Surface Capping Ligands Research Articles

2-Thiopheneacetic Acid Directed Synthesis of Au Nanorosette as an SERS-Active Substrate

Rosette-like nanoscale Au materials were simply prepared through one-pot reduction of the AuCl₄⁻ precursor by 2-thiopheneacetic acid (2-TAA) without extra surface capping ligands at room temperature. 2-TAA underwent polymerization into polythiophene derivatives while the AuCl₄⁻ precursor was simultaneously reduced into various Au nanostructures. In situ generated polythiophene derivatives played a significant role of surface passivation in guiding the shape of Au nanostructures. The morphology of Au nanostructures was strongly dependent on the molar ratio of 2-TAA to AuCl₄⁻. At lower [2-TAA]/[AuCl₄⁻] ratios, uniform rosette-like Au microparticles consisting of 30-nm-thick Au nanoplates were observed. The Au nanoplates had either triangular prismatic or hexagonal geometry with many defects. Uniform Au nanorosettes could be easily deposited on the Si substrate by drop-casting and were subsequently used as highly active SERS substrates for the detection of methylene blue and crystal violet by Raman spectroscopy. Upon increasing the ratio of [2-TAA]/[AuCl₄⁻], Au nanoparticles or nanorods heavily surrounded with polythiophene polymers were obtained.

Synthesis of low-temperature-processable and highly conductive Ag ink by a simple ligand modification: the role of adsorption energy

Acetic acid (AA) has been employed to reduce the surface capping ligands of Ag nanoparticles (NPs) for the fabrication of low-temperature-processable and highly conductive Ag ink. The ligand reduction of the Ag NPs was achieved using a one-step method, in which oleylamine (OA)-capped Ag NPs were immersed in AA for different durations (1, 2, 3, 5 and 10 h). The weight of the total capping ligand was reduced from 12.1 wt% to 2.3 wt% by 10 h AA immersion. According to in situ transmission electron microscopy (TEM) and electrical resistivity, the ligand-reduced Ag NPs were cured at a much lower temperature (approximately 100 °C) and showed better electrical performance than OA-capped NPs under the same conditions. To investigate the reason for this enhancement of the electrical properties, we characterized the surface chemistry of the Ag NPs by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS), which revealed that the surface capping ligand was exchanged from the OA to the acetate ion. In addition, the adsorption energy of the ligand was increased by the ligand exchange, which was studied using density functional theory (DFT) calculations. DFT was effective in explaining the adsorption of each ligand on Ag NPs and indicated that the ligand can be exchanged by AA immersion.

Phase Transfer of CdS Nanocrystals Mediated by Heptamine β-Cyclodextrin

A fundamental and systematic study on the fabrication of a supramolecularly assembled nanostructure of an organic ligand-capped CdS nanocrystal (NC) and multiple heptamine β-cyclodextrin ((NH(2))(7)βCD) molecules in aqueous solution has been here reported. The functionalization process of presynthesized hydrophobic CdS NCs by means of (NH(2))(7)βCD has been extensively investigated by using different spectroscopic and structural techniques, as a function of different experimental parameters, such as the composition and the concentration of CD, the concentration of CdS NCs, the nature of the NC surface capping ligand (oleic acid and octylamine), and the organic solvent. The formation of a complex based on the direct coordination of the (NH(2))(7)βCD amine groups at the NC surface has been demonstrated and found responsible for the CdS NC phase transfer process. The amine functional group in (NH(2))(7)βCD and the appropriate combination of pristine capping agent coordinating the NC surface and a suitable solvent have been found decisive for the success of the CdS NC phase transfer process. Furthermore, a layer-by-layer assembly experiment has indicated that the obtained (NH(2))(7)βCD functionalized CdS NCs are still able to perform the host-guest chemistry. Thus, they offer a model of a nanoparticle-based material with molecular receptors, useful for bio applications.

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.

Chemical synthesis of monodispersed ZnSe nanowires and its functional properties

Monodispersed ZnSe nanowires have been synthesized by wet chemical method using edamine as a surface capping ligand. The structure, morphology and chemical compositions of the as synthesized samples were investigated by X-ray diffractometer, field emission scanning electron microscopy, transmission electron microscopy and energy dispersive X-ray analysis. Ultraviolet visible absorption spectrum confirms that the absorption edge is located at 371nm which is blue shifted when compared to the value of bulk ZnSe. The photoluminescence spectrum shows that the emission peak is located at 442nm which corresponds to near band edge emission. The nanowires have uniform average diameter of 80nm and the length of about few micrometers. The presence of Edamine is confirmed by the Fourier transform spectrophotometer. The possible growth mechanism is addressed.

