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The described method enables facile gram scale preparation of CuFeS2 nanocrystals form simple and readily available precursors, exhibiting interesting thermoelectric properties. Exchange of primary organic ligands for inorganic ones using either (NH4)2S or triethyloxonium tetrafuoroborate (Meerwein's salt) resulted in nanocrystals from which n-type bulk thermoelectric materials could be obtained through sintering under pressure. The measured physical properties of the fabricated bulk thermoelectrics depended on the type of inorganic ligands used for the exchange. In particular, materials surface modified with Meerwein's salt showed higher Seebeck coefficient (ǀSǀ = 238 V K-1) as compared to those modified with (NH4)2S whereas the latter exhibited higher electrical conductivity (8500 S m-1) and lower thermal conductivity (0.5 W m-1 K-1), both parameters favorable for thermoelectric applications.

Chalcopyrite-type (Cu–Fe–S2) ternary nanocrystals stabilized by long aliphatic chain ligands could be considered as isolated hard nanoobjects dispersed in a soft network of organic ligands. The main attention was paid to the behavior of the particles whose average size was varied in a controllable manner from 3 to 20 nm. Dynamics of the nanoparticles was studied by applying Mossbauer spectroscopy. The fast dynamics could be described by a two-level environment. The deeper level (atomic) was practically the same as for bulk material except for the Debye temperature, but the higher level (particle motion) was described by the classical harmonic oscillator with the spring constant dramatically softening with increasing temperature. Such behavior led to a fast decrease of the fraction detectable by Mossbauer spectroscopy with increasing temperature. The induced internal oscillations within a particle by the surrounding thermal bath additionally contribute to the shift of measured spectra. Slow dynamics was ch...

Ternary Ag–In–S or quaternary Ag–In–Zn–S nanocrystals were prepared from simple precursors (silver nitrate, indium(III) chloride, zinc stearate in a mixture of DDT and ODE) by injecting a solution of elemental sulfur into OLA. Ternary nanocrystals were modified by depositing either a ZnS or a CdS shell, yielding type I and type II core/shell systems exhibiting photoluminescence QY in the range of 12–16%. Careful optimization of the reaction conditions allowed alloyed quaternary Ag–In–Zn–S nanocrystals exhibiting tunable photoluminescence in the spectral range of 520–720 nm with a QY of 48% and 59% for green and red radiations, respectively, to be obtained. 1H NMR analysis of the nanocrystal organic shell, after dissolution of its inorganic core, indicated that surfacial sulfur atoms were covalently bonded to aliphatic chains whereas surfacial cations were coordinated by amines and carboxylate anions. No thiol-type ligands were detected. Transfer of the prepared nanocrystals to water could be achieved in one step by exchanging the initial ligands for 11-mercaptoundecanoic ones resulting in a QY value of 31%. A new Ag–In–Zn–S nanocrystal preparation method was elaborated in which indium and zinc salts of fatty acids were used as cation precursors and DDT was replaced by thioacetamide. This original DDT-free method enabled similar tuning of the photoluminescence properties of the nanocrystals as in the previous method; however the measured photoluminescence QYs were three times lower. Hence, further optimization of the new method is required.

Cu-Fe-S nanocrystals exhibiting a strong localized surface plasmon resonance (LSPR) effect were synthesized for the first time. The elaborated reproducible preparation procedure involved copper(II) oleate, iron(III) stearate, and sulfur powder dissolved in oleylamine (OLA) as precursors. The wavelength of the plasmonic resonance maximum could be tuned by changing the Cu/Fe ratio in the resulting nanocrystals, being the most energetic for the 1:1 ratio (486 nm) and undergoing a bathochromic shift to ca. 1200 nm with an increase to 6:1. LSPR could also be observed in nanocrystals prepared from the same metal precursors and sulfur powder dissolved in 1-octadecene (ODE), provided that the sulfur precursor was taken in excess. Detailed analysis of the reaction mixture by chromatographic techniques, supplemented by mass spectrometry and (1)H NMR spectroscopy enabled the identification of the true chemical nature of the sulfur precursor in S/OLA, namely, (C18H35NH3(+))(C18H35NH-S8(-)), a reactive product of the reduction of elemental sulfur by the amine groups of OLA. In the case of the S/ODE precursor, the true precursors are much less reactive primary or secondary thioethers and dialkyl polysulfides.

