Operando time-gated Raman spectroscopy of solid catalysts.

Operando Raman spectroscopy is a powerful analytical tool to provide new insights in the working and deactivation principles of solid catalysts. Intense fluorescence can obscure Raman spectra to the extent that they become uninterpretable. Time-gated Raman spectroscopy, based on pulsed excitation and time-gated detection, suppresses background fluorescence based on its slower time dynamics compared to Raman scattering. In this work, we demonstrate and quantify the benefit of time gating for operando Raman spectroscopy, using the propane dehydrogenation reaction over Pt-Sn-based catalyst materials as a case study. Experimental time-gated Raman spectroscopy data are fitted to a time-trace model that is used to optimize time gating for the maximum signal-to-background-noise ratio. Time-gated Raman spectra of a spent propane dehydrogenation catalyst material show lower background fluorescence compared to the time-integrated Raman spectra counterparts. Simultaneous operando time-gated and time-integrated Raman spectroscopy experiments demonstrate the benefit of time gating to obtain more distinct Raman features, especially in the early coking stages where spectra are dominated by background fluorescence.

Which Ion Dominates the Temperature and Pressure Response of Halide Perovskites and Elpasolites?

Halide perovskites and elpasolites are key for optoelectronic applications due to their exceptional performance and adaptability. However, understanding their crucial elastic properties for synthesis and device operation remains limited. We performed temperature- and pressure-dependent synchrotron-based powder X-ray diffraction at low pressures (ambient to 0.06 GPa) to investigate their elastic properties in their ambient-pressure crystal structure. We found common trends in bulk modulus and thermal expansivity, with an increased halide ionic radius (Cl to Br to I) resulting in greater softness, higher compressibility, and thermal expansivity in both materials. The A cation has a minor effect, and mixed-halide compositions show intermediate properties. Notably, thermal phase transitions in MAPbI3 and CsPbCl3 induced lattice softening and negative expansivity for specific crystal axes, even at temperatures far from the transition point. These results emphasize the significance of considering temperature-dependent elastic properties, which can significantly impact device stability and performance during manufacturing or temperature sweeps.

Probing nearby molecular vibrations with lanthanide-doped nanocrystals.

The photoluminescence (PL) of lanthanide-doped nanocrystals can be quenched by energy transfer to vibrations of molecules located within a few nanometers from the dopants. Such short-range electronic-to-vibrational energy transfer (EVET) is often undesired as it reduces the photoluminescence efficiency. On the other hand, EVET may be exploited to extract information about molecular vibrations in the local environment of the nanocrystals. Here, we investigate the influence of solvent and gas environments on the PL properties of NaYF4:Er3+,Yb3+ upconversion nanocrystals. We relate changes in the PL spectrum and excited-state lifetimes in different solvents and their deuterated analogues to quenching of specific lanthanide levels by EVET to molecular vibrations. Similar but weaker changes are induced when we expose a film of nanocrystals to a gas environment with different amounts of H2O or D2O vapor. Quenching of green- and red-emitting levels of Er3+ can be explained in terms of EVET-mediated quenching that involves molecular vibrations with energies resonant with the gap between the energy levels of the lanthanide. Quenching of the near-infrared-emitting level is more complex and may involve EVET to combination-vibrations or defect-mediated quenching. EVET-mediated quenching holds promise as a mechanism to probe the local chemical environment-both for nanocrystals dispersed in a liquid and for nanocrystals exposed to gaseous molecules that adsorb onto the nanocrystal surface.

The Formation of NaYF4 : Er3+ , Yb3+ Nanocrystals Studied by In Situ X-ray Scattering: Phase Transition and Size Focusing.

ß-NaYF4 nanocrystals are a popular class of optical materials. They can be doped with optically active lanthanide ions and shaped into core-multi-shell geometries with controlled dopant distributions. Here, we follow the synthesis of ß-NaYF4 nanocrystals from α-NaYF4 precursor particles using in situ small-angle and wide-angle X-ray scattering and ex situ electron microscopy. We observe an evolution from a unimodal particle size distribution to bimodal, and eventually back to unimodal. The final size distribution is narrower in absolute numbers than the initial distribution. These peculiar growth dynamics happen in large part before the α-to-ß phase transformation. We propose that the splitting of the size distribution is caused by variations in the reactivity of α-NaYF4 precursor particles, potentially due to inter-particle differences in stoichiometry. Rate equation modeling confirms that a continuous distribution of reactivities can result in the observed particle growth dynamics.

