Joanna Kolny-Olesiak

Synthesis and Shape Control of CuInS2 Nanoparticles

Cu(2)S-CuInS(2) hybrid nanostructures as well as pure CuInS(2) (CIS) nanocrystals were synthesized by methods of colloidal chemistry. The structure, the shape and the composition of these nanomaterials were investigated with transmission electron microscopy (TEM), powder X-ray diffraction (XRD) and energy dispersive X-ray analysis (EDX). By changing the reaction conditions, CuInS(2) nanorods with different aspect ratio, dimeric nanorods as well as hexagonal discs and P-shaped particles could be synthesized. Under our reaction conditions, CIS nanoparticles crystallize in the hexagonal wurtzite structure, as confirmed by Rietveld analysis of the X-ray diffraction patterns. The formation of Cu(2)S-CuInS(2) hybrid nanostructures turned out to be an essential intermediate step in the growth of CIS nanoparticles, the copper sulphide part of the hybrid material playing an important role in the shape control of the CIS nanocrystals. By a treatment of Cu(2)S-CuInS(2) with 1,10-phenanthroline, Cu(2)S parts of the hybrid nanostructures could be removed, and pure CIS nanoparticles with shapes not accessible with other methods can be obtained. Our synthetic procedure turned out to be suitable to synthesize also other compounds, like CuInS(2)-ZnS alloys, and to modify, in this way, the optical properties of the nanocrystals.

Synthesis and Application of Colloidal CuInS2 Semiconductor Nanocrystals

Semiconductor nanocrystals possess size-dependent properties, which make them interesting candidates for a variety of applications, e.g., in solar energy conversion, lighting, display technology, or biolabelling. However, many of the best studied nanocrystalline materials contain toxic heavy metals; this seriously limits their potential for widespread application. One of the possible less toxic alternatives to cadmium- or lead-containing semiconductors is copper indium disulfide (CIS), a direct semiconductor with a bandgap in the bulk of 1.45 eV and a Bohr exciton radius of 4.1 nm. This Review gives an overview of the methods developed during the last years to synthesize CIS nanocrystals and summarizes the possibilities to influence their shape, composition and crystallographic structure. Also the potential of the application of CIS nanocrystals in biolabellling, photocatalysis, solar energy conversion, and light-emitting devices is discussed.

Size and shape control of colloidal copper(I) sulfide nanorods.

Many physical and chemical properties of semiconducting nanocrystals strongly depend on their spatial dimensions and crystallographic structure. For these reasons, achieving a high degree of size and shape control plays an important role with respect to their application potential. In this report we present a facile route for the direct colloidal synthesis of copper(I) sulfide nanorods. A high reactivity of the starting materials is essential to obtain nanorods. We achieve this by using a thiol that thermally decomposes easily and serves as the sulfur source. The thiol is mixed in a noncoordinating solvent, which acts as the reaction medium. Adjustment of the nucleation temperature makes it possible to tailor uniform nanorods with lengths from 10 to 100 nm. The nanorods are single crystalline, and the growth direction is shown to occur along the a-axis of djurleite. The growth process and character of the nanorods were investigated through UV-vis and NIR absorption spectroscopy, transmission electron microscopy, and powder X-ray diffraction measurements.

Spectral features above LO phonon frequency in resonant Raman scattering spectra of small CdSe nanoparticles

We report unusual spectral features in the resonant Raman scattering spectra of colloidal CdSe nanoparticles as small as 2–3 nm. High-frequency shoulders of the longitudinal optical phonon peak and its overtones were observed and their dependence on the excitation wavelength, temperature, nanoparticle size, and surface passivation with ZnS shell studied. As the probable origin of the uncommon spectral feature the participation of acoustic phonons and manifestation of the density of surface-related vibrational states is discussed.

Colloidal synthesis and structural control of PtSn bimetallic nanoparticles.

PtSn bimetallic nanoparticles with different particle sizes (1-9 nm), metal compositions (Sn content of 10-80 mol %), and organic capping agents (e.g., amine, thiol, carboxylic acid and polymer) were synthesized by colloidal chemistry methods. Transmission electron microscopy (TEM) measurements show that, depending on the particle size, the as-prepared bimetallic nanocrystals have quasi-spherical or faceted shapes. Energy-dispersive X-ray (EDX) analyses indicate that for all samples the signals of both Pt and Sn can be detected from single nanoparticles, confirming that the products are actually bimetallic but not only a physical mixture of pure Pt and Sn metal nanoparticles. X-ray diffraction (XRD) measurements were also conducted on the bimetallic particle systems. When compared with the diffraction patterns of monometallic Pt nanoparticles, the bimetallic samples show distinct shifts of the Bragg reflections to lower degrees, which gives clear proof of the alloying of Pt with Sn. However, a quantitative analysis of the lattice parameter shifts indicates that only part of the Sn atoms are incorporated into the alloy nanocrystals. This is consistent with X-ray photoelectron spectroscopy (XPS) measurements that reveal the segregation of Sn at the surfaces of the nanocrystals. Moreover, short PtSn bimetallic nanowires were synthesized by a seed-mediated growth method with amine-capped bimetallic particles as precursors. The resulting nanowires have an average width of 2.3 nm and lengths ranging from 5 to 20 nm.

