When Social Media Empowers Analytical Chemists to Explore Millions of Spectra Derived from a Complex Sample.

Analytical chemistry has never yielded such a wealth of experimental data as it does today, and this exponential trend shows no sign of abating. We continually advance the capabilities of our instruments and conceive innovative concepts, all in a concerted effort to naturally push the boundaries of our understanding regarding intricate sample matrices. Spectroscopic imaging, in the broadest sense, is certainly the field where we observe this acceleration even more pronouncedly. Analytical chemistry swiftly grasped the significance of processing acquired data for comprehensive exploration through utilization of chemometrics or machine learning tools. One can assert today that chemometrics undeniably constitutes an integral facet in the advancement of an analytical approach. However, we are now faced with a new challenge, as the experimental data accumulated for certain analytical techniques are so vast and massive that exploring them with such tools has become unfeasible, and this is by no means a computational capacity issue. Analytical chemistry is far from being the sole field affected by this issue, and one could argue that others have grappled with it long before us, such as, for instance, social media, to name just one. The purpose of this paper is to demonstrate that such a domain, which may initially seem distant from our concerns, can offer novel tools capable of overcoming these barriers, even though we are not necessarily dealing with the same objects. More specifically, we delve into the clustering of over 10 million LIBS spectra acquired as part of an imaging experiment aimed at exploring a singular rock sample. This will serve to demonstrate that an open-source library developed by Meta (formerly known as Facebook) can enable us to conduct a comprehensive exploration of this sample, a feat deemed impossible with conventional data analysis approaches.

Lattice Expansion in Rb-Doped Hybrid Organic-Inorganic Perovskite Crystals Resulting in Smaller Band-Gap and Higher Light-Yield Scintillators.

Two-dimensional hybrid-organic-inorganic perovskite (2D-HOIP) lead bromide perovskite crystals have demonstrated great potential as scintillators with high light yields and fast decay times while also being low cost with solution-processable materials for wide energy radiation detection. Ion doping has been also shown to be a very promising avenue for improvements of the scintillation properties of 2D-HOIP crystals. In this paper, we discuss the effect of rubidium (Rb) doping on two previously reported 2D-HOIP single crystals, BA2PbBr4 and PEA2PbBr4. We observe that doping the perovskite crystals with Rb ions leads to an expansion of the crystal lattices of the materials, which also leads to narrowing of band gaps down to 84% of the pure compounds. Rb doping of BA2PbBr4 and PEA2PbBr4 shows a broadening in the photoluminescence and scintillation emissions of both perovskite crystals. Rb doping also leads to faster γ-ray scintillation decay times, as fast as 4.4 ns, with average decay time decreases of 15% and 8% for Rb-doped BA2PbBr4 and PEA2PbBr4, respectively, compared to those of undoped crystals. The inclusion of Rb ions also leads to a slightly longer afterglow, with residual scintillation still being below 1% after 5 s at 10 K, for both undoped and Rb-doped perovskite crystals. The light yield of both perovskites is significantly increased by Rb doping with improvements of 58% and 25% for BA2PbBr4 and PEA2PbBr4, respectively. This work shows that Rb doping leads to a significant enhancement of the 2D-HOIP crystal performance, which is of particular significance for high light yield and fast timing applications, such as photon counting or positron emission tomography.

Optical properties of fully inorganic core/gradient-shell CdSe/CdZnS nanocrystals at the ensemble and single-nanocrystal levels.

We report the synthesis and optical characterization of fully inorganic gradient-shell CdSe/CdZnS nanocrystals (NCs) with high luminescence quantum yield (QY, 50%), which were obtained by replacing native oleic-acid (OA) ligands with halide ions (Cl-and Br-). Absorption, photoluminescence excitation (PLE) and photoluminescence (PL) spectra in solution were unaffected by the ligand-exchange procedure. The halide-capped NCs were stable in solution for several weeks without modification of their PL spectra; once deposited as unprotected thin films and exposed to air, however, they did show signs of aging which we attribute to increasing heterogeneity of (effective) NC size. Time-resolved PL measurements point to the existence of four distinct emissive states, which we attribute to neutral, singly-charged and multi-excitonic entities. We found that the relative contribution of these four components to the overall PL decay is modified by the OA-to-halide ligand exchange, while the excited-state lifetimes themselves, surprisingly, remain largely unaffected. The high PL quantum yield of the halide-capped NCs allowed observation of single particle blinking and photon-antibunching; one surprising result was that aging processes that occurs during the first few days after deposition on glass seemed to offer a certain increased protection against photobleaching. These results suggest that halide-capped CdSe/CdZnS NCs are promising candidates for incorporation into opto-electronic devices, based on, for example, hybrid perovskite matrices, which require eliminating the steric hindrance and electronic barrier of bulky organic ligands to ensure efficient coupling.

