Jae Sung Son

Large-scale soft colloidal template synthesis of 1.4 nm thick CdSe nanosheets.

Two-dimensional (2D) nanocrystals have attracted tremendous attention from many researchers in various disciplines because of their unique properties. Since ways of making graphene were devised, there have been significant research efforts to synthesize free-standing 2D nanocrystals of various materials, including metals, oxides, and chalcogenides. Many of these 2D nanocrystals have been generated from exfoliation of materials with layered structures, and tiny amounts of products are generally produced. CdSe nanocrystals are among the most intensively studied nanostructured materials, owing to their many size-dependent optical and electrical characteristics and resulting exciting applications. Herein, we report on the large-scale synthesis of single-layered and lamellar-structured 2D CdSe nanocrystals with wurtzite crystal structure as thin as 1.4 nm by a soft colloidal template method. These free-standing 2D nanocrystals with insulating organic layers at the interface could find many interesting electronic and optoelectronic applications, including in quantum cascade lasers and resonant tunneling diodes utilizing their multiple quantum well structures. Compared to materials with layered crystal structures such as graphite, the synthesis of free-standing 2D nanocrystals of nonlayered materials such as CdSe is extremely challenging, because selective growth along one specific facet among several with similar energies is required. For example, in CdSe with a hexagonal wurtzite crystal structure, a (0001) facet has significantly higher surface energy than other facets, which leads to the formation of many one-dimensional nanostructures. Although there is a slight difference in the surface energies of (1120) and (1100) facets, quantum-confined thin CdSe 2D nanocrystals could not be synthesized using a conventional colloidal chemical route that employs thermal decomposition of precursors at high temperature, because the small difference in the surface energies of these two facets is negated by the high reaction temperature. Consequently, there have been only a few reports on the successful chemical synthesis of 2D CdSe nanocrystals. For example, CdSe inorganic–organic hybrid lamellar structures and CdSe nanoplatelets with zinc-blende structure were synthesized using colloidal chemical routes. However, their 2D growth mechanism has not been clearly elucidated. Furthermore, nanostructural control to form single-layered or multiple-layered nanosheets has not been demonstrated. In the current approach to creating 2D CdSe nanocrystals, we employed a soft template method, and we were able to synthesize not only free-standing single-layered CdSe nanosheets but also lamellar-structured nanosheets by controlling the interaction between organic layers in 2D templates of cadmium chloride alkyl amine complexes. It has been reported that the complex of cadmium halide and diamine can form a cadmium halide /diamine alternating layered structure through diamine bridging and hydrogen bonding between hydrogen atoms of the amine and halogen atoms. Likewise, a [CdCl2(RNH2)2] lamellar complex, which is used herein as a soft template, is expected to form lamellar structures composed of 2D arrays of CdCl2 and alkyl amine by van der Waals attraction between hydrocarbon sidechains of the alkyl amine. The small-angle X-ray scattering (SAXS) patterns of [CdCl2(RNH2)2] complexes with butylamine (BA), octylamine (OA), and dodecylamine (DA) show 00l orders of reflection, which confirms that the complexes formed typical lamellar structures (Supporting Information, Figure S1). A [CdCl2(OA)2] lamellar complex was chosen as the soft template for the synthesis of lamellarstructured CdSe nanosheets because of its optimum reactivity. [*] J. S. Son, Dr. J. Joo, K. Park, Dr. J. H. Kim, Dr. K. An, J. H. Yu, S. G. Kwon, Dr. S.-H. Choi, Prof. T. Hyeon National Creative Research Initiative Center for Oxide Nanocrystalline Materials and School of Chemical and Biological Engineering Seoul National University Seoul 151-744 (Korea) Fax: (+82)2-886-8457 E-mail: thyeon@snu.ac.kr

