can be effectively synthesized with a high Co2+ doping concentration of ∼10%. Optical spectroscopy and mass spectrometry suggest that one or two Co2+ ions are substitutionally embedded into (CdSe)13 clusters, which is known as one of the smallest CdSe clusters. Using magnetic circular dichroism spectroscopy on the intrinsic ligand field transitions between the different 3d orbitals of the transition metal dopants, we demonstrate that the Co2+ dopants are embedded on pseudotetrahedral selenium coordinated sites despite the limited number of atoms in the clusters. A significant shortening of Co-Se bond lengths compared to bulk or nanocrystals is observed, which results in the metastability of Co2+ doping. Our results not only extend the doping chemistry of magic-sized semiconductor nanoclusters, but also suggest an effective method to characterize the local structure of these extremely small-sized clusters.

Evolution of Two Types of CdTe Magic-Size Clusters from a Single Induction Period Sample.

There are two types of colloidal semiconductor nanocrystals (NCs) that exhibit band gap absorption that is relatively sharp compared to conventional quantum dots (QDs). One type displays an absorption doublet, while the other displays an absorption singlet. Here, we report the evolution of the two types of NCs at room temperature from a single CdTe sample extracted during the induction period (IP) prior to nucleation and growth of conventional QDs. The resulting NCs exhibit band gap absorption peaking at ∼371 nm and are magic-size clusters (MSCs), labeled as dMSC-371 and sMSC-371 for the doublet and singlet cases, respectively. We demonstrate that dMSC-371 (with another peak at ∼350 nm) evolves when the sample is incubated. When the sample is dispersed without incubation into a toluene and octylamine mixture, dMSC-371 or sMSC-371 grows depending on the amine amount. We propose that dMSC-371 and sMSC-371 are a pair of polymorphs (with identical CdTe core compositions). The present study brings insight into the formation relationship between dMSCs and sMSCs.