Growth and Self-Assembly of CsPbBr3 Nanocrystals in the TOPO/PbBr2 Synthesis as Seen with X-ray Scattering.

Despite broad interest in colloidal lead halide perovskite nanocrystals (LHP NCs), their intrinsic fast growth has prevented controlled synthesis of small, monodisperse crystals and insights into the reaction mechanism. Recently, a much slower synthesis of LHP NCs with extreme size control has been reported, based on diluted TOPO/PbBr2 precursors and a diisooctylphosphinate capping ligand. We report new insights into the nucleation, growth, and self-assembly in this reaction, obtained by in situ synchrotron-based small-angle X-ray scattering and optical absorption spectroscopy. We show that dispersed 3 nm Cs[PbBr3] agglomerates are the key intermediate species: first, they slowly nucleate into crystals, and then they release Cs[PbBr3] monomers for further growth of the crystals. We show the merits of a low Cs[PbBr3] monomer concentration for the reaction based on oleate ligands. We also examine the spontaneous superlattice formation mechanism occurring when the growing nanocrystals in the solvent reach a critical size of 11.6 nm.

The Role of Water in Carbon Dioxide Adsorption in Porphyrinic Metal-Organic Frameworks.

Capturing and converting CO2 through artificial photosynthesis using photoactive, porous materials is a promising approach for addressing increasing CO2 concentrations. Porphyrinic Zr-based metal-organic frameworks (MOFs) are of particular interest as they incorporate a photosensitizer in the porous structure. Herein, the initial step of the artificial photosynthesis is studied: CO2 sorption and activation in the presence of water. A combined vibrational and visible spectroscopic approach was used to monitor the adsorption of CO2 into PCN-222 and PCN-223 MOFs, and the photophysical changes of the porphyrinic linker as a function of water concentration. A shift in CO2 sorption site and bending of the porphyrin macrocycle in response to humidity was observed, and CO2/H2O competition experiments revealed that the exchange of CO2 with H2O is pore-size dependent. Therefore, humidity and pore-size can be used to tune CO2 sorption, CO2 capacity, and light harvesting in porphyrinic MOFs, which are key factors for CO2 photoreduction.

Bifunctional Europium for Operando Catalyst Thermometry in an Exothermic Chemical Reaction.

Often the reactor or the reaction medium temperature is reported in the field of heterogeneous catalysis, even though it could vary significantly from the reactive catalyst temperature. The influence of the catalyst temperature on the catalytic performance and vice versa is therefore not always accurately known. We here apply EuOCl as both solid catalyst and thermometer, allowing for operando temperature determination. The interplay between reaction conditions and the catalyst temperature dynamics is studied. A maximum temperature difference between the catalyst and oven of +16 °C was observed due to the exothermicity of the methane oxychlorination reaction. Heat dissipation by radiation appears dominating compared to convection in this set-up, explaining the observed uniform catalyst bed temperature. Application of operando catalyst thermometry could provide a deeper mechanistic understanding of catalyst performances and allow for safer process operation in chemical industries.

Slow Hole Localization and Fast Electron Cooling in Cu-Doped InP/ZnSe Quantum Dots.

Impurity doping of low-dimensional semiconductors is an interesting route towards achieving control over carrier dynamics and energetics, e.g., to improve hot carrier extraction, or to obtain strongly Stokes shifted luminescence. Such studies remain, however, underexplored for the emerging family of III-V colloidal quantum dots (QDs). Here, we show through a detailed global analysis of multiresonant pump-probe spectroscopy that electron cooling in copper-doped InP quantum dot (QDs) proceeds on subpicosecond time scales. Conversely, hole localization on Cu dopants is remarkably slow (1.8 ps), yet still leads to very efficient subgap emission. Due to this slow hole localization, common Auger assisted pathways in electron cooling cannot be blocked by Cu doping III-V systems, in contrast with the case of II-VI QDs. Finally, we argue that the structural relaxation around the Cu dopants, estimated to impart a reorganization energy of 220 meV, most likely proceeds simultaneously with the localization itself leading to efficient luminescence.

Optically Detected Magnetic Resonance Spectroscopy of Cu-Doped CdSe/CdS and CuInS2 Colloidal Quantum Dots.

