There is a considerable interest in producing and understanding the optical and spectroscopic properties of ordered nanoparticle assemblies. Herein, we describe and interpret the optical absorbance and Raman propertie...There is a considerable interest in producing and understanding the optical and spectroscopic properties of ordered nanoparticle assemblies. Herein, we describe and interpret the optical absorbance and Raman properties of 5.9 nm ± 0.3 nm diameter silver nanocrystals coated with dodecanethiol and organized in highly ordered 3D superlattices of different heights. Each superlattice was studied individually, which allowed to elaborate a model based on Maxwell-Garnett theory to reproduce qualitatively the height and wavelength dependence of the absorbance. Importantly, because of their small size compared to that of traditional nanoparticles used in Surface Enhanced Raman Spectroscopy （SERS）, the large 3D distribution of hot spots generated by the silver superlattices allowed to easily obtain SERS spectra of the surrounding ligands despite their intrinsic low Raman cross section. Accordingly, traces of thiophenol could be detected very easily.展开更多
The growth of nanocrystal superlattices of 5 nm single domain Au nanocrystals at an air-toluene interface induces formation of well-defined thin films （300--400 nm） with large coherence lengths. High-resolution elec...The growth of nanocrystal superlattices of 5 nm single domain Au nanocrystals at an air-toluene interface induces formation of well-defined thin films （300--400 nm） with large coherence lengths. High-resolution electron microscopy showed that polyhedral holes （negative supracrystal） were formed on the nanocrystal superlattice surface. Formation of negative supracrystals is attributed to inclusion in the superlattice of organic molecules （dodecanethiol）, which are present in concentrated zones at the air-toluene interface. The coexistence of two supracrystalline structures （bcc/fcc） is attributed to diffusion of dodecanethiol molecules resulting in a Bain deformation of the nanocrystal array.展开更多
Here, we report on hierarchical mechanical behavior of 500-nm-thick Conanocrystal 3D superlattices （supracrystals） induced by either the crystalline structure （nanocrystallinity） or the length of the coating agent...Here, we report on hierarchical mechanical behavior of 500-nm-thick Conanocrystal 3D superlattices （supracrystals） induced by either the crystalline structure （nanocrystallinity） or the length of the coating agent of Co nanocrystals. Increasing the nanocrystal shape anisotropy of Co nanocrystals through the control of their nanocrystallinities induces a higher level of ordering with both translational and orientational alignment of nanocrystals within the supracrystals. The hierarchy in ordering at various scales, i.e., from the atomic lattice within the nanocrystals to the nanocrystal superlattices within supracrystals, is correlated with marked changes in the Young＇s modulus of supracrystals： From 0.7 ±0.4 to 1.7 ±0.5 and to 6.6 ±1.5 GPa as the crystalline structure of Co nanoparticles changes from amorphous-Co to ε-Co and to hexagonal compact packing （hcp）-Co, respectively. Moreover, for supracrystals of 7 nm amorphous Co nanoparticles, the Young＇s modulus decreases by one order of magnitude from 0.7 ±0.4 to 0.08 ±0.03 GPa upon reducing the alkyl chain length of the ligands coating the Co nanoparticles from C18 （oleic acid） to C12 （lauric acid）. The hierarchical mechanical behavior is rationalized using a dimensional model of the stress-strain relationship in supracrystals.展开更多
A colloidal solution of 5 nm Au tetradecanethiol-coated nanoparticles is syn-thesized. After fast evaporation of one drop, ordered monolayers both composed of single domain and polycrystalline nanocrystals are obtaine...A colloidal solution of 5 nm Au tetradecanethiol-coated nanoparticles is syn-thesized. After fast evaporation of one drop, ordered monolayers both composed of single domain and polycrystalline nanocrystals are obtained. On increasing the amount of materials and the evaporation time, nanocrystal films with irregular outlines are produced together with close-packed 3D superlattices exhibiting a truncated-tetrahedral shape. Using low-frequency micro-Raman scattering spectroscopy and electron microscopy the building block nanocrystallinity is characterized. Spontaneous nanocrystallinity segregation is revealed： the truncated-tetrahedral supracrystals are shown to mainly contain single domain building blocks while the supracrystalline films are composed of a mixture of single domain and polycrystalline nanocrystals. This observation points out the correlation between the nanocrystallinity segregation involved in the growth of the nanocrystal superlattices and their morphology.展开更多
