The two-photon luminescence (TPL) of small 10 nm x 40 nm colloidal gold nanorods (GNR) is investigated at the single object level, combining polarization resolved TPL and simultaneously acquired topography. A very high dependence of the TPL signal with both the nanorods longitudinal axis and the incident wavelength is observed confirming the plasmonic origin of the signal and pointing the limit of the analogy between GNRs and molecules. The spectral analysis of the TPL evidences two emission bands peaks: in the visible (in direct connection with the gold band structure), and in the infrared. Both bands are observed to vary quadradically with the incident excitation beam but exhibit different polarization properties. The maximum two-photon brightness of a single GNR is measured to be a few millions higher than the two-photon brightness of fluorescein molecules. We show that the important TPL observed in these small gold nanorods results from resonance effects both at the excitation and emission level : local field enhancement at the longitudinal surface plasmon resonances (LSPR) first results in an increase of the electron-hole generation. Further relaxation of electron-hole pairs then mostly leads to the excitation of the GNR transverse plasmon mode and its subsequent radiative relaxation.
We report on the passivation of surface defects of ZnO nanorods by surface layer deposition. ZnO nanorods and ZnS-ZnO hybrid nanostructures are grown on FTO coated glass substrate by chemical bath deposition method. XRD spectrum of ZnO nanorods shows the preferential growth along the c-axis. SEM analysis confirms the nearly aligned growth of the ZnO nanorods with a hexagonal shape. XPS measurements were performed to confirm the deposition of the surface layer and surface stoichiometry. Room temperature photoluminescence of ZnO nanorods showed two emission bands, viz. the band edge emission and…
Strong Stokes and anti-Stokes one-photon luminescence from single gold nanorods is measured in experiments. It is found that the intensity and polarization of the Stokes and anti-Stokes emissions are in strong correlation. Our experimental observation discovered a coherent process in light emission from single gold nanorods. We present a theoretical mode, based on the concept of cavity resonance, for consistently understanding both Stokes and anti-Stokes photoluminescence. Our theory is in good agreement of all our measurements.
The two-photon luminescence (TPL) of gold nanoparticles (NP) was shown to result from the excitation of hot carriers, the plasmonic NP resonances playing an important role both for plasmon enhanced absorption and plasmon enhanced emission. However, the exact parameters enabling to control or optimize the NP nonlinear luminescence still need to be understood in detail. In this paper, we report the two-photon excited photoluminescence of single gold nanorods exhibiting identical aspect ratio (close to 4) and thus identical plasmonic resonances, but increasing volumes V (707 <V< 160 103 nm3 i.e. …
The dynamics of the luminescence decay from germanium nanocrystals embedded in crystalline silicon has been studied for temperatures varied between 16 K and room temperature. At room temperature the characteristic decay time is of the order of 50 nanoseconds while it extends into the microsecond range at low temperatures. The decay is dominated by non-radiative processes, which show a typical thermal activation energy of a few meV.
We study how shape affects multiexciton generation (MEG) rates in a semiconducting nanocrystal by considering CdSe nanorods with varying diameters and aspect ratios. The calculations employ an atomistic semiempirical pseudopotential model combined with an efficacious stochastic approach applied to systems containing up to 20,000 atoms. The effect of nanorod diameter and aspect ratio on multiexciton generation rates is analyzed in terms of the scaling of the density of trion states and the scaling of the Coulomb couplings. Both show distinct scaling from spherical nanocrystals leading to a surp…
We perform first-principles calculations of wurtzite GaAs nanorods to explore the factors determining charge distributions in polar nanostructures. We show that both the direction and magnitude of the dipole moment $\mathbf{d}$ of a nanorod, and its electic field, depend sensitively on how its surfaces are terminated and do not depend strongly on the spontaneous polarization of the underlying lattice. We identify two physical mechanisms by which $\mathbf{d}$ is controlled by the surface termination, and we show that the excess charge on the nanorod ends is not strongly localized. We discuss th…
In recent years many experiments have demonstrated the possibility to achieve efficient photoluminescence from Si/SiO2 nanocrystals. While it is widely known that only a minor portions of the nanocrystals in the samples contribute to the observed photoluminescence, the high complexity of the Si/SiO2 interface and the dramatic sensitivity to the fabrication conditions make the identification of the most active structures at the experimental level not a trivial task. Focusing on this aspect we have addressed the problem theoretically, by calculating the radiative recombination rates for differen…
A theory of the electronic structure and excitonic absorption spectra of PbS and PbSe nanowires and nanorods in the framework of a four-band effective mass model is presented. Calculations conducted for PbSe show that dielectric contrast dramatically strengthens the exciton binding in narrow nanowires and nanorods. However, the self-interaction energies of the electron and hole nearly cancel the Coulomb binding, and as a result the optical absorption spectra are practically unaffected by the strong dielectric contrast between PbSe and the surrounding medium. Measurements of the size-dependent …
Metal-halide perovskite nanocrystals have demonstrated excellent optoelectronic properties for light-emitting applications. Isovalent doping with various metals (M2+) can be used to tailor and enhance their light emission. Although crucial to maximize performance, an understanding of the universal working mechanism for such doping is still missing. Here, we directly compare the optical properties of nanocrystals containing the most commonly employed dopants, fabricated under identical synthesis conditions. We show for the first time unambiguously and supported by first principles calculations …