Copper-doped II-VI and copper-based I-III-VI2 colloidal quantum dots (CQDs) have been at the forefront of interest in nanocrystals over the past decade, attributable to their optically activated copper states. However, the related recombination mechanisms are still unclear. The current work elaborates on recombination processes in such materials by following the spin properties of copper-doped CdSe/CdS (Cu@CdSe/CdS) and of CuInS2 and CuInS2/(CdS, ZnS) core/shell CQDs using continuous-wave and time-resolved optically detected magnetic resonance (ODMR) spectroscopy. The Cu@CdSe/CdS ODMR showed two distinct resonances with different g factors and spin relaxation times. The best fit by a spin Hamiltonian simulation suggests that emission comes from recombination of a delocalized electron at the conduction band edge with a hole trapped in a Cu2+ site with a weak exchange coupling between the two spins. The ODMR spectra of CuInS2 CQDs (with and without shells) differ significantly from those of the copper-doped II-VI CQDs. They are comprised of a primary resonance accompanied by another resonance at half-field, with a strong correlation between the two, indicating the involvement of a triplet exciton and hence stronger electron-hole exchange coupling than in the doped core/shell CQDs. The spin Hamiltonian simulation shows that the hole is again associated with a photogenerated Cu2+ site. The electron resides near this Cu2+ site, and its ODMR spectrum shows contributions from superhyperfine coupling to neighboring indium atoms. These observations are consistent with the occurrence of a self-trapped exciton associated with the copper site. The results presented here support models under debate for over a decade and help define the magneto-optical properties of these important materials.

In Situ Optical and X-ray Spectroscopy Reveals Evolution toward Mature CdSe Nanoplatelets by Synergetic Action of Myristate and Acetate Ligands.

The growth of two-dimensional platelets of the CdX family (X = S, Se, or Te) in an organic solvent requires the presence of both long- and short-chain ligands. This results in nanoplatelets of atomically precise thickness and long-chain ligand-stabilized Cd top and bottom surfaces. The platelets show a bright and spectrally pure luminescence. Despite the enormous interest in CdX platelets for optoelectronics, the growth mechanism is not fully understood. Riedinger et al. studied the reaction without a solvent and showed the favorable role for short-chain carboxylates for growth in two dimensions. Their model, based on the total energy of island nucleation, shows favored side facet growth versus growth on the top and bottom surfaces. However, several aspects of the synthesis under realistic conditions are not yet understood: Why are both short- and long-chain ligands required to obtain platelets? Why does the synthesis result in both isotropic nanocrystals and platelets? At which stage of the reaction is there bifurcation between isotropic and 2D growth? Here, we report an in situ study of the CdSe nanoplatelet reaction under practical synthesis conditions. We show that without short-chain ligands, both isotropic and mini-nanoplatelets form in the early stage of the process. However, most remaining precursors are consumed in isotropic growth. Addition of acetate induces a dramatic shift toward nearly exclusive 2D growth of already existing mini-nanoplatelets. Hence, although myristate stabilizes mini-nanoplatelets, mature nanoplatelets only grow by a subtle interplay between myristate and acetate, the latter catalyzes fast lateral growth of the side facets of the mini-nanoplatelets.

The Fine-Structure Constant as a Ruler for the Band-Edge Light Absorption Strength of Bulk and Quantum-Confined Semiconductors.

Low-dimensional semiconductors have found numerous applications in optoelectronics. However, a quantitative comparison of the absorption strength of low-dimensional versus bulk semiconductors has remained elusive. Here, we report generality in the band-edge light absorptance of semiconductors, independent of their dimensions. First, we provide atomistic tight-binding calculations that show that the absorptance of semiconductor quantum wells equals mπα (m = 1 or 2 with α as the fine-structure constant), in agreement with reported experimental results. Then, we show experimentally that a monolayer (superlattice) of quantum dots has similar absorptance, suggesting an absorptance quantum of mπα per (confined) exciton diameter. Extending this idea to bulk semiconductors, we experimentally demonstrate that an absorptance quantum equal to mπα per exciton Bohr diameter explains their widely varying absorption coefficients. We thus provided compelling evidence that the absorptance quantum πα per exciton diameter rules the band-edge absorption of all direct semiconductors, regardless of their dimension.

Extended Nucleation and Superfocusing in Colloidal Semiconductor Nanocrystal Synthesis.