Liquid-Crystalline Suspensions of Photosensitive Paramagnetic CeF3 Nanodiscs.

The design of high-performance energy-converting materials is an essential step for the development of sensors, but the production of the bulk materials currently used remains costly and difficult. Therefore, a different approach based on the self-assembly of nanoparticles has been explored. We report on the preparation by solvothermal synthesis of highly crystalline CeF3 nanodiscs. Their surface modification by bisphosphonate ligands led to stable, highly concentrated, colloidal suspensions in water. Despite the low aspect ratio of the nanodiscs (∼6), a liquid-crystalline nematic phase spontaneously appeared in these colloidal suspensions. Thanks to the paramagnetic character of the nanodiscs, the nematic phase was easily aligned by a weak (0.5 T) magnetic field, which provides a simple and convenient way of orienting all of the nanodiscs in suspension in the same direction. Moreover, the more dilute, isotropic, suspensions displayed strong (electric and magnetic) field-induced orientation of the nanodiscs (Kerr and Cotton-Mouton effects), with fast enough response times to make them suitable for use in electro-optic devices. Furthermore, an emission study showed a direct relation between the luminescence intensity and magnetic-field-induced orientation of the colloids. Finally, with their fast radiative recombination decay rates, the nanodiscs show luminescence properties that compare quite favorably with those of bulk CeF3. Therefore, these CeF3 nanodiscs are very promising building blocks for the development and processing of photosensitive materials for sensor applications.

Consequences of Ca Codoping in YAlO3 :Ce Single Crystals.

The influence of Ca codoping on the optical absorption, photo-, radio-, and thermo-luminescence properties of YAlO3 :Ce (YAP:Ce) crystals has been studied for four different calcium concentrations ranging from 0 to 500 ppm. Ca codoping results in a partial oxidation of Ce3+ into Ce4+ , The luminescence time response under pulsed X-ray excitation of the Ce3+ /Ce4+ admixure clearly demonstrates the role of hole migration on both the rise time and the generally observed slow components. From an application point of view, Ca codoping significantly improves the timing performances, but the induced presence of Ce4+ ions is also the cause of a reduction in scintillation efficiency.

Deep traps can reduce memory effects of shallower ones in scintillators.

X-ray induced luminescence sensitization results have been obtained on three commercially relevant scintillators, namely CsI:Tl, YAG:Ce and LSO:Ce. The obtained curves have been used to validate a model based on the competition among trapping and recombination of free charge carriers. The model was able to accurately describe the complex phenomenology of the detected sensitization curves. We also used the model to predict the role of a high temperature and concentration trap in shaping the sensitization curves. Based on these modelling results we also proposed a novel, and rather counterintuitive, strategy to deal with the sensitization phenomenon based on the deliberate introduction of deep traps which can significantly reduce the bright burn effect.

Atomistic Mechanisms for the Nucleation of Aluminum Oxide Nanoparticles.

A predictive model for nanoparticle nucleation has not yet been successfully achieved. Classical nucleation theory fails because the atomistic nature of the seed has to be considered. Indeed, geometrical structure as well as stoichiometry do not always match the bulk values. We present a fully microscopic approach based on a first-principle study of aluminum oxide clusters. We calculated stable structures of AlxOy and their associated thermodynamic properties. From these data, the chemical composition of a gas composed of aluminum and oxygen atoms can be calculated as a function of temperature, pressure, and aluminum to oxygen ratio. We demonstrate the accuracy of this approach in reproducing experimental results obtained with time-resolved spectroscopy of a laser-induced plasma from an Al2O3 target. We thus extended the calculation to lower temperatures, i.e., longer time scales, to propose a scenario of composition gas evolution leading to the first alumina seeds.

Anomalous discrete disorder response of high-symmetry impurity centers spectra in garnet solid solutions.

The zero-phonon electronic transitions in Cr(3+) and Ce(3+) impurity ions in a series of Lu3xY3-3xAl5O12 (0 < x < 1) garnet solid solution crystals were studied experimentally. It was observed that in contrast to the case of Ce(3+), the modification of zero-phonon R-line ((2)E-(4)A2) fluorescence spectra of Cr(3+) ions with changing x occurs in a discrete fashion and is not accompanied by strong inhomogeneous broadening, as usually happens in solid solutions. The effect is ascribed to the high C3i symmetry of the Cr(3+)(Al(3+)) sites that allows only a limited number of non-equivalent Cr(3+) centers in a mixed environment. The energies and radiative lifetimes of the (2)E states of locally identical Cr(3+) centers inside different mixed garnet matrices were studied and the observed dependences on the Lu content x are discussed in terms of lattice compression and dilation.

Light yield sensitization by X-ray irradiation of the BaAl4O7:Eu(2+)ceramic scintillator obtained by full crystallization of glass.

We report the scintillation properties of BaAl4O7:Eu(2+), a transparent polycrystalline ceramic prepared by full and congