III–V colloidal nanocrystals: control of covalent surfaces

Colloidal quantum dots (QDs) are nanosized semiconductors whose electronic features are dictated by the quantum confinement effect. The optical, electrical, and chemical properties of QDs are influenced by their dimensions and surface landscape. The surface of II–VI and IV–VI QDs has been extensively explored; however, in-depth investigations on the surface of III–V QDs are still lagging behind. This Perspective discusses the current understanding of the surface of III–V QDs, outlines deep trap states presented by surface defects, and suggests strategies to overcome challenges associated with deep traps. Lastly, we discuss a route to create well-defined facets in III–V QDs by providing a platform for surface studies and a recently reported approach in atomistic understanding of covalent III–V QD surfaces using the electron counting model with fractional dangling bonds.

Unveiling the atomistic surface structure of colloidal quantum dots may provide the route to rational design of highly performing III–V nanocrystals with control over energy levels position, surface energy, trap passivation, and heterojunction interface.     

Electrochemical control of adsorption dynamics of surface layer proteins on gold

The kinetics and mechanism of the adsorption of the surface layer proteins of Lysinibacillus sphaericus CCM2177 on gold depend on the charging conditions of the electrochemical double layer and the addition of Ca(2+) ions. The electrical and mass charging was monitored by an in situ electrochemical quartz microbalance. Adsorption and monolayer formation of the protein molecules occur in the positive potential region where solvated anions form the electrochemical double layer. The crystalline character of the surface layer was diagnosed by an atomic force microscope. Negative of the point of zero charge, multilayer island structures were found.     

Shape separation of colloidal gold nanoparticles through salt-triggered selective precipitation

Highly effective separation of colloidal gold nanorods/nanoplates from co-produced isotropic nanoparticles has been achieved by selective precipitation triggered by salt.     

Influence of surface modification on the luminescence of colloidal ZnO nanocrystals

The influence of surface modification on the luminescence of colloidal ZnO nanocrystals is described, with particular emphasis given to factors increasing excitonic emission quantum yields. Changes in nanocrystal size, shape, and luminescence intensities have been measured for nanocrystals capped by dodecylamine (DDA) and trioctylphosphine oxide after different growth times. Green trap emission intensities show a direct correlation with surface hydroxide concentrations. Contrary to expectations, there is no direct correlation between excitonic emission quenching and surface hydroxide concentrations. The nearly pure excitonic emission observed after heating in DDA is attributed to the removal of surface defects from the ZnO nanocrystal surfaces and to the relatively high packing density of DDA on the ZnO surfaces. Rapid, nondispersive ripening of ZnO nanocrystals upon heating in DDA is observed and explained using a colloidal growth model.     

A generalized ligand-exchange strategy enabling sequential surface functionalization of colloidal nanocrystals

The ability to engineer surface properties of nanocrystals (NCs) is important for various applications, as many of the physical and chemical properties of nanoscale materials are strongly affected by the surface chemistry. Here, we report a facile ligand-exchange approach, which enables sequential surface functionalization and phase transfer of colloidal NCs while preserving the NC size and shape. Nitrosonium tetrafluoroborate (NOBF4) is used to replace the original organic ligands attached to the NC surface, stabilizing the NCs in various polar, hydrophilic media such as N,N-dimethylformamide for years, with no observed aggregation or precipitation. This approach is applicable to various NCs (metal oxides, metals, semiconductors, and dielectrics) of different sizes and shapes. The hydrophilic NCs obtained can subsequently be further functionalized using a variety of capping molecules, imparting different surface functionalization to NCs depending on the molecules employed. Our work provides a versatile ligand-exchange strategy for NC surface functionalization and represents an important step toward controllably engineering the surface properties of NCs.     

Shape control of semiconductor and metal oxide nanocrystals through nonhydrolytic colloidal routes

Inorganic nanocrystals with tailored geometries exhibit unique shape-dependent phenomena and subsequent utilization of them as building blocks for the fabrication of nanodevices is of significant interest. Herein, we review the recent developments in the shape control of colloidal nanocrystals with a focus on the scientifically and technologically important semiconductor and metal oxide nanocrystals obtained by nonhydrolytic synthetic methods. Many structurally unprecedented motifs have been discovered including polyhedrons, rods and wires, plates and prisms, and other advanced shapes such as branched rods, stars, inorganic dendrites, and dumbbells. The currently proposed shape-guiding mechanisms are presented and the important pioneering studies on the assembly of shape-controlled nanocrystals into ordered superlattices and the fabrication of prototype advanced nanodevices are discussed.     

Synthesis of colloidal uranium-dioxide nanocrystals

In this paper, we have developed an organic-phase synthesis method for producing size-controlled, nearly monodispersed, colloidal uranium-dioxide nanocrystals. These UO2 nanocrystals are potentially important to applications such as nuclear fuel materials, catalysts, and thermopower materials. In addition, we have systematically mapped out the functions of the solvents (oleic acid, oleylamine, and 1-octadecene) in the synthesis, and we found that N-(cis-9-octadecenyl)oleamide-a product of the condensation of oleic acid and oleylamine-can substantially affect the formation of UO2 nanocrystals. Importantly, these results provide fundamental insight into the mechanisms of UO2 nanocrystal synthesis. Moreover, because a mixture of oleic acid and oleylamine has been widely used in synthesizing a variety of high-quality metal or metal-oxide nanocrystals, the results herein should also be important for understanding the detailed mechanisms of these syntheses.     

