Anisotropic gold nanoparticles and in particular with shapes exhibiting tips are known to present an extremely strong localized electromagnetic field. This field is mostly located at the top of the tips and can be used in various optical applications. Moreover, as a consequence of their anisotropy, they present two plasmon resonance bands corresponding to the transverse and longitudinal resonance modes. Tuning the aspect ratio it becomes possible to display SPR bands near the near infrared region. This was particularly investigated in the case of nanorods and also for bipyramids. In this paper we report a high yield synthesis approach that allows one to precisely control the aspect ratio of bipyramids and to elongate the structure until they adopt a javelin-like aspect. We were able to prepare nano-javelins with surface plasmon resonances up to 1850 nm, opening important perspectives in terms of optical applications in the NIR and IR regions. The synthetic methods are fully reported and the optical properties were correlated with the theoretical approach, taking into consideration not only the aspect ratio but also the truncation of the nano-objects.
Research on hybrid inorganic‐organic materials has experienced an explosive growth since the 1980s, with the expansion of soft inorganic chemistry based processes. Indeed, mild synthetic conditions, low processing temperatures provided by “chimie douce” and the versatility of the colloidal state allow for the mixing of the organic and inorganic components at the nanometer scale in virtually any ratio to produce the so called hybrid materials. Today a high degree of control over both composition and nanostructure of these hybrids can be achieved allowing tunable structure‐property relationships. This, in turn, makes it possible to tailor and fine‐tune many properties (mechanical, optical, electronic, thermal, chemical…) in very broad ranges, and to design specific multifunctional systems for applications. In particular, the field of “Hybrid‐Optics” has been very productive not only scientifically but also in terms of applications. Indeed, numerous optical devices based on hybrids are already in, or very close, to the market. This review describes most of the recent advances performed in this field. Emphasis will be given to luminescent, photochromic, NLO and plasmonic properties. As an outlook we show that the controlled coupling between plasmonics and luminescence is opening a land of opportunities in the field of “Hybrid‐Optics”.
High-performance Li-ion batteries require materials with well-designed and controlled structures on nanometre and micrometre scales. Electrochemical properties can be enhanced by reducing crystallite size and by manipulating structure and morphology. Here we show a method for preparing hierarchically structured Li4Ti5O12 yielding nano- and microstructure well-suited for use in lithium-ion batteries. Scalable glycothermal synthesis yields well-crystallized primary 4–8 nm nanoparticles, assembled into porous secondary particles. X-ray photoelectron spectroscopy reveals presence of Ti+4 only; combined with chemical analysis showing lithium deficiency, this suggests oxygen non-stoichiometry. Electron microscopy confirms hierarchical morphology of the obtained material. Extended cycling tests in half cells demonstrates capacity of 170 mAh g−1 and no sign of capacity fading after 1,000 cycles at 50C rate (charging completed in 72 s). The particular combination of nanostructure, microstructure and non-stoichiometry for the prepared lithium titanate is believed to underlie the observed electrochemical performance of material.
The development of new photonic materials is a key step toward improvement of existing optical devices and for the preparation of a new generation of systems. Therefore synthesis of photonic hybrid materials with a thorough understanding and control of the microstructure-to-properties relationships is crucial. In this perspective, a new preparation method based on fast gelation reactions using simple dispersion of dyes without strong covalent bonding between dye and matrix has been developed. This new sol-gel method is demonstrated through synthesis of monolithic siloxane-based hybrid materials highly doped by various platinum(II) acetylide derivatives. Concentrations of the chromophores as high as 400 mM were obtained and resulted in unprecedented optical power limiting (OPL) performance at 532 nm of the surface-polished solids. Static and time-resolved photoluminescence of the prepared hybrid materials were consistent with both OPL data and previous studies of similar Pt(II) compounds in solution. The impacts of the microstructure and the chemical composition of the matrix on the spectroscopic properties, are discussed.
A great number of works focus their interest on the study of gold nanoparticle plasmonic properties. Among those, sharp nanostructures appear to exhibit the more interesting features for further developments. In this paper, a complete study on bipyramidal-like gold nanostructures is presented. The nano-objects are prepared in high yield using an original method. This chemical process enables a precise control of the shape and the size of the particles. The specific photophysical properties of gold bipyramids in suspension are ripened by recording the plasmonic response of single and isolated objects. Resulting extinction spectra are precisely correlated to their geometrical structure by mean of electron tomography at the single-particle level. The interplay between the geometrical structure and the optical properties of twisted gold bipyramids is further discussed on the basis of numerical calculations. The influence of several parameters is explored such as the structural aspect ratio or the tip truncation. In the case of an incident excitation polarized along the particle long axis, this study shows how the plasmon resonance position can be sensitive to these parameters and how it can then be efficiently tuned on a large wavelength range.
The synthesis of trans‐di(arylalkynyl)diphosphine platinum(II) complexes bearing trialkoxysilane groups is described, as well as the preparation of siloxane‐based hybrid materials from organometallic chromophores through a modified sol–gel process. Glass materials prepared from trans‐[P(n–Bu)3]2Pt[(C≡C–p–C6H4–C≡C–p–C6H4–CH2O(CO)NH(CH2)3Si(OC2H5)3]2 generally show spectral transmittance, absorption and luminescence similar to that of solutions reported in the literature. Measurements of optical power limiting for the hybrid glass are carried out, and show broadband nonlinear absorption throughout the whole visible wavelength range with clamping values in the range 0.2–7 µJ at 120 mM chromophore concentration. The sol–gel process using urethane‐propyltriethoxysilane‐functionalized chromophores as precursors appears to be a valid method for formation of robust silicate materials with grafted diarylethynyl Pt(II) complexes for OPL devices.
A great number of works have focused their research on the synthesis, design and optical properties of gold nanoparticles for potential biological applications (bioimaging, biosensing). For this kind of application, sharp gold nanostructures appear to exhibit the more interesting features since their surface plasmon bands are very sensitive to the surrounding medium. In this paper, a complete study of PEGylated gold nanostars and PEGylated bipyramidal-like nanostructures is presented. The nanoparticles are prepared in high yield and their surfaces are covered with a biocompatible polymer. The photophysical properties of gold bipyramids and nanostars, in suspension, are correlated with the optical response of single and isolated objects. The resulting spectra of isolated gold nanoparticles are subsequently correlated to their geometrical structure by transmission electron microscopy. Finally, the PEGylated gold nanoparticles were incubated with melanoma B16-F10 cells. Dark-field microscopy showed that the biocompatible gold nanoparticles were easily internalized and most of them localized within the cells.
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