major contributions, peer journals

Light–heat conversion dynamics in highly diversified water-dispersed hydrophobic nanocrystal assemblies

A.Mazzanti, Z. Yang, M. G. Silva, N. Yang, G. Rizza, P.E. Coulon, C. Manzonif, A. M. de Paula, G. Cerullo, G. Della Valle and M.P. Pileni
Proc. Natl. Acad. Sci. USA, 2019, 116,  8161-8166

We investigate, with a combination of ultrafast optical spec- troscopy and semiclassical modeling, the photothermal proper- ties of various water-soluble nanocrystal assemblies. Broadband pump–probe experiments with ∼100-fs time resolution in the vis- ible and near infrared reveal a complex scenario for their transient optical response that is dictated by their hybrid composition at the nanoscale, comprising metallic (Au) or semiconducting (Fe3 O4 ) nanostructures and a matrix of organic ligands. We track the whole chain of energy flow that starts from light absorption by the individual nanocrystals and subsequent excitation of out-of- equilibrium carriers followed by the electron–phonon equilibra- tion, occurring in a few picoseconds, and then by the heat release to the matrix on the 100-ps timescale. Two-dimensional finite- element method electromagnetic simulations of the composite nanostructure and multitemperature modeling of the energy flow dynamics enable us to identify the key mechanism presiding over the light–heat conversion in these kinds of nanomaterials. We demonstrate that hybrid (organic–inorganic) nanocrystal assem- blies can operate as efficient nanoheaters by exploiting the high absorption from the individual nanocrystals, enabled by the dilu- tion of the inorganic phase that is followed by a relatively fast heating of the embedding organic matrix, occurring on the 100-ps timescale.

peer journals

Influence of Cracks on the Optical Properties of Silver Nanocrystals Supracrystal Films

J.Wei, C.Deeb, J.L.Pelouard, M.PLPileni ACS Nano DOI: 10.1021/acsnano.8b07435

Physical properties of nanocrystals self-assembled into 3D superlattices called supracrystals are highly specific with unexpected behavior. The best example to support such claim was given, through STM/STS experiments at low temperature, of very thick supracrystals (around 1000 layers) where it was possible to image the surpracrystal surface and study their electronic properties. From previous studies, we know the optical properties of Ag nanocrystals self-assembled in hexagonal network (2D) or forming small 3D superlattices (from around 2 to 7 layers) are governed by dipolar interactions. Here, we challenge to study the optical properties of Ag supracrystals film characterized by large thicknesses (from around 27 to 180 Ag nanocrystals layers). In such experimental conditions, accordingtothe classical Beer-Lambert law, the absorption of Ag films is expected to be very large and the film transmission is closed to zero. Very surprisingly, we observe reduced transmission intensity with an increase of the notch linewidth, in the 300-800 nm wavelength range, as the supracrystal film thickness increased. By calculating the transmission through the supracrystal films, we deduced that the films were dominated by the presence of cracks with wetting layers existing at their bottoms. This result was also confirmed by optical micrographs. The cracks widths increased with increasing the film thickness leading to more complex wetting layers. We also demonstrated the formation of small Ag clusters at the nanocrystal surface. These results pave the way towards a class of plasmonic supracrystals.


peer journals

Au nanocrystal superlattices: nanocrystallinity, vicinal surfaces, and growth processes

D.M. Smilgies,Ruipeng Liand M. P. Pileni Nanoscale, 2018, DOI: 10.1039/C8NR04606A

Vicinal Au supracrystal surfaces were prepared  from Ausinglesingle domain nanocrystals (NCs) whereas by replacing Ausingleby their polycrystalline counterparts common low-energy supracrystal surfaces are produced.  By analogy to atomic crystalline surfaces, we propose a mechanism to explain formation of such unexpected supracrystal vicinal surfaces, composed of only AusingleNCs are non-compact (bctstructure) with coherent alignment of the atomic planes oriented along the [111] superlattice axis and a slight tilt configuration  (8.1°) of NCs.  In presence of Co() NCs, these Ausinglesupracrystals loose both the slightly tilted configuration of NCs and their orientational order leading to a superlattice transition from bctto fcc. In contrast, supracrystals of AupolyNCs are unsensitive to the presence of Co() NCs. These intriguing structural changes obtained with Ausinglecompared to Aupolysupracrystals in absence and presence of Co() NCs could explain the formation of vicinal surfaces. Note, the solvent used to disperse the nanocrystals plays a key parameter in the formation of supracrystal vicinal surfaces. Here a new analogy between supracrystals and atomic crystals is presented.

peer journals

Self-organization of inorganic nanocrystals.

Self-organizations of inorganic nanocrystals in 1D, 2D and 3D superlattices are described. In the latter case, supra-crystals with face-centred-cubic (fcc) structure are demonstrated. Collective properties due to the nanocrystal organization are described. These properties are either intrinsic or due to dipolar interactions.



Self-organization of inorganic nanocrystals.  M.P.Pileni J. Phys.: Condens. Matter,2006, 18, S67–S84.

peer journals

Do Binary Supracrystals Enhance the Crystal Stability?

Zhijie Yang, Thomas Altantzis,Sara Bals, Gustaaf Van Tendeloo, Marie-Paule Pileni

We study the oxygen thermal stability of two binary systems. The larger particles are magnetic amorphous Co (7.2 nm) or Fe3O4 (7.5 nm) nanocrystals whereas the smaller ones (3.7 nm) are Au nanocrystals. The nanocrystal ordering, as well as the choice of the magnetic nanoparticles very much influence the stability of the binary system. A perfect crystalline structure is obtained with the Fe3O4/Au binary supracrystals. For the Co/Au binary system, oxidation of Co results in the chemical transformation from Co to CoO, where the size of the amorphous Co nanoparticles increases from 7.2 to 9.8 nm in diameter. During the volume expansion of the Co nanoparticles, Au nanoparticles within the binary assemblies coalesce and are at the origin of the instability of the binary nanoparticle supracrystals. On the other hand, for the Fe3O4/Au binary system, the oxidation of Fe3O4 to Fe2Odoes not lead to a size change of the nanoparticles, which maintains the stability of the binary nanoparticle supracrystals. A similar behavior is observed for an AlB2type Co-Ag binary system: The crystalline structure is maintained, whereas in disordered assemblies, coalescence of Ag nanocrystals is observed




peer journals

Control of the size and shape of inorganic nanocrystals at various scales from nano to macrodomains.

In this paper, we propose the hypothesis that, in highly pure media, the cluster shape can be retained at various scales. Impurities and/or the additives can control the shape of the developing crystals by adsorption on selective sites. We demonstrate that the shape of clusters is retained at the nanoscale. This is supported by structural studies and both experiment and simulated optical properties of nanocrystal assemblies. We compare the data to those obtained by using a large variety of techniques and observation of crystal growth in nature.

Source : Control of the size and shape of inorganic nanocrystals at various scales from nano to macrodomains. M.P. Pileni J. Phys. Chem. C 111, 2007, 9019-9038