Synthesis of Uniform Hollow Oxide Nanoparticles through Nanoscale Acid Etching

We synthesized various hollow oxide nanoparticles from as-prepared MnO and iron oxide nanocrystals. Heating metal oxide nanocrystals dispersed in technical grade trioctylphosphine oxide (TOPO) at 300 degrees C for hours yielded hollow nanoparticles retaining the size and shape uniformity of the original nanocrystals. The method was highly reproducible and could be generalized to synthesize hollow oxide nanoparticles of various sizes, shapes, and compositions. Control experiments revealed that the impurities in technical grade TOPO, especially alkylphosphonic acid, were responsible for the etching of metal oxide nanocrystals to the hollow structures. Elemental mapping analysis revealed that the inward diffusion of phosphorus and the outward diffusion of metal took place in the intermediate stages during the etching process. The elemental analysis using XPS, EELS, and EDX showed that the hollow nanoparticles were amorphous metal oxides containing significant amount of phosphorus. The hollow nanoparticles synthesized from MnO and iron oxide nanocrystals were paramagnetic at room temperature and when dispersed in water showed spin relaxation enhancement effect for magnetic resonance imaging (MRI). Because of their morphology and magnetic property, the hollow nanoparticles would be utilized for multifunctional biomedical applications such as the drug delivery vehicles and the MRI contrast agents.

n-Type Nanostructured Thermoelectric Materials Prepared from Chemically Synthesized Ultrathin Bi2Te3 Nanoplates

We herein report on the large-scale synthesis of ultrathin Bi(2)Te(3) nanoplates and subsequent spark plasma sintering to fabricate n-type nanostructured bulk thermoelectric materials. Bi(2)Te(3) nanoplates were synthesized by the reaction between bismuth thiolate and tri-n-octylphosphine telluride in oleylamine. The thickness of the nanoplates was ~1 nm, which corresponds to a single layer in Bi(2)Te(3) crystals. Bi(2)Te(3) nanostructured bulk materials were prepared by sintering of surfactant-removed Bi(2)Te(3) nanoplates using spark plasma sintering. We found that the grain size and density were strongly dependent on the sintering temperature, and we investigated the effect of the sintering temperature on the thermoelectric properties of the Bi(2)Te(3) nanostructured bulk materials. The electrical conductivities increased with an increase in the sintering temperature, owing to the decreased interface density arising from the grain growth and densification. The Seebeck coefficients roughly decreased with an increase in the sintering temperature. Interestingly, the electron concentrations and mobilities strongly depended on the sintering temperature, suggesting the potential barrier scattering at interfaces and the doping effect of defects and organic residues. The thermal conductivities also increased with an increase in the sintering temperature because of grain growth and densification. The maximum thermoelectric figure-of-merit, ZT, is 0.62 at 400 K, which is one of the highest among the reported values of n-type nanostructured materials based on chemically synthesized nanoparticles. This increase in ZT shows the possibility of the preparation of highly efficient thermoelectric materials by chemical synthesis.

Giant Zeeman splitting in nucleation-controlled doped CdSe:Mn2+ quantum nanoribbons

Doping of semiconductor nanocrystals by transition-metal ions has attracted tremendous attention owing to their nanoscale spintronic applications. Such doping is, however, difficult to achieve in low-dimensional strongly quantum confined nanostructures by conventional growth procedures. Here we demonstrate that the incorporation of manganese ions up to 10% into CdSe quantum nanoribbons can be readily achieved by a nucleation-controlled doping process. The cation-exchange reaction of (CdSe)(13) clusters with Mn(2+) ions governs the Mn(2+) incorporation during the nucleation stage. This highly efficient Mn(2+) doping of the CdSe quantum nanoribbons results in giant exciton Zeeman splitting with an effective g-factor of approximately 600, the largest value seen so far in diluted magnetic semiconductor nanocrystals. Furthermore, the sign of the s-d exchange is inverted to negative owing to the exceptionally strong quantum confinement in our nanoribbons. The nucleation-controlled doping strategy demonstrated here thus opens the possibility of doping various strongly quantum confined nanocrystals for diverse applications.

Simple and Generalized Synthesis of Oxide−Metal Heterostructured Nanoparticles and their Applications in Multimodal Biomedical Probes

Heterostructured nanoparticles composed of metals and Fe3O4 or MnO were synthesized by thermal decomposition of mixtures of metal-oleate complexes (for the oxide component) and metal-oleylamine complexes (for the metal component). The products included flowerlike-shaped nanoparticles of Pt-Fe3O4 and Ni-Fe3O4 and snowmanlike-shaped nanoparticles of Ag-MnO and Au-MnO. Powder X-ray diffraction patterns showed that these nanoparticles were composed of face-centered cubic (fcc)-structured Fe3O4 or MnO and fcc-structured metals. The relaxivity values of the Au-MnO and Au-Fe3O4 nanoparticles were similar to those of the MnO and Fe3O4 nanoparticles, respectively. Au-Fe3O4 heterostructured nanoparticles conjugated with two kinds of 12-base oligonucleotide sequences were able to sense a complementary 24-mer sequence, causing nanoparticle aggregation. This hybridization-mediated aggregation was detected by the overall size increase indicated by dynamic light scattering data, the red shift of the surface plasmon band of the Au component, and the enhancement of the signal intensity of the Fe3O4 component in T2-weighted magnetic resonance imaging.