Phonon Raman spectra of colloidal CdTe nanocrystals: effect of size, non-stoichiometry and ligand exchange

Resonant Raman study reveals the noticeable effect of the ligand exchange on the nanocrystal (NC) surface onto the phonon spectra of colloidal CdTe NC of different size and composition. The oleic acid ligand exchange for pyridine ones was found to change noticeably the position and width of the longitudinal optical (LO) phonon mode, as well as its intensity ratio to overtones. The broad shoulder above the LO peak frequency was enhanced and sharpened after pyridine treatment, as well as with decreasing NC size. The low-frequency mode around 100 cm-1 which is commonly related with the disorder-activated acoustical phonons appears in smaller NCs but is not enhanced after pyridine treatment. Surprisingly, the feature at low-frequency shoulder of the LO peak, commonly assigned to the surface optical phonon mode, was not sensitive to ligand exchange and concomitant close packing of the NCs. An increased structural disorder on the NC surface, strain and modified electron-phonon coupling is discussed as the possible reason of the observed changes in the phonon spectrum of ligand-exchanged CdTe NCs.PACS: 63.20.-e, 78.30.-j, 78.67.-n, 78.67.Bf

Role of copper sulfide seeds in the growth process of CuInS2 nanorods and networks.

CuInS2 nanorods and networks are interesting candidates for applications requiring efficient charge transport, such as solar energy conversion, because of the increased electrical conductivity in elongated or interconnected nanocrystals, compared to isolated, quasi-spherical ones. However, little is known about the growth mechanisms involved in the formation of this kind of nanostructures, yet. Here, CuInS2 nanorods and networks were synthesized through a facile low-cost and phosphine-free method. Copper and indium sources were added together in the presence of oleylamine and oleic acid. Changing the amount of oleic acid present in the reaction solution influenced the reactivity of the monomers, and consequently, the size of copper sulfide seeds formed in situ after the injection of tert-dodecanethiol, serving as the source of sulfur. Two different growth mechanisms of CuInS2 nanorods were observed, depending on the size of the copper sulfide seeds. Larger seeds (8 nm), which were generated with relatively small amounts of oleic acid, resulted in the formation of hybrid copper sulfide-copper indium disulfide nanocrystals as intermediates in the growth process of the nanorods, while smaller seeds (4 nm) obtained with relatively large amounts of oleic acid were gradually converted to copper indium sulfide nanorods. At longer reaction times, these nanorods formed network structures. The reaction between oleylamine and oleic acid at high temperature turned out to be the crucial factor to induce the attachment of nanorods to multipods and networks.

Synthesis of copper sulphide-based hybrid nanostructures and their application in shape control of colloidal semiconductor nanocrystals

Copper sulphide is a material with low toxicity and high application potential. Colloidal synthesis allows its incorporation into hybrid nanostructures, which not only combine the properties of different materials within one nanocrystal, but also exhibit new features due to the interaction of the building blocks connected on the nanometer scale. Starting with copper sulphide seeds, such hybrid nanocrystals composed of copper sulphide and semiconductors like CuInS2, CuInxGa1−xS2, Cu2ZnSnS4, ZnS, CdS, and PbS have been synthesized. In some of these reactions the main focus lies on the formation of new hybrid nanocrystals; in others copper sulphide plays the role of a catalyst, and copper sulphide containing hybrid nanoparticles are only intermediates in the synthesis and shape control of other semiconductor materials. Both possibilities and the underlying growth mechanisms are discussed in this article.

Recent Developments in Colloidal Synthesis of CuInSe2 Nanoparticles

Ternary semiconductor nanocrystals, such as CuInSe2 , are of high interest for photovoltaic application due to their relatively low toxicity and unique properties. During the last decades great success has been achieved in the colloidal synthesis of binary nanoparticles, but for ternary compounds this research is still in an early stage of development. These materials are a challenge for synthetic chemistry, because the interaction between the three components (copper, indium, and selenium) plays a major role for the production of high quality material. The purpose of this Minireview is to provide a summary of the achievements in colloidal synthesis of CuInSe2 nanoparticles--in particular, details of reaction mechanism and its characterization possibilities, which might be useful also for the colloidal synthesis of other multicomponent systems.

Influence of particle size in hybrid solar cells composed of CdSe nanocrystals and poly(3-hexylthiophene)

Inorganic semiconductor nanoparticles, such as CdSe quantum dots, are considered to be a promising alternative to fullerene derivates for application as electron acceptors in polymer-based bulk heterojunction solar cells. The main potential advantage is the strong light absorption of CdSe nanoparticles with a spectral bandwidth, which can even be tuned, due to the quantum size effect. However, the impact of the particle size on the performance of polymer/CdSe solar cells has remained largely unexplored so far. Therefore, the influence of particle size in hybrid solar cells using a blend of poly(3-hexylthiophene) (P3HT) and quasi-spherical CdSe nanoparticles on relevant cell parameters and the overall solar cell performance is systematically studied in the present work. As the most important result, an increase of the open-circuit voltage (VOC) can be found for smaller nanoparticles and can be explained by an “effective bandgap” model. In contrast, no significant changes of the short-circuit current densit...