The rapid development of nanomaterials with unique size-tunable properties forms the basis for a variety of new applications, including temperature sensing. Luminescent nanoparticles (NPs) have demonstrated potential as sensitive nanothermometers, especially in biological systems. Their small size offers the possibility of mapping temperature profiles with high spatial resolution. The temperature range is however limited, which prevents use in high-temperature applications such as, for example, nanoelectronics, thermal barrier coatings, and chemical reactors. In this work, we extend the temperature range for nanothermometry beyond 900 K using silica-coated NaYF4 nanoparticles doped with the lanthanide ions Yb3+ and Er3+. Monodisperse ∼20 nm NaYF4:Yb,Er nanocrystals were coated with a ∼10 nm silica shell. Upon excitation with infrared radiation, bright green upconversion (UC) emission is observed. From the intensity ratio between 2H11/2 and 4S3/2 UC emission lines at 520 and 550 nm, respectively, the temperature can be determined up to at least 900 K with an accuracy of 1–5 K for silica-coated NPs. For bare NaYF4:Yb,Er NPs, the particles degrade above 600 K. Repeated thermal cycling experiments demonstrate the high durability and reproducibility of the silica-coated nanocrystals as temperature probes without any loss of performance. The present results open avenues for the development of a new class of highly stable nanoprobes by applying a silica coating around a wide variety of lanthanide-doped NPs.

The thermal reshaping and its influence on the plasmonic properties of gold nanostars are investigated using a combination of in situ tomography and a state-of-the-art fast acquisition approach.

Circular dichroism (CD) spectroscopy is a powerful optical technique for the study of chiral materials and molecules. It gives access to an enantioselective signal based on the differential absorption of right and left circularly polarized light, usually obtained through polarization analysis of the light transmitted through a sample of interest. CD is routinely used to determine the secondary structure of proteins and their conformational state. However, CD signals are weak, limiting the use of this powerful technique to ensembles of many molecules. Here, we experimentally realize the concept of photothermal circular dichroism, a technique that combines the enantioselective signal from circular dichroism with the high sensitivity of photothermal microscopy, achieving a superior signal-to-noise ratio to detect chiral nano-objects. As a proof of principle, we studied the chiral response of single plasmonic nanostructures with CD in the visible range, demonstrating a signal-to-noise ratio better than 40 with only 30 ms integration time for these nanostructures. The high signal-to-noise ratio allows us to quantify the CD signal for individual nanoparticles. We show that we can distinguish relative absorption differences for right circularly and left circularly polarized light as small as gmin = 4 × 10–3 for a 30 ms integration time with our current experimental settings. The enhanced sensitivity of our technique extends CD studies to individual nano-objects and opens CD spectroscopy to numbers of molecules much lower than those in conventional experiments.

Colloidal CsPbBr3 nanocrystals (NCs) have emerged as promising candidates for various opto-electronic applications, such as light-emitting diodes, photodetectors, and solar cells. Here, we report on the self-assembly of cubic NCs from an organic suspension into ordered cuboidal supraparticles (SPs) and their structural and optical properties. Upon increasing the NC concentration or by addition of a nonsolvent, the formation of the SPs occurs homogeneously in the suspension, as monitored by in situ X-ray scattering measurements. The three-dimensional structure of the SPs was resolved through high-angle annular dark-field scanning transmission electron microscopy and electron tomography. The NCs are atomically aligned but not connected. We characterize NC vacancies on superlattice positions both in the bulk and on the surface of the SPs. The occurrence of localized atomic-type NC vacancies—instead of delocalized ones—indicates that NC–NC attractions are important in the assembly, as we verify with Monte Carlo simulations. Even when assembled in SPs, the NCs show bright emission, with a red shift of about 30 meV compared to NCs in suspension.

Solids composed of colloidal quantum dots hold promise for third generation highly efficient thin-film photovoltaic cells. The presence of well-separated conduction electron states opens the possibility for an energy-selective collection of hot and equilibrated carriers, pushing the efficiency above the one-band gap limit. However, in order to reach this goal the decay of hot carriers within a band must be better understood and prevented, eventually. Here, we present a two-photon photoemission study of the 1Pe→1Se intraband relaxation dynamics in a CdSe quantum dot solid that mimics the active layer in a photovoltaic cell. We observe fast hot electron relaxation from the 1Pe to the 1Se state on a femtosecond-scale by Auger-type energy donation to the hole. However, if the oleic acid capping is exchanged for hexanedithiol capping, fast deep hole trapping competes efficiently with this relaxation pathway, blocking the Auger-type electron-hole energy exchange. A slower decay becomes then visible; we provide evidence that this is a multistep process involving the surface.

Anisotropic bimetallic nanoparticles are promising candidates for plasmonic and catalytic applications. Their catalytic performance and plasmonic properties are closely linked to the distribution of the two metals, which can change during applications in which the particles are exposed to heat. Due to this fact, correlating the thermal stability of complex heterogeneous nanoparticles to their microstructural properties is of high interest for the practical applications of such materials. Here, we employ quantitative electron tomography in high-angle annular darkfield scanning transmission electron microscopy (HAADF-STEM) mode to measure the 3D elemental diffusion dynamics in individual anisotropic Au-Ag nanoparticles upon heating in situ.This approach allows us to study the elemental redistribution in complex, asymmetric nanoparticles on a single particle level, which was inaccessible to other techniques so far. In this work, we apply the proposed method to compare the alloying dynamics of Au-Ag nanoparticles with different shapes and compositions and find that the shape of the nanoparticle does not exhibit a significant effect on the alloying speed whereas the composition does. Finally, comparing the experimental results to diffusion simulations allows us to estimate the diffusion coefficients of the metals for individual nanoparticles.

Semiconductor quantum wells are ubiquitous in high-performance optoelectronic devices such as solar cells and lasers. Understanding and controlling of the (hot) carrier dynamics is essential to optimize their performance. Here, we study hot electron cooling in colloidal CdSe quantum-well nanoplatelets using ultrafast two-photon photoemission spectroscopy at low excitation intensities, resulting typically in 1-5 hot electrons per platelet. We observe initial electron cooling in the femtosecond time domain that slows down with decreasing electron energy and is finished within 2 ps. The cooling is considerably faster at cryogenic temperatures than at room temperature, and at least for the systems that we studied, independent of the thickness of the platelets (here 3-5 CdSe units) and the presence of a CdS shell. The cooling rates that we observe are orders of magnitude faster than reported for similar CdSe platelets under strong excitation. Our results are understood by a classic cooling mechanism with emission of longitudinal optical phonons without a significant influence of the surface.

Thermal stability of gold/palladium octopods studied in situ in 3D : understanding design rules for thermally stable metal nanoparticles ACS nano -