Composition-matched molecular “solders” for semiconductors

Soldering semiconductor nanoparticles The optical and electronic properties of semiconductor nanoparticles can be tuned through changes in their size and composition. However, poor contact between interfaces can degrade nanoparticle performance in devices. Dolzhnikov et al. report the synthesis of a gel-like “solder” for metal chalcogenide nanoparticles, such as cadmium selenide and lead telluride, by cross-linking molecular wires of these materials. Science, this issue p. 425 A gel material mechanically bonds semiconductor nanoparticles and improves their electronic properties. We propose a general strategy to synthesize largely unexplored soluble chalcogenidometallates of cadmium, lead, and bismuth. These compounds can be used as “solders” for semiconductors widely used in photovoltaics and thermoelectrics. The addition of solder helped to bond crystal surfaces and link nano- or mesoscale particles together. For example, CdSe nanocrystals with Na2Cd2Se3 solder was used as a soluble precursor for CdSe films with electron mobilities exceeding 300 square centimeters per volt-second. CdTe, PbTe, and Bi2Te3 powders were molded into various shapes in the presence of a small additive of composition-matched chalcogenidometallate or chalcogel, thus opening new design spaces for semiconductor technologies.

Reconstructing a solid-solid phase transformation pathway in CdSe nanosheets with associated soft ligands.

Integrated single-crystal-like small and wide-angle X-ray diffraction images of a CdSe nanosheet under pressure provide direct experimental evidence for the detailed pathway of transformation of the CdSe from a wurtzite to a rock-salt structure. Two consecutive planar atomic slips [(001) 〈110〉 in parallel and (102) with a distortion angle of ∼40°] convert the wurtzite-based nanosheet into a saw-like rock-salt nanolayer. The transformation pressure is three times that in the bulk CdSe crystal. Theoretical calculations are in accord with the mechanism and the change in transformation pressure, and point to the critical role of the coordinated amines. Soft ligands not only increase the stability of the wurtzite structure, but also improve its elastic strength and fracture toughness. A ligand extension of 2.3 nm appears to be the critical dimension for a turning point in stress distribution, leading to the formation of wurtzite (001)/zinc-blende (111) stacking faults before rock-salt nucleation.

Dimension-Controlled Synthesis of CdS Nanocrystals: From 0D Quantum Dots to 2D Nanoplates

The dimension-controlled synthesis of CdS nanocrystals in the strong quantum confinement regime is reported. Zero-, one-, and two-dimensional CdS nanocrystals are selectively synthesized via low-temperature reactions using alkylamines as surface-capping ligands. The shape of the nanocrystals is controlled systematically by using different amines and reaction conditions. The 2D nanoplates have a uniform thickness as low as 1.2 nm. Furthermore, their optical absorption and emission spectra show very narrow peaks indicating extremely uniform thickness. It is demonstrated that 2D nanoplates are generated by 2D assembly of CdS magic-sized clusters formed at the nucleation stage, and subsequent attachment of the clusters. The stability of magic-sized clusters in amine solvent strongly influences the final shapes of the nanocrystals. The thickness of the nanoplates increases in a stepwise manner while retaining their uniformity, similar to the growth behavior of inorganic clusters. The 2D CdS nanoplates are a new type of quantum well with novel nanoscale properties in the strong quantum confinement regime.