Hot-injection synthesis is renowned for producing semiconductor nanocolloids with superb size dispersions. Burst nucleation and diffusion-controlled size focusing during growth have been invoked to rationalize this characteristic yet experimental evidence supporting the pertinence of these concepts is scant. By monitoring a CdSe synthesis in-situ with X-ray scattering, we find that nucleation is an extended event that coincides with growth during 15-20% of the reaction time. Moreover, we show that size focusing outpaces predictions of diffusion-limited growth. This observation indicates that nanocrystal growth is dictated by the surface reactivity, which drops sharply for larger nanocrystals. Kinetic reaction simulations confirm that this so-called superfocusing can lengthen the nucleation period and promote size focusing. The finding that narrow size dispersions can emerge from the counteracting effects of extended nucleation and reaction-limited size focusing ushers in an evidence-based perspective that turns hot injection into a rational scheme to produce monodisperse semiconductor nanocolloids.

Unraveling the Growth Mechanism of Magic-Sized Semiconductor Nanocrystals.

Magic-sized clusters (MSCs) of semiconductor are typically defined as specific molecular-scale arrangements of atoms that exhibit enhanced stability. They often grow in discrete jumps, creating a series of crystallites, without the appearance of intermediate sizes. However, despite their long history, the mechanism behind their special stability and growth remains poorly understood. It is particularly difficult to explain experiments that have shown discrete evolution of MSCs to larger sizes well beyond the "cluster" regime and into the size range of colloidal quantum dots. Here, we study the growth of MSCs, including these larger magic-sized CdSe nanocrystals, to unravel the underlying growth mechanism. We first introduce a synthetic protocol that yields a series of nine magic-sized nanocrystals of increasing size. By investigating these crystallites, we obtain important clues about the mechanism. We then develop a microscopic model that uses classical nucleation theory to determine kinetic barriers and simulate the growth. We show that magic-sized nanocrystals are consistent with a series of zinc-blende crystallites that grow layer by layer under surface-reaction-limited conditions. They have a tetrahedral shape, which is preserved when a monolayer is added to any of its four identical facets, leading to a series of discrete nanocrystals with special stability. Our analysis also identifies strong similarities with the growth of semiconductor nanoplatelets, which we then exploit to further increase the size range of our magic-sized nanocrystals. Although we focus here on CdSe, these results reveal a fundamental growth mechanism that can provide a different approach to nearly monodisperse nanocrystals.

Unusual Spectral Diffusion of Single CuInS2 Quantum Dots Sheds Light on the Mechanism of Radiative Decay.

The luminescence of CuInS2 quantum dots (QDs) is slower and spectrally broader than that of many other types of QDs. The origin of this anomalous behavior is still under debate. Single-QD experiments could help settle this debate, but studies by different groups have yielded conflicting results. Here, we study the photophysics of single core-only CuInS2 and core/shell CuInS2/CdS QDs. Both types of single QDs exhibit broad PL spectra with fluctuating peak position and single-exponential photoluminescence decay with a slow but fluctuating lifetime. Spectral diffusion of CuInS2-based QDs is qualitatively and quantitatively different from CdSe-based QDs. The differences reflect the dipole moment of the CuInS2 excited state and hole localization on a preferred site in the QD. Our results unravel the highly dynamic photophysics of CuInS2 QDs and highlight the power of the analysis of single-QD property fluctuations.

Exciton Fine Structure and Lattice Dynamics in InP/ZnSe Core/Shell Quantum Dots.

Nanocrystalline InP quantum dots (QDs) hold promise for heavy-metal-free optoelectronic applications due to their bright and size-tunable emission in the visible range. Photochemical stability and high photoluminescence (PL) quantum yield are obtained by a diversity of epitaxial shells around the InP core. To understand and optimize the emission line shapes, the exciton fine structure of InP core/shell QD systems needs be investigated. Here, we study the exciton fine structure of InP/ZnSe core/shell QDs with core diameters ranging from 2.9 to 3.6 nm (PL peak from 2.3 to 1.95 eV at 4 K). PL decay measurements as a function of temperature in the 10 mK to 300 K range show that the lowest exciton fine structure state is a dark state, from which radiative recombination is assisted by coupling to confined acoustic phonons with energies ranging from 4 to 7 meV, depending on the core diameter. Circularly polarized fluorescence line-narrowing (FLN) spectroscopy at 4 K under high magnetic fields (up to 30 T) demonstrates that radiative recombination from the dark F = ±2 state involves acoustic and optical phonons, from both the InP core and the ZnSe shell. Our data indicate that the highest intensity FLN peak is an acoustic phonon replica rather than a zero-phonon line, implying that the energy separation observed between the F = ±1 state and the highest intensity peak in the FLN spectra (6 to 16 meV, depending on the InP core size) is larger than the splitting between the dark and bright fine structure exciton states.

