Two-phase synthesis of shape-controlled colloidal zirconia nanocrystals and their characterization

We have developed a two-phase approach for the synthesis of shape-controlled colloidal zirconia nanocrystals, including spherical-, teardrop-, rod-, and rice grain-shaped particles. We found that the key factors for controlling the shape were the reaction time, the nature of the capping agent, and the monomer concentration. We have analyzed the morphologies, crystallinity, optical properties, and structural features of the as-prepared ZrO2 nanoparticles by using transmission electron microscopy (TEM), high-resolution TEM, X-ray powder diffraction, and UV-vis absorption and fluorescence spectroscopy. The possible nucleation and growth process is also discussed.     

Solvothermal synthesis of PbTe/SnTe hybrid nanocrystals

PbTe/SnTe hybrid nanocrystals with designed shape, chemical composition and narrow size distribution were synthesized by an efficient solvothermal approach. This approach enables mass and economical synthesis of PbTe-based nanocrystals. The organic ligands were completely removed by pretreatment with a super-hydride solution, making it possible to fabricate fully dense and robust thermoelectric devices with increased electrical conductivity.     

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.     

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.     

One-step synthesis of highly water-soluble magnetite colloidal nanocrystals

A high-temperature solution-phase hydrolysis approach has been developed for the synthesis of colloidal magnetite nanocrystals with well-controlled size and size distribution, high crystallinity, and high water solubility. The synthesis was accomplished by the hydrolysis and reduction of iron(III) cations in diethylene glycol with a rapidly injected solution of sodium hydroxide at an elevated temperature. The high reaction temperature allows for control over size and size distribution and yields highly crystalline products. The superior water solubility is achieved by using a polyelectrolyte, that is, poly(acrylic acid) as the capping agent, the carboxylate groups of which partially bind to the nanocrystal surface and partially extend into the surrounding water. The direct synthesis of water-soluble nanocrystals eliminates the need for additional surface modification steps which are usually required for treating hydrophobic nanocrystals produced in nonpolar solvents through the widely recognized pyrolysis route. The abundant carboxylate groups on the nanocrystal surface allow further modifications, such as bioconjugation, as demonstrated by linking cysteamine to the particle surface. The monodisperse, highly water-soluble, superparamagnetic, and biocompatible magnetite nanocrystals should find immediate important biomedical applications.     

Ag/ZnO heterostructure nanocrystals: synthesis, characterization, and photocatalysis

A high yield of the dimer-type heterostructure of Ag/ZnO nanocrystals with different Ag contents is successfully prepared through a simple solvothermal method in the absence of surfactants. The samples are characterized by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, UV-vis spectroscopy, and IR spectroscopy. The results show that all samples are composed of metallic Ag and ZnO; Ag nanoparticles locate on the surface of ZnO nanorods; the binding energy of Ag 3d(5/2) for the Ag/ZnO sample with a Ag content of 5.0 atom % shifts remarkably to the lower binding energy compared with the corresponding value of pure metallic Ag because of the interaction between Ag and ZnO nanocrystals; the concentration of oxygen vacancy for the as-synthesized samples varies with the increasing Ag content, and the Ag/ZnO sample with a Ag content of 5.0 atom % has the largest density of oxygen vacancy. In addition, the relationship between their structure and photocatalytic property is investigated in detail. It is found that the photocatalytic property is closely related to its structure, such as heterostructure, oxygen defect, and crystallinity. The presence of metallic Ag nanoparticles and oxygen vacancy on the surface of ZnO nanorods promotes the separation of photogenerated electron-hole pairs and thus enhances the photocatalytic activity.     

Synthesis and characterization of sulfide and selenide colloidal semiconductor nanocrystals

In this paper, we demonstrate the synthesis of sulfide and selenide nanocrystals in a water-ethanol mixed solution system. This synthetic way was based on the direct reactions between metal ions and S(2-)/Se. Linoleic acid was adopted to protect the nanocrystals from agglomeration. Without involving extreme experimental conditions, this less toxic synthetic route can be expected to bring more opportunities to nanocrystal-related research and application fields.     

False multiple exciton recombination and multiple exciton generation signals in semiconductor quantum dots arise from surface charge trapping

Multiple exciton recombination (MER) and multiple exciton generation (MEG) are two of the main processes for assessing the usefulness of quantum dots (QDs) in photovoltaic devices. Recent experiments, however, have shown that a firm understanding of both processes is far from well established. By performing surface-dependent measurements on colloidal CdSe QDs, we find that surface-induced charge trapping processes lead to false MER and MEG signals resulting in an inaccurate measurement of these processes. Our results show that surface-induced processes create a significant contribution to the observed discrepancies in both MER and MEG experiments. Spectral signatures in the transient absorption signals reveal the physical origin of these false signals.     