Microwave-assisted synthesis of colloidal inorganic nanocrystals

Colloidal inorganic nanocrystals stand out as an important class of advanced nanomaterials owing to the flexibility with which their physical-chemical properties can be controlled through size, shape, and compositional engineering in the synthesis stage and the versatility with which they can be implemented into technological applications in fields as diverse as optoelectronics, energy conversion/production, catalysis, and biomedicine. The use of microwave irradiation as a non-classical energy source has become increasingly popular in the preparation of nanocrystals (which generally involves complex and time-consuming processing of molecular precursors in the presence of solvents, ligands and/or surfactants at elevated temperatures). Similar to its now widespread use in organic chemistry, the efficiency of "microwave flash heating" in dramatically reducing overall processing times is one of the main advantages associated with this technique. This Review illustrates microwave-assisted methods that have been developed to synthesize colloidal inorganic nanocrystals and critically evaluates the specific roles that microwave irradiation may play in the formation of these nanomaterials.     

Anchoring molecular chromophores to colloidal gold nanocrystals: surface-enhanced Raman evidence for strong electronic coupling and irreversible structural locking

High-affinity anchoring groups such as isothiocyanate (ITC, -N═C═S) are often used to attach organic chromophores (reporter molecules) to colloidal gold nanocrystals for surface-enhanced Raman scattering (SERS), to atomically smooth gold surfaces for tip-enhanced Raman scattering, and to scanning tunneling microscopy probes (nanosized electrodes) for single-molecule conductance measurements. However, it is still unclear how the attached molecules interact electronically with the underlying surface, and how the anchoring group might affect the electronic and optical properties of such nanoscale systems. Here we report systematic surface-enhanced Raman studies of two organic chromophores, malachite green (MG) and its ITC derivative (MGITC), that have very different functional groups for surface binding but nearly identical spectroscopic properties. A surprise finding is that, under the same experimental conditions, the SERS signal intensities for MGITC are nearly 500-fold higher than those of MG. Correcting for the intrinsic difference in scattering cross sections of these two dyes, we estimate that the MGITC enhancement factors are ~200-fold higher than for MG. Furthermore, pH-dependent studies reveal that the surface structure of MGITC is irreversibly stabilized or "locked" in its π-conjugated form and is no longer responsive to pH changes. In contrast, the electronic structure of adsorbed MG is still sensitive to pH and can be switched between its localized and delocalized electronic forms. These results indicate that ITC is indeed an unusual anchoring group that enables strong electronic coupling between gold and the adsorbed dye, leading to more efficient chemical enhancement and higher overall enhancement factors.     

Surface chemistry of colloidal PbSe nanocrystals

Solution nuclear magnetic resonance spectroscopy (NMR) is used to identify and quantify the organic capping of colloidal PbSe nanocrystals (Q-PbSe). We find that the capping consists primarily of tightly bound oleic acid ligands. Only a minor part of the ligand shell (0-5% with respect to the number of oleic acid ligands) is composed of tri- n-octylphosphine. As a result, tuning of the Q-PbSe size during synthesis is achieved by varying the oleic acid concentration. By combining the NMR results with inductively coupled plasma mass spectrometry, a complete Q-PbSe structural model of semiconductor core and organic ligands is constructed. The nanocrystals are nonstoichiometric, with a surface that is composed of lead atoms. The absence of surface selenium atoms is in accordance with an oleic acid ligand shell. NMR results on a Q-PbSe suspension, stored under ambient conditions, suggest that oxidation leads to the loss of oleic acid ligands and surface Pb atoms, forming dissolved lead oleate.     

Effect of medium pH on the optical properties of CdTe nanocrystals at colloidal synthesis and postsynthetic treatment

Physicochemical properties of low-dimensional structures based on CdTe obtained by colloidal synthesis method were studied. Effect of thioglycolic, hydroxyethylidenediphosphonic, and ethylenediaminetetraacetic acids as well as L-cysteine and thiourea on the processes of formation of CdTe nanocrystals in aqueous solutions was examined. Medium pH was shown to have a considerable effect on the process of their colloidal synthesis. The features of preparation of concentrated colloidal solutions of CdTe nanocrystals stabilized by thioglycolic acid and further sedimentational precipitation of monodisperse fractions from polydisperse solutions were studied. Optical absorption and photoluminescence spectra of the studied materials immediately after synthesis completion and after postsynthetic treatment were obtained and analyzed.     

Photoinduced thermal copper reduction onto gold nanocrystals under potentiostatic control

We study the photoreduction of adsorbed copper ions onto Au nanoparticles, on an indium tin oxide (ITO) electrode in an aqueous electrochemical cell, as a function of applied voltage and laser intensity. The photocurrent is a nonlinear function of laser intensity and increases sharply with cathodic voltage in the underpotential deposition region. The photoreduction is attributed to laser heating of the Au nanoparticles rather than "hot electron" processes. Numerical simulation of the Butler-Volmer kinetic equation using experimental parameters predicts a several orders of magnitude increase in current for a temperature rise of a few Kelvin.     