Synthesis of CdS, ZnS, and CdS/ZnS Core/Shell Nanocrystals Using Dodecanethiol

We report a new route to synthesize high quality zinc blende CdS and ZnS nanocrystals in noncoordinating solvent 1-octadecene, using dodecanethiol (DDT) molecules as both the sulfur source and surface capping ligands. Different reaction temperatures and Cd(Zn)/DDT molar ratios were tested to optimize the synthesis conditions. Absorption photoluminescence (PL) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) pattern, and transmission electron microscopy (TEM) were used to characterize assynthesized nanocrystals. The narrow half width at the half-maximum on the long wavelength side of the firstexcitonic absorption peak and TEM images demonstrated nearly monodisperse size distributions of asprepared CdS, ZnS, and CdS/ZnS core/shell nanocrystals. Only trap emissions of the nanocrystals were detected when the amount of DDT was excessive, this came from the strong quenching effect of thiol groups on the nanocrystal surfaces. After overcoating with ZnS shells, band-gap emissions of CdS nanocrystals were partially recovered.

Weakly-coordinated stable platinum nanocrystals

Stable platinum nanocrystals with small diameters (1.0–2.3 nm), that are stable for a long time, with narrow size distributions were easily and reproducibly prepared without any additional stabilizers in glycol, glycerol, the ionic liquids (ILs) 1-n-butyl-3-methyl-imidazolium tetrafluoroborate [BMIm][BF4] and N-butyl-N-trimethyl-ammonium bis(trifluoromethylsulfonyl)imide [N4111][NTf2] or diphenylmethane (CH2Ph2) by thermal, photolytic or microwave assisted decomposition of the organometallic precursor methylcyclopentadienyl-trimethylplatinum(IV), (MeCp)PtMe3. Decomposition of the easily dispensible, air and moisture stable organometallic Pt(IV) precursor (MeCp)PtMe3 leads to well defined, small, crystalline and longterm stable Pt-nanoparticle (Pt-NP) dispersions without any additional surface-capping ligands. The Pt-NP/IL dispersion was shown to be a highly active catalyst (TOF 96 000 h−1 at 0.0125 mol% Pt and quantitative conversion) for the biphasic hydrosilylation of phenylacetylene with triethylsilane, to the distal and proximal products triethyl(2- and1-phenylvinyl)silane.

Facile Synthesis of Straight and Branched CdTe Nanowires Using CdO as Precursor

High-quality colloidal CdTe nanowires (NWs) containing both straight and branched ones were controllably prepared via a solution-based approach, using a low melting Bi nanoparticles as catalysts, CdO and tributylphosphine telluride (TBP-Te) as precursors, and a tri-n-octylphosphine oxide/tri-n-octylphosphine (TOPO/TOP) mixture as solvent. The resulting straight CdTe NWs have typical diameters below 20 nm accompanying with lengths exceeding 10 microm. In the case of branched CdTe NWs, tripod, V-shaped and y-shaped morphologies are obtained by decreasing the apparent Cd/Te molar ratio. It is found that, as the surface capping ligands, di-n-octylphosphinic acid (DOPA) is superior to decylphosphonic acid (DPA) in the reproducible growth of high-quality CdTe NWs. Since highly toxic dimethylcadmium, a cadmium precursor widely used in literatures, is replaced by CdO and the amount of the TOPO/TOP solvent mixture is significantly reduced, a relative safe and economical synthetic approach of high-quality colloidal CdTe NWs with controllable morphology is thus presented.