Crystallization of Nanocrystals in Spherical Confinement Probed by in Situ X-ray Scattering.

We studied the formation of supraparticles from nanocrystals confined in slowly evaporating oil droplets in an oil-in-water emulsion. The nanocrystals consist of an FeO core, a CoFe2O4 shell, and oleate capping ligands, with an overall diameter of 12.5 nm. We performed in situ small- and wide-angle X-ray scattering experiments during the entire period of solvent evaporation and colloidal crystallization. We observed a slow increase in the volume fraction of nanocrystals inside the oil droplets up to 20%, at which a sudden crystallization occurs. Our computer simulations show that crystallization at such a low volume fraction is only possible if attractive interactions between colloidal nanocrystals are taken into account in the model as well. The spherical supraparticles have a diameter of about 700 nm and consist of a few crystalline face-centered cubic domains. Nanocrystal supraparticles bear importance for magnetic and optoelectronic applications, such as color tunable biolabels, color tunable phosphors in LEDs, and miniaturized lasers.

Quenching Pathways in NaYF4:Er3+,Yb3+ Upconversion Nanocrystals.

Lanthanide-doped upconversion (UC) phosphors absorb low-energy infrared light and convert it into higher-energy visible light. Despite over 10 years of development, it has not been possible to synthesize nanocrystals (NCs) with UC efficiencies on a par with what can be achieved in bulk materials. To guide the design and realization of more efficient UC NCs, a better understanding is necessary of the loss pathways competing with UC. Here we study the excited-state dynamics of the workhorse UC material ß-NaYF4 co-doped with Yb3+ and Er3+. For each of the energy levels involved in infrared-to-visible UC, we measure and model the competition between spontaneous emission, energy transfer between lanthanide ions, and other decay processes. An important quenching pathway is energy transfer to high-energy vibrations of solvent and/or ligand molecules surrounding the NCs, as evidenced by the effect of energy resonances between electronic transitions of the lanthanide ions and vibrations of the solvent molecules. We present a microscopic quantitative model for the quenching dynamics in UC NCs. It takes into account cross-relaxation at high lanthanide-doping concentration as well as Förster resonance energy transfer from lanthanide excited states to vibrational modes of molecules surrounding the UC NCs. Our model thereby provides insight in the inert-shell thickness required to prevent solvent quenching in NCs. Overall, the strongest contribution to reduced UC efficiencies in core-shell NCs comes from quenching of the near-infrared energy levels (Er3+: 4I11/2 and Yb3+: 2F5/2), which is likely due to vibrational coupling to OH- defects incorporated in the NCs during synthesis.

Near-Infrared-Emitting CuInS2/ZnS Dot-in-Rod Colloidal Heteronanorods by Seeded Growth.

Synthesis protocols for anisotropic CuInX2 (X = S, Se, Te)-based heteronanocrystals (HNCs) are scarce due to the difficulty in balancing the reactivities of multiple precursors and the high solid-state diffusion rates of the cations involved in the CuInX2 lattice. In this work, we report a multistep seeded growth synthesis protocol that yields colloidal wurtzite CuInS2/ZnS dot core/rod shell HNCs with photoluminescence in the NIR (∼800 nm). The wurtzite CuInS2 NCs used as seeds are obtained by topotactic partial Cu+ for In3+ cation exchange in template Cu2- xS NCs. The seed NCs are injected in a hot solution of zinc oleate and hexadecylamine in octadecene, 20 s after the injection of sulfur in octadecene. This results in heteroepitaxial growth of wurtzite ZnS primarily on the Sulfur-terminated polar facet of the CuInS2 seed NCs, the other facets being overcoated only by a thin (∼1 monolayer) shell. The fast (∼21 nm/min) asymmetric axial growth of the nanorod proceeds by addition of [ZnS] monomer units, so that the polarity of the terminal (002) facet is preserved throughout the growth. The delayed injection of the CuInS2 seed NCs is crucial to allow the concentration of [ZnS] monomers to build up, thereby maximizing the anisotropic heteroepitaxial growth rates while minimizing the rates of competing processes (etching, cation exchange, alloying). Nevertheless, a mild etching still occurred, likely prior to the onset of heteroepitaxial overgrowth, shrinking the core size from 5.5 to ∼4 nm. The insights provided by this work open up new possibilities in designing multifunctional Cu-chalcogenide based colloidal heteronanocrystals.

NaYF4:Er3+,Yb3+/SiO2 Core/Shell Upconverting Nanocrystals for Luminescence Thermometry up to 900 K.

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.