Size control of gold nanocrystals in citrate reduction: the third role of citrate

Growth kinetics and temporal size/shape evolution of gold nanocrystals by citrate reduction in boiling water were studied systematically and quantitatively. Results reveal that the size variation and overall reaction mechanism were mostly determined by the solution pH that was in turn controlled by the concentration of sodium citrate (Na3Ct) in the traditional Frens's synthesis. This conclusion was further confirmed by the reactions with variable pH but fixed concentrations of the two reactants, HAuCl4 and Na3Ct. Two substantially different reaction pathways were identified, with the switching point at pH = 6.2-6.5. The first pathway is for the low pH range and consists of three overlapping steps: nucleation, random attachment to polycrystalline nanowires, and smoothing of the nanowires via intra-particle ripening to dots. The second pathway that occurred above the pH switching point is consistent with the commonly known nucleation-growth route. Using the second pathway, we demonstrated a new synthetic route for the synthesis of nearly monodisperse gold nanocrystals in the size range from 20 to 40 nm by simply varying the solution pH with fixed concentrations of HAuCl4 and Na3Ct. The switching of the reaction pathways is likely due to the integration nature of water as a reaction medium. In the citrate reduction, the solution pH was varied by changing the initial HAuCl4/Na3Ct ratio. Consequently, when pH was higher than about 6.2, the very reactive [AuCl3(OH)]- would be converted to less reactive [AuCl2(OH)2]- and [AuCl(OH)3]-.     

Symmetry-controlled colloidal nanocrystals: nonhydrolytic chemical synthesis and shape determining parameters

Since inorganic nanocrystals exhibit unique shape-dependent nanoscale properties and can be utilized as basic building blocks for futuristic nanodevices, a systematic study on the shape control of these nanocrystals remains an important subject in materials and physical chemistry. In this feature article, we overview the recent progress on the synthetic development of symmetry-controlled colloidal nanocrystals of semiconductor and metal oxide, which are prepared through nonhydrolytic chemical routes. We describe their shape-guiding processes and illustrate the detailed key factors controlling their growth by examining various case studies of zero-dimensional spheres and cubes, one-dimensional rods, and quasi multidimensional structures such as disks, multipods, and stars. Specifically, the crystalline phase of nucleating seeds, surface energy, kinetic vs thermodynamic growth, and selective adhesion processes of capping ligands are found to be most crucial for the determination of the nanocrystal shape.     

Synthesis and magnetic properties of colloidal MnPt3 nanocrystals

The colloidal synthesis and magnetic properties of MnPt(3) nanocrystals are reported. The nanocrystal size depended on the Mn reactant used, but the Mn:Pt stoichiometry was always 1:3. As synthesized, the nanocrystals are compositionally disordered with the face-centered cubic (fcc) A1 phase. Annealing at 580 degrees C changed the MnPt(3) crystal structure to the compositionally ordered L1(2) phase (AuCu(3) structure) with higher magnetocrystalline anisotropy. Magnetization measurements showed that the A1 nanocrystals are paramagnetic and the L1(2) MnPt(3) nanocrystals are superparamagnetic.     

One-dimensional colloidal gold and silver nanostructures

One-dimensional (1-D) metallic nanoscale materials have long been of interest to many groups of scientists. Within the last 2 decades, great advances in the synthesis of metallic nanorods and nanowires have been made, with a variety of templating methods. More recently, bottom-up chemical syntheses of these materials have become increasingly reported in the literature. This Forum Article describes the synthesis, physical properties, and potential applications of 1-D metals, with an emphasis on silver and gold derived from studies in the authors' laboratories.     

Ligand bonding and dynamics on colloidal nanocrystals at room temperature: the case of alkylamines on CdSe nanocrystals

With CdSe nanocrystals stabilized with very weak ligands (pyridine) as the starting materials, NMR techniques were applied to distinguish the bonded and free alkylamine ligands in an equilibrated adsorption/desorption system for the CdSe-amine nanocrystal-ligand pair. NMR and photoluminescence (PL) measurements were further correlated to identify the linear relationship between PL intensity and the surface ligand coverage of the amine-coated CdSe nanocrystals. For 3.5 nm CdSe nanocrystals and octylamine ligands, the chemical equilibrium constant (K) of the CdSe-amine nanocrystal-ligand adsorption/desorption process was found to be around 50-100, and the corresponding Delta(r)G(o) was calculated as 9.8-11.5 kJ/mol. With a proposed mathematic method, the corresponding chemical kinetic constants for the desorption (kd) and adsorption (ka) processes were measured to be 0.01 s(-1) and 0.5 L mol(-1) s(-1), respectively. K, kd, and ka obtained here are generally 2-4 magnitudes different from those estimated in literature. Analysis indicates that these constants are well consistent with the existing experimental observations.