PbTe nanostructures: Microwave-assisted synthesis by using lead Schiff-base precursor,characterization and formation mechanism

Pure cubic phase lead telluride (PbTe) nanostructures have been produced by using a Schiff-base complex as a precursor in the presence of microwave irradiation. The Schiff base used as ligand was derived from salicylaldehyde and ethylenediamine. The Schiff-base complex was marked as [Pb(salen)]. In addition, the effect of the irradiation time and the type of reducing agent on the morphology and purity of the final products was investigated. The as-synthesized PbTe nanostructures were characterized extensively by techniques like X-ray powder diffraction (XRD), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The microwave formation mechanism of the PbTe nanostructures was studied by XRD patterns of the products. Although it was found that both ionic and atomic mechanisms could take place for the preparation of PbTe, the main steps were according to the atomic reaction process, which could occur between elemental Pb and Te.     

PVP-coated iron nanocrystals: Anhydrous synthesis, characterization, and electrocatalysis for two species

We report the synthesis of Fe nanocrystals (approximately 9 nm) in an anhydrous media, formamide, using poly(N-vinyl-2-pyrrolidone) (PVP) as a protecting agent. The morphology, structure, and composition of the PVP-coated Fe nanocrystals are studied by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and FT-Raman spectroscopy. The surface properties of the PVP-coated Fe nanocrystals are studied by electrochemistry and micro-surface-enhanced Raman scattering (mSERS) using pyridine as a probing molecule. The PVP-coated Fe nanocrystals, when immobilized on an electrode substrate, display very good electrocatalytic activities in the selective reduction of H2O2 in the presence of oxygen and in the oxidation of NO.     

MnO octahedral nanocrystals and MnO@C core-shell composites: synthesis, characterization, and electrocatalytic properties

We present a simple and facile synthesis of MnO octahedral nanocrystals and MnO@C core-shell composite nanoparticles. The synthesis is accomplished by a single-step direct pyrolysis of cetyltrimethylammonium permanganate in specially made Let-lock union cells. The products are characterized by HRSEM, HRTEM, Raman spectroscopy, and cyclic voltammetry (CV). The product consists mainly of octahedral MnO nanocrystals and MnO coated with carbon (MnO@C). The core-shell particles are observed only when the core size is smaller than 150 nm. The shape of the nanocrystals can be controlled by varying parameters such as reaction temperature and duration. As the temperature increases from 600 to 800 degrees C, the octahedral MnO crystals observed are without any carbon shell. The effect of time and temperature on the octahedral MnO nanocrystal formation is described. The electrocatalytic activities of the products are studied for oxygen reduction reaction in aqueous basic medium and are compared with bulk MnO. The MnO nanocrystals and core-shell composites exhibit higher activity than that of bulk MnO.     

Highly temperature responsive core-shell magnetic particles: synthesis, characterization and colloidal properties

Three new dimeric cholesterol-based compounds of A(LS)(2) type, where A stands for aromatic component, S steroid moiety, and L a linker connecting the two units, have been designed and prepared. Gelation test in 30 solvents demonstrated that the compounds can gel some of the solvents and form 37 gels, of which 16 form spontaneously at room temperature (~25 °C). These gels possess smart thixotropic properties as revealed by rheological studies. FTIR and (1)H NMR measurements revealed that hydrogen bonding is an important driving force for the formation of the gel networks. XRD analysis demonstrated that unlike commonly found layered structures adopted by dimeric cholesterol-based low-molecular mass gelators (LMMGs), one of the gelators created in this study adopts a hexagonal packing structure in its benzene gel.     

Controlled synthesis and size-dependent polarization domain structure of colloidal germanium telluride nanocrystals

Germanium telluride (GeTe) exhibits interesting materials properties, including a reversible amorphous-to-crystalline phase transition and a room-temperature ferroelectric distortion, and has demonstrated potential for nonvolatile memory applications. Here, a colloidal approach to the synthesis of GeTe nanocrystals over a wide range of sizes is demonstrated. These nanocrystals have size distributions of 10-20% and exist in the rhombohedral structure characteristic of the low-temperature polar phase. The production of nanocrystals of widely varying sizes is facilitated by the use of Ge(II) precursors with different reactivities. A transition from a monodomain state to a state with multiple polarization domains is observed with increasing size, leading to the formation of richly faceted nanostructures. These results provide a starting point for deeper investigation into the size-scaling and fundamental nature of polar-ordering and phase-change processes in nanoscale systems.     