Influence of Surfactants and Charges on CdSe Quantum Dots

Surface effects significantly influence the functionality of semiconductor nanocrystals. High quality nanocrystals can be achieved with good control of surface passivation by various hydrophobic ligands. In this work, the chemistry between CdSe quantum dots and common surface capping ligands is investigated using density functional theory (DFT). We discuss the electronic structures and optical properties of small CdSe clusters controlled by their size of particle, self-organization, capping ligands, and positive charges. The chosen model ligands reproduce good structural and energetic description of the interactions between the ligands and quantum dots. In order to capture the chemical nature and energetics of the interactions between the capping ligands and CdSe quantum dots, we found that PMe3 is needed to adequately model trioctylphosphine (TOP), NH3 is sufficient for amines, while OPH2Me could be used to model trioctylphosphine oxide. The relative binding interaction strength between ligands was found to decrease in order Cd–O > Cd–N > Cd–P with average binding energy per ligand being −25 kcal/mol for OPH2Me, −20 kcal/mol for NH3 and −10 kcal/mol for PMe3. Charges on studied stoichiometric clusters were found to have a significant effect on their structures, binding energies, and optical properties.

Fabrication of Core–Shell-Type Copper Indium Selenide and Zinc Selenide Composite Quantum Dots and Their Optical Properties

We successfully fabricated core/shell-type composite QDs based on the ternary-CuInSe2. For the CuInSe2/ZnSe core/shell QDs, an enhanced photoluminescence (PL) emission intensity, such as 16% of the photoluminescence quantum yield (PLQY), and a blue-shift in the emission after the ZnSe coating, were observed. The increase in the PLQY was the result of an exchange of the surface capping ligand from the organic hexadecylamine to the inorganic ZnSe and the smoothing of the confining profile due to the alloying. The blue-shift was attributed to the shrinkage of the effective size of the core-CuInSe2 region due to the partial alloying of the core-CuInSe2 with the ZnSe-shell around their interfaces. For the inverted core/shell QDs, i.e., the nominally ZnSe/CuIn5Se8 core/shell QDs, they showed a red emission at 619 nm. The emission wavelength is the shortest among the previously reported QDs in Cu-In-Se system.

UV luminescent organic-capped ZnO quantum dots synthesized by alkoxide hydrolysis with dilute water

A novel synthesis route to organic-capped and colloidal ZnO quantum dots (QDs) has been developed. Specifically, zinc-di- t-butoxide and zinc-di- n-butoxide are hydrolyzed by very dilute water (400–600 mass ppm) in hydrophilic benzylamine and polymerized to ZnO by dehydration and/or a butanol elimination reaction. Growth of the ZnO QDs and exchange of the surface capping ligand from the hydroxyl groups and/or benzylamine to the oleylamine occur by heating the colloidal solution after addition of the oleylamine at 100–180 °C. The final ZnO QDs with diameters in the range of 3–7 nm are highly dispersible in various organic solvents. The ZnO QDs exhibit the quantum size effect upon UV emission; it was controlled between 3.39 and 3.54 eV in the present study. The defect-related Vis emission decreased and the UV emission becomes dominant when zinc-di- n-butoxide with a 99.99% zinc purity is used as the starting material. The intensity of the photoluminescence UV emission is 1.5 times higher than that of the Vis emission.

Photocatalytic study of two-dimensional ZnO nanopellets in the decomposition of methylene blue

We report several significant photodecomposition rates of methylene blue (MB) obtained before and after the refluxing process of own-synthesized two-dimensional (2D) zinc oxide (ZnO) nanopellets. Each photodecomposition rate of MB was found highly dependent on the weight of photocatalyst. The existing photodecomposition rate has been successfully improved to a factor of 22.0 times through refluxing process in excessive pyridine where the surface capping ligand (oleic acid) is removed from the 2D ZnO nanopellets. On the other hand, the refluxed photocatalyst (0.04 g) in this study was found to exhibit excellent recyclability up to three cycles. Furthermore, X-ray powder diffraction spectrums for the refluxed photocatatalyst, respectively, before and after three cycles of photocatalytic reactions, has generated the same patterns showing that the photocatalyst is stable and feasible to be used as an efficient photocatalyst material. Hence, these 2D ZnO nanopellets would provide a new alternative route as a highly efficient photocatalyst for wastewater treatment.