Large‐Scale Synthesis and Characterization of the Size‐Dependent Thermoelectric Properties of Uniformly Sized Bismuth Nanocrystals

Highly efficient thermoelectric materials have attracted tremendous attention because of various technological applications such as power generation from waste heat and environmentally friendly refrigeration. The efficiency of thermoelectric materials is generally evaluated in terms of thermoelectric figure of merit ZT= (sS/k)T, where s is the electrical conductivity, S is the Seebeck coefficient, k is the thermal conductivity, and T is the absolute temperature. Recently, various nanostructured thermoelectric materials have been reported to exhibit high ZT values. This increase in thermoelectric efficiency was attributed to the decrease of thermal conductivity caused by the increased interfaces to scatter phonons or the enhancement of power factor (sS) by quantum confinement effects. However, most of the highZT nanostructured materials were prepared by costly and complicated processes, making it very difficult to inexpensively synthesize a large quantity of nanostructured materials. More recently, several kinds of nanostructured bulk materials with high ZT values were fabricated in large quantity by a ball-milling process and subsequent hot-press process. Recently, colloidal chemical methods have been used to synthesize large quantities of uniform-sized nanocrystals. These chemical methods can synthesize uniform-sized nanocrystals in a size-controlled manner, allowing the characterization of size-dependent properties, which is very difficult to perform using top-down physical methods, such as the ballmilling process. Over the past few decades, intensive research has attempted to characterize the electrical properties of bulk bismuth (Bi), because it is semimetallic with a small band overlap and has high carrier mobility and extremely small carrier effective mass. Furthermore, thermoelectric properties of Bi nanocrystals were intensively studied, because theoretical calculations predicted that Bi nanocrystals can exhibit a ZT value as high as 10 at 77 K. Moreover, Bi costs around one tenth of the price of bismuth telluride, which is one of the most popular thermoelectric materials. However, a high ZT value has not yet been realized experimentally for Bi nanostructured materials. Although several chemical syntheses of Bi nanocrystals have been reported, the thermoelectric properties of spherical Bi nanocrystals have rarely been studied. Herein, we report a simple and largescale synthetic method to produce uniform-sized Bi nanocrystals with controlled sizes and characterized their sizedependent thermoelectric properties. The size-dependant electrical and thermal properties were clearly demonstrated using uniform Bi nanocrystals with controlled particle sizes. Interestingly, the ratio of electrical to thermal conductivity increased with decreasing particle size, which leads to the enhancement of the ZT values. Bi nanocrystals were synthesized by reducing bismuth dodecanethiolate, which was generated by the reaction of dodecanethiol and bismuth neodecanoate in octadecene. Bismuth thiolate was so reactive that Bi nanocrystals could be readily produced by injecting the mild reducing agent tri-noctylphosphine (TOP) into bismuth dodecanethiolate solution at a temperature as low as 80 8C. The sizes of Bi nanocrystals could be easily tuned by varying the aging temperature and time. Transmission electron microscopy (TEM) images (Figure 1a–f) show uniform-sized Bi nanocrystals with sizes ranging from 6 to 27 nm. All of the nanocrystals exhibited narrow size distribution with standard deviation of less than 10%. The electron diffraction patterns (Figure 1a–f, insets) revealed the highly crystalline nature of the Bi nanocrystals. The X-ray diffraction (XRD) patterns (Figure 1g) showed that all of the nanocrystals had a rhombohedral Bi structure (JCPDS 85-1331), while the peaks became broader as the size decreases. To demonstrate large-scale production, we performed the reaction with 20 mmol of bismuth precursor and obtained as much as [*] J. S. Son, K. Park, Prof. T. Hyeon National Creative Research Initiative Center for Oxide Nanocrystalline Materials World Class University (WCU) Program of Chemical Convergence for Energy & Environment (C2E2) School of Chemical and Biological Engineering Seoul National University, Seoul 151-744 (Korea) Fax: (+ 82)2-886-8457 E-mail: thyeon@snu.ac.kr

Temperature-Dependent Hall and Field-Effect Mobility in Strongly Coupled All-Inorganic Nanocrystal Arrays

We report on the temperature-dependent Hall effect characteristics of nanocrystal (NC) arrays prepared from colloidal InAs NCs capped with metal chalcogenide complex (MCC) ligands (In2Se4(2-) and Cu7S4(-)). Our study demonstrates that Hall effect measurements are a powerful way of exploring the fundamental properties of NC solids. We found that solution-cast 5.3 nm InAs NC films capped with copper sulfide MCC ligands exhibited high Hall mobility values over 16 cm(2)/(V s). We also showed that the nature of MCC ligands can control doping in NC solids. The comparative study of the temperature-dependent Hall and field-effect mobility values provides valuable insights concerning the charge transport mechanism and points to the transition from a weak to a strong coupling regime in all-inorganic InAs NC solids.