We introduce a general method which allows reconstruction of electronic band structure of nanocrystals from ordinary real-space electronic structure calculations. A comprehensive study of band structure of a realistic nanocrystal is given including full geometric and electronic relaxation with the surface passivating groups. In particular, we combine this method with large scale density functional theory calculations to obtain insight into the luminescence properties of silicon nanocrystals of up to 3 nm in size depending on the surface passivation and geometric distortion. We conclude that th…
The instability of metal halide perovskites upon exposure to moisture or heat strongly hampers their applications in optoelectronic devices. Here, we report the large-yield synthesis of highly water-resistant total-inorganic green luminescent CsPbBr3/CsPb2Br5 core/shell heteronanocrystals (HNCs) by developing an in situ phase transition approach. It is implemented via water-driven phase transition of the original monoclinic CsPbBr3 nanocrystal and the resultant tetragonal CsPb2Br5 nanoshell has small lattice mismatch with the CsPbBr3 core, which ensures formation of an epitaxial interface for …
Rare-earth doped nanocrystals possess optical transitions with significant either electric or magnetic dipole characters. They are of strong interest for understanding and engineering light-matter interactions at the nanoscale with numerous applications in nanophotonics. Here, we study the $^5$D$_0\rightarrow ^7$F$_1$ transition dipole vector in individual NaYF$_4$:Eu$^{3+}$ nanorod crystals by Fourier and confocal microscopies. {Single crystalline host matrix leads to narrow emission lines at room temperature that permit to separate Stark sublevels resulting from the crystal field splitting}.…
Silicon photoluminescence and lasing have been critical issues to breakthrough bottlenecks in the understanding of luminescence mechanisms. Unfortunately, long-standing disputes about the exciton recombination mechanism and fluorescence lifetime remain unresolved, especially about whether silicon nanocrystals (Si NCs) can realize fast direct-bandgap-like optical transitions. Here, using ground-state and excited-state density functional theory (DFT), we obtained intrinsic phonon-free optical transitions at sizes from Si22 to Si705, showing that very small Si NCs can realize a strong direct opti…
We show that the positioning of a nanometer length scale dielectric object, such as a diamond nanocrystal, in the vicinity of a gold bowtie nanoantenna can be used to tune the plasmonic mode spectrum on the order of a linewidth. We further show that the intrinsic luminescence of gold enhanced in the presence of nanometer-scale roughness couples efficiently to the plasmon mode and carries the same polarization anisotropy. Our findings have direct implications for cavity quantum electrodynamics related applications of hybrid antenna-emitter complexes.
The easily tunable emission of halide perovskite nanocrystals throughout the visible spectrum makes them an extremely promising material for light-emitting applications. Whereas high quantum yields and long-term colloidal stability have already been achieved for nanocrystals emitting in the red and green spectral range, the blue region currently lags behind, with low quantum yields, broad emission profiles and insufficient colloidal stability. In this work, we present a facile synthetic approach for obtaining two-dimensional CsPbBr3 nanoplatelets with monolayer-precise control over their thick…
Quench, Glow, or Stay Silent: Distance-Controlled Up-Conversion Emission near Metallic Nanowires
Nicolaus Copernicus University in Toruń（托伦哥白尼大学）；Université Bourgogne Europe, CNRS, Laboratoire Interdisciplinaire Carnot de Bourgogne ICB UMR 6303（勃艮第欧洲大学、法国国家科学研究中心、勃艮第跨学科卡诺实验室）；Institute of Physical Chemistry Polish Academy of Sciences（波兰科学院物理化学研究所）；Wroclaw University of Science and Technology（弗罗茨瓦夫科技大学）
Hybrid nanocrystals (HNCs), based on ZnO nanorods (NRs) decorated with magnetic Fe-based domains, were synthesized via a colloidal seeded-growth method. The approach involved heterogeneous nucleation of Fe nanocrystals on size-tailored ZnO nanorod seeds in a noncoordinating solvent, followed by partial surface oxidation of the former to the corresponding Fe@FexOy core@shell domains. HNCs with variable population and size of the Fe-based nanodomains could be synthesized depending on the surface reactivity of the ZnO seeds. The structure-property relationships in these HNCs were carefully studie…
Copper-doped zinc sulfide (ZnS:Cu) exhibits down-conversion luminescence in the UV, visible, and IR regions of the electromagnetic spectrum; the visible red, green, and blue emission is referred to as R-Cu, G-Cu, and B-Cu, respectively. The sub-bandgap emission arises from optical transitions between localized electronic states created by point defects, making ZnS:Cu a prolific phosphor material and an intriguing candidate material for quantum information science, where point defects excel as single-photon sources and spin qubits. Colloidal nanocrystals (NCs) of ZnS:Cu are particularly interes…
It is challenging to strongly localize temperature in small volumes because heat transfer is a diffusive process. Here we show how to overcome this limitation using electrodynamic hot spots and interference effects in the regime of continuous-wave (CW) excitation. We introduce a set of figures of merit for the localization of temperature and for the efficiency of the plasmonic photo-thermal effect. Our calculations show that the temperature localization in a trimer nanoparticle assembly is a complex function of the geometry and sizes. Large nanoparticles in the trimer play the role of the nano…
We study the quantum-mechanical effects arising in a single semiconductor core/shell quantum dot controllably sandwiched between two plasmonic nanorods. Control over the position and the sandwich confinement structure is achieved by the use of a linear-trap, liquid-crystal line defect and laser tweezers that push the sandwich together. This arrangement allows for the study of exciton plasmon interactions in a single structure, unaltered by ensemble effects or the complexity of dielectric interfaces. We demonstrate the effect of plasmonic confinement on the photon-antibunching behavior of the q…