Synthesis and characterization of perovskite PbTiO3 nanoparticles with solution processability

Ferroelectrics with perovskite structure (ABO3), for example, lead titanate (PbTiO3), are the most studied ferroelectric oxides because of their versatile properties for use in thin film capacitors, electronic transducers, actuators, high-k dielectrics, pyroelectric sensors, and nonlinear optics. The studies on nanostructured PbTiO3 are limited, mainly due to the lack of facile synthetic techniques to prepare nano-sized PbTiO3, i.e., colloidal PbTiO3 nanoparticles. Herein, we presented a novel nonaqueous, relatively low temperature, and highly scalable route to PbTiO3 nanoparticles. The use of oleic acid as surface capping ligand provides nanoparticles with good solubility in organic solvents, thereby enabling the low-cost solution based processing. Rather than the use of expensive bimetallic alkoxide precursors, common chemicals were utilized in this non-hydrolytic thermal decomposition approach; moreover, there is no need for extremely high temperature and long reaction time, making it possible for the large scale synthesis.

Synthesis of Organic Capped Colloidal Zinc Oxide Quantum Dots and Their UV Dominant Emission Property

AbstractA novel synthesis route to organic-capped and colloidal ZnO quantum dots (QDs) has been developed. Specifically, zinc-di-butoxide was hydrolyzed with very dilute water (100˜600 mass ppm) dissolved in hydrophilic benzylamine and polymerized to ZnO by dehydration condensation. After formation of ZnO QDs with 2˜3 nm in diameter, growth of the QDs and exchange the surface capping ligand from hydroxyl groups and/or benzylamine to oleylamine were developed by heating the colloidal solution with oleylamine. The size of the ZnO QDs finally obtained was in the range 3˜5 nm in diameter. The QDs show high dispersibility in various organic solvents. Clear UV emission due to exciton recombination was observed; and its energy was varied according to the quantum size effect from 3.39 to 3.54 eV. By using lithium-free zinc-di-butoxide as a starting material, the defect-related VIS emission was successfully decreased and the UV emission becomes dominant. The influence of water concentration in benzylamine and oleylamine on UV emission intensity was also investigated.

Nanoparticle-assisted high photoconductive gain in composites of polymer and fullerene

Polymer-inorganic nanocrystal composites offer an attractive means to combine the merits of organic and inorganic materials into novel electronic and photonic systems. However, many applications of these composites are limited by the solubility and distribution of the nanocrystals in the polymer matrices. Here we show that blending CdTe nanoparticles into a polymer-fullerene matrix followed by solvent annealing can achieve high photoconductive gain under low applied voltages. The surface capping ligand renders the nanoparticles highly soluble in the polymer blend, thereby enabling high CdTe loadings. An external quantum efficiency as high as approximately 8,000% at 350 nm was achieved at -4.5 V. Hole-dominant devices coupled with atomic force microscopy images show a higher concentration of nanoparticles near the cathode-polymer interface. The nanoparticles and trapped electrons assist hole injection into the polymer under reverse bias, contributing to efficiency values in excess of 100%.

Reagent control over the size, uniformity, and composition of Co–Fe–O nanoparticles

Cobalt–iron–oxide (Co–Fe–O) nanoparticles have been prepared by the thermal decomposition in benzyl ether of Fe(acac)3 and Co(acac)2 in the presence of a mixture of oleic acid and oleylamine templating (surface capping) ligands, and 1,2-hexadecanediol (HDD) as an accelerating agent. The Co percentage may be tuned by adjusting the amount of Co(acac)2 precursor without influencing the average particle size or particle size distribution. Counter to prior reports the presence of the HDD accelerating agent results in broader nanoparticle diameter distribution; however, for the smallest average sizes a small amount of HDD appears to be beneficial. The effects of changes in the templating ligand concentration and the relative amounts of oleic acidversusoleylamine have been investigated to optimize particle size distribution. Dilution of all the reagents is detrimental to particle size control. Our method for producing 5 nm Co–Fe–O nanoparticles with narrow distributions has reduced the amount of HDD while simultaneously reducing the reaction time.

Synthesis of CdSeS Nanocrystals in Coordinating and Noncoordinating Solvents: Solvent's Role in Evolution of the Optical and Structural Properties

CdSexSy nanocrystals were synthesized in eight solvents that have different coordinating properties, trioctylphosphine oxide, trioctylphosphine, triphenylphosphine, oleylamine, hexadecylamine, dioctylamine, trioctylamine, and 1-octadecene at 230−300 °C. These nanocrystals exhibited high photoluminescence, which could be tuned over most of the visible region by changing the Se/S ratio or the solvent. The nanocrystals were characterized using UV−vis and IR spectroscopy, TEM, EDS, XRD, and NMR. 31P NMR and IR studies provided vital information about the nanocrystal surface capping ligands, indicating that those prepared in noncoordinating solvents were stabilized in solution mainly by oleic acid while those prepared in the coordinating solvents were stabilized mainly by solvent, phosphine and phosphine sulfide ligands, and some oleic acid. The hexagonal or cubic phase of these nanocrystals can be selectively prepared at temperatures as high as 300 °C by choosing the appropriate solvent.