The role of the solvent in the preparation of ternary CuInX2 (X = S or Se) nanocrystals was investigated. It was found that the use of oleylamine as a solvent with copper(II) oleate, indium(III) acetate diphenyl diselenide as precursors yields copper-rich, wurtzite-type Cu2.0In1.0Se2.5 (2Cu2Se–In2Se3) nanocrystals which after size sorting exhibit the quantum confinement effect. Changing oleylamine for 1-octadecene, while keeping the same set of precursors and reaction conditions, results in the formation of indium-rich chalcopyrite nanocrystals Cu1.0In1.8Se3.2 (Cu2Se-1.8 In2Se3). The differences in the stoichiometry can be rationalized on the basis of stronger reducing properties of oleylamine which more effectively reduces Cu(II) to Cu(I) in the reaction medium. Stoichiometric chalcopyrite CuInSe2 nanocrystals can be obtained in the same conditions by exchanging diphenyl diselenide for the Woollins' reagent, never previously applied to the preparation of Cu–In–Se nanocrystals. In the case of Cu–In–S nanocrystals the chemical composition is governed not by the type of the solvent but by the reducing properties of 1-dodecanethiol, the precursor of sulfur. Independently of the solvent copper-rich nanocrystals are obtained of either wurtzite-type Cu1.6In1.0S2.3 (1.6 Cu2S–In2S3) in 1-octadecene or chalcopyrite-type Cu1.8In1.0S2.4 (1.8 Cu2S–In2S3) in oleylamine.

A two-step procedure is reported enabling preparation of quaternary Cu–In–Zn–S nanocrystals with electrochemically active ligands consisting of 4-dodecylphenylaminobenzene and amine, thiol, or carboxylic anchor groups. Detailed 1H NMR and IR studies of nanocrystals dispersion as well as free ligands recovered via nanocrystals dissolution indicate that in the organic shell of initial ligands weakly (1-octadecene (ODE)) and more strongly (1-dodecanethiol (DDT) and oleylamine (OLA)) bound ligands coexist. Treating the nanocrystals with pyridine removes weakly bound ligands; however, DDT and OLA molecules remain present as coligands with pyridine. Labile pyridine ligands can then be exchanged for the target 4-dodecylphenylaminobenzene derivatives with different anchor groups. 1H NMR lines of these ligands are broadened due to their restricted rotation; this broadening is especially pronounced for the lines corresponding to the anchor group protons. Electrochemical activity of the ligands is significantly alte...

International audience; A novel synthesis method for the preparation of Cu2ZnSnS4 nanocrystals is presented using a liquid precursor of tin, namely tin(II) 2-ethylhexanoate, which yields small and nearly monodisperse NCs either in the kesterite or in the wurtzite phase depending on the sulfur source (elemental sulfur in oleylamine vs. dodecanethiol).

We report on a simplified procedure of InP/In 2 O 3 core/shell nanocrystals preparation in which indium(III) carboxylates are used as indium precursors and at the same time as a source of capping ligands whereas phosphine (PH 3 ), generated in situ in the reaction of HCl with zinc phosphide, (Zn 3 P 2 ), is used as a source of phosphorus. This modified one-step, one-pot procedure, exploiting a smaller number of components in the reaction mixture, extends the range of obtainable nanocrystals’ sizes below 3.0 nm while retaining their low polydispersity. Initial ligands can be readily exchanged at ambient conditions for aliphatic diamines such as hexane-1,6-diamine (HDA) or ethane-1,2-diamine (EDA), as evidenced by IR and NMR investigations. EDA-capped nanocrystals can be transferred to aqueous solution forming colloidal dispersions. This property is of significant importance in the view of their potential use in biolabeling. The prepared nanocrystals can also be surface functionalized with electroactive molecules such as N -(4-aminophenyl)- N ′-(4-nitrophenyl)benzene-1,4-diamine (nitroderivative of aniline trimer) yielding an electrochemically interesting hybrid nanomaterials whose conductivity, magnetic and spectral properties can be controlled by the applied potential.