文摘There is a considerable interest in producing and understanding the optical and spectroscopic properties of ordered nanoparticle assemblies. Herein, we describe and interpret the optical absorbance and Raman properties of 5.9 nm ± 0.3 nm diameter silver nanocrystals coated with dodecanethiol and organized in highly ordered 3D superlattices of different heights. Each superlattice was studied individually, which allowed to elaborate a model based on Maxwell-Garnett theory to reproduce qualitatively the height and wavelength dependence of the absorbance. Importantly, because of their small size compared to that of traditional nanoparticles used in Surface Enhanced Raman Spectroscopy （SERS）, the large 3D distribution of hot spots generated by the silver superlattices allowed to easily obtain SERS spectra of the surrounding ligands despite their intrinsic low Raman cross section. Accordingly, traces of thiophenol could be detected very easily.
文摘The growth of nanocrystal superlattices of 5 nm single domain Au nanocrystals at an air-toluene interface induces formation of well-defined thin films （300--400 nm） with large coherence lengths. High-resolution electron microscopy showed that polyhedral holes （negative supracrystal） were formed on the nanocrystal superlattice surface. Formation of negative supracrystals is attributed to inclusion in the superlattice of organic molecules （dodecanethiol）, which are present in concentrated zones at the air-toluene interface. The coexistence of two supracrystalline structures （bcc/fcc） is attributed to diffusion of dodecanethiol molecules resulting in a Bain deformation of the nanocrystal array.
文摘Here, we report on hierarchical mechanical behavior of 500-nm-thick Conanocrystal 3D superlattices （supracrystals） induced by either the crystalline structure （nanocrystallinity） or the length of the coating agent of Co nanocrystals. Increasing the nanocrystal shape anisotropy of Co nanocrystals through the control of their nanocrystallinities induces a higher level of ordering with both translational and orientational alignment of nanocrystals within the supracrystals. The hierarchy in ordering at various scales, i.e., from the atomic lattice within the nanocrystals to the nanocrystal superlattices within supracrystals, is correlated with marked changes in the Young＇s modulus of supracrystals： From 0.7 ±0.4 to 1.7 ±0.5 and to 6.6 ±1.5 GPa as the crystalline structure of Co nanoparticles changes from amorphous-Co to ε-Co and to hexagonal compact packing （hcp）-Co, respectively. Moreover, for supracrystals of 7 nm amorphous Co nanoparticles, the Young＇s modulus decreases by one order of magnitude from 0.7 ±0.4 to 0.08 ±0.03 GPa upon reducing the alkyl chain length of the ligands coating the Co nanoparticles from C18 （oleic acid） to C12 （lauric acid）. The hierarchical mechanical behavior is rationalized using a dimensional model of the stress-strain relationship in supracrystals.
文摘A colloidal solution of 5 nm Au tetradecanethiol-coated nanoparticles is syn-thesized. After fast evaporation of one drop, ordered monolayers both composed of single domain and polycrystalline nanocrystals are obtained. On increasing the amount of materials and the evaporation time, nanocrystal films with irregular outlines are produced together with close-packed 3D superlattices exhibiting a truncated-tetrahedral shape. Using low-frequency micro-Raman scattering spectroscopy and electron microscopy the building block nanocrystallinity is characterized. Spontaneous nanocrystallinity segregation is revealed： the truncated-tetrahedral supracrystals are shown to mainly contain single domain building blocks while the supracrystalline films are composed of a mixture of single domain and polycrystalline nanocrystals. This observation points out the correlation between the nanocrystallinity segregation involved in the growth of the nanocrystal superlattices and their morphology.