Synthesis and Characterization of Colloidal CuInS2 Nanoparticles from a Molecular Single-Source Precursor

Thermal decomposition of the molecular single-source precursor (PPh3)2CuIn(SEt)4 in the presence of hexanethiol in dioctylphthalate forms colloidal CuInS2 at 200 °C. The colloidal solution displays size-dependent quantum confinement behavior in the absorption and photoluminescence spectra. The average size of the nanocrystals can be increased from 2 to 4 nm by raising the reaction temperature from 200 °C to 250 °C. The nanoparticles are capped with hexanethiol ligands; these ligands can be exchanged with trioctylphosphine oxide or pyridine. The nature of the surface-capping ligands has a significant effect on the photoluminescence emission intensity. Investigation of the effect of synthesis parameters and postsynthesis treatments on the optical properties of the nanocrystals leads to the conclusion that the room-temperature emission originates in donor−acceptor defects.

Design of Water-Soluble Quantum Dots with Novel Surface Ligands for Biological Applications

ABSTRACTWe have designed a series of organic oligo- and polyethylene glycol (PEG) based surface capping ligands that allow for QD manipulation in aqueous media. We utilized readily available thioctic acid and various oligo- and polyethylene glycols in simple esterification schemes, followed by reduction of the dithiolane to produce multi-gram quantities of capping substrates. Cap exchange of the native trioctyl-phosphine and -phosphine oxide based ligands with the PEG-terminated dithiol-alkyl cap readily resulted in aqueous dispersions of QDs that were homogeneous and stable in various pH ranges over an extended period of time. Mixed surface capping strategies utilizing ratios of dihydrolipoic acid to the pegylated dihydrolipoic acid were also prepared. We anticipate that such systems should allow one to covalently attach amine containing biomolecules to nanoparticle systems bearing carboxylates, employing known coupling agents, such as (dimethylamino) propyl-3-ethyl-carbodiimide (EDC). This design and conjugation strategy may facilitate the development of a new generation of QD-bioconjugates, which can be directly utilized in bio-related applications such as sensing and cellular imaging.

Size-Dependent Optical Spectroscopy of a Homologous Series of CdSe Cluster Molecules

The optical properties and electronic structure of a homologous series of CdSe cluster molecules covering a size range between 0.7 and 2 nm are investigated. CdSe cluster molecules with 4, 8 10, 17, and 32 Cd atoms, capped by selenophenol ligands, were crystallized from solution and their structures determined by single-crystal X-ray diffraction. The cluster molecules are composed of a combination of adamanthane and barylene-like cages, the building blocks of the zinc blende and the wurtzite structures of the bulk CdSe. The onset of the room temperature absorption and low-temperature photoluminescence excitation spectra exhibit a systematic blue shift with reduced cluster size manifesting the quantum confinement effect down to the molecular limit of the bulk semiconductor. Blue-green emission, shifted substantially to lower energy from the absorption onset, is observed only at low temperature and its position is nearly independent of cluster size. The wavelength dependence of both photoluminescence and photoluminescence excitation was measured. The emission is assigned to forbidden transitions involving the cluster-molecule surface-capping ligands. This assignment is supported by the emission decay which exhibits distributed kinetics with microsecond time scale. The temperature dependence of the emission intensity is quantitatively explained by multiphonon-induced nonradiative relaxation mediated by low-frequency vibrations of the selenophenol capping ligands. Upon irradiation, the emission of all cluster molecules is quenched. Warming up and recooling leads to recovery of the emission (partial or complete) for all but the cluster molecule with 10 Cd atoms. This temporary darkening is assigned to the photoinduced charging of the cluster-molecule surface ligands, resembling the reversible on-off blinking of the emission observed for larger CdSe nanocrystals.