Shape evolution and self assembly of monodisperse PbTe nanocrystals

In this communication, we report our recent achievement in synthesis and self-assembly of both spherical and cubic PbTe nanocrystals using a high-temperature solution-phase synthesis approach. The possible mechanism of nanocrystalline evolution from spherical to cubic structure has also been discussed. It is possible to use the highly orientated PbTe nanocrystals as building blocks to achieve thickness-controlled film for further manipulation into thermoelectric devices.     

Electronic and surface properties of PbS nanoparticles exhibiting efficient multiple exciton generation

Ultrafast transient absorption measurements have been used to study multiple exciton generation in solutions of PbS nanoparticles vigorously stirred to avoid the effects of photocharging. The threshold and slope efficiency of multiple exciton generation are found to be 2.5 ± 0.2 ×E(g) and 0.34 ± 0.08, respectively. Photoemission measurements as a function of nanoparticle size and ageing show that the position of the valence band maximum is pinned by surface effects, and that a thick layer of surface oxide is rapidly formed at the nanoparticle surfaces on exposure to air.     

Size-controlled chalcopyrite CuInS2 nanocrystals: One-pot synthesis and optical characterization

Chalcopyrite ternary CuInS2 semiconductor nanocrystals have been synthesized via a facile one-pot chemical approach by using oleylamine and oleic acid as solvents.The as-prepared CuInS2 nanocrystals have been characterized by instrumental analyses such as X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS),transmission electron microscopy(TEM)/high-resolution TEM(HRTEM),energy-dispersive X-ray spectroscopy(EDS),UV-vis absorption spectroscopy(UV-vis) and photoluminescence(PL) spectroscopy.The particle sizes of the CuInS2 nanocrystals could be tuned from 2 to 10 nm by simply varying reaction conditions.Oleylamine,which acted as both a reductant and an effective capping agent,plays an important role in the size-controlled synthesis of CuInS2 nanocrystals.Based on a series of comparative experiments under different reaction conditions,the probable formation mechanism of CuInS2 nanocrystals has been proposed.Furthermore,the UV-vis absorption and PL emission spectra of the chalcopyrite CuInS2 nanocrystals have been found to be adjustable in the range of 527-815 nm and 625-800 nm,respectively,indicating their potential application in photovoltaic devices.     

Solar cells from colloidal nanocrystals: Fundamentals,materials, devices,and economics

Recent advances in colloidal science are having a dramatic impact on the development of next generation low-cost and/or high-efficiency solar cells. Simple and safe solution phase syntheses that yield monodisperse, passivated, non-aggregated semiconductor nanocrystals of high optoelectronic quality have opened the door to several routes to new photovoltaic devices which are currently being explored. In one route, colloidal semiconductor nanocrystal “inks” are used primarily to lower the fabrication cost of the photoabsorbing layer of the solar cell. Nanocrystals are cast onto a substrate to form either an electronically coupled nanocrystal array or are sintered to form a bulk semiconductor layer such that the bandgap of either is optimized for the solar spectrum (1.0–1.6 eV if the photon to carrier quantum yields less than 100%). The sintered devices (and without special efforts, the nanocrystal array devices as well) are limited to power conversion efficiencies less than the Shockley–Queisser limit of 33.7% but may possibly be produced at a fraction of the manufacturing cost of an equivalent process that uses vacuum-based deposition for the absorber layer. However, some quantum confined nanocrystals display an electron-hole pair generation phenomena with greater than 100% quantum yield, called “multiple exciton generation” (MEG) or “carrier multiplication” (CM). These quantum dots are being used to develop solar cells that theoretically may exceed the Shockley–Queisser limit. The optimum bandgap for such photoabsorbers shifts to smaller energy (0.6–1.1 eV), and thus colloidal quantum dots of low bandgap materials such as PbS and PbSe have been the focus of research efforts, although multiple exciton generation has also been observed in several other systems including InAs and Si. This review focuses on the fundamental physics and chemistry of nanocrystal solar cells and on the device development efforts to utilize colloidal nanocrystals as the key component of the absorber layer in next generation solar cells. Development efforts are put into context on a quantitative and up-to-date map of solar cell cost and efficiency to clarify efforts and identify potential opportunities in light of technical limitations and recent advances in existing technology. Key nanocrystal/material selection issues are discussed, and finally, we present four grand challenges that must be addressed along the path to developing low-cost high-efficiency nanocrystal based solar cells.