Exchange of initial, predominantly stearate ligands for pyridine in the first step and butylamine (BA) or 11-mercaptoundecanoic acid (MUA) in the second one was studied for alloyed quaternary Cu-In-Zn-S nanocrystals. The NMR results enabled us to demonstrate, for the first time, direct binding of the pyridine labile ligand to the nanocrystal surface as evidenced by paramagnetic shifts of the three signals attributed to its protons to 7.58, 7.95 and 8.75 ppm. XPS investigations indicated, in turn, a significant change in the composition of the nanocrystal surface upon the exchange of initial ligands for pyridine, which being enriched in indium in the 'as prepared' form became enriched in zinc after pyridine binding. This finding indicated that the first step of ligand exchange had to involve the removal of the surface layer enriched in indium with simultaneous exposure of a new, zinc-enriched layer. In the second ligand exchange step (replacement of pyridine with BA or MUA) the changes in the nanocrystal surface compositions were much less significant. The presence of zinc in the nanocrystal surface layer turned out necessary for effective binding of pyridine as shown by a comparative study of ligand exchange in Cu-In-Zn-S, Ag-In-Zn-S and CuInS2, carried out by complementary XPS and NMR investigations.

It is demonstrated that ternary Cu–Fe–S nanocrystals differing in composition (from Cu-rich to Fe-rich), structure (chalcopyrite or high bornite) and size can be obtained from a mixture of CuCl, FeCl3, thiourea and oleic acid (OA) in oleylamine (OLA) using the heating up procedure. This new preparation method yields the smallest Cu–Fe–S nanocrystals ever reported to date (1.5 nm for the high bornite structure and 2.7 nm for the chalcopyrite structure). A comparative study of nanocrystals of the same composition (Cu1.6Fe1.0S2.0) but different in size (2.7 nm and 9.3 nm) revealed a pronounced quantum confinement effect, confirmed by three different techniques: UV-vis spectroscopy, cyclic voltammetry and Mossbauer spectroscopy. The optical band gap increased from 0.60 eV in the bulk material to 0.69 eV in the nanocrystals of 9.3 nm size and to 1.39 eV in nanocrystals of 2.7 nm size. The same trend was observed in the electrochemical band gaps, derived from cyclic voltammetry studies (band gaps of 0.74 eV and 1.54 eV). The quantum effect was also manifested in Mossbauer spectroscopy by an abrupt change in the spectrum from a quadrupole doublet to a Zeeman sextet below 10 K, which could be interpreted in terms of the well defined energy states in these nanoparticles, resulting from quantum confinement. The Mossbauer spectroscopic data confirmed, in addition to the results of XPS spectroscopy, the co-existence of Fe(III) and Fe(II) in the synthesized nanocrystals. The organic shell composition was investigated by NMR (after dissolution of the inorganic core) and IR spectroscopy. Both methods identified oleylamine (OLA) and 1-octadecene (ODE) as surfacial ligands, the latter being formed in situ via an elimination–hydrogenation reaction occurring between OLA and the nanocrystal surface.

A novel synthesis method for the preparation of Cu2ZnSnS4 nanocrystals is presented using a liquid precursor of tin, namely tin(II) 2-ethylhexanoate, which yields small and nearly monodisperse NCs either in the kesterite or in the wurtzite phase depending on the sulfur source (elemental sulfur in oleylamine vs. dodecanethiol).

A convenient method of the preparation of alloyed quaternary Ag-In-Zn-S nanocrystals is elaborated, in which a multicomponent mixture of simple and commercially available precursors, namely, silver nitrate, indium(III) chloride, zinc stearate, 1-dodecanethiol, and sulfur, is used with 1-octadecene as a solvent. The formation of quaternary nanocrystals necessitates the use of an auxiliary sulfur precursor, namely, elemental sulfur dissolved in oleylamine, in addition to 1-dodecanethiol. Without this additional precursor binary ZnS nanocrystals are formed. The optimum reaction temperature of 180 °C was also established. In these conditions shape, size, and composition of the resulting nanocrystals can be adjusted in a controlled manner by changing the molar ratio of the precursors in the reaction mixture. For low zinc stearate contents anisotropic rodlike (ca.3 nm x 10 nm) and In-rich nanocrystals are obtained. This is caused by a significantly higher reactivity of the indium precursor as compared to the zinc one. With increasing zinc precursor content the reactivities of both precursors become more balanced, and the resulting nanocrystals are smaller (1.5-4.0 nm) and become Zn-rich as evidenced by transmission electron microscopy, X-ray diffraction, and energy-dispersive spectrometry investigations. Simultaneous increases in the zinc and sulfur precursor content result in an enlargement of nanocrystals (2.5 to 5.0 nm) and further increase in the molar ZnS content (up to 0.76). The prepared nanoparticles show stable photoluminescence with the quantum yield up to 37% for In and Zn-rich nanocrystals. Their hydrodynamic diameter in toluene dispersion, determined by dynamic light scattering, is roughly twice larger than the diameter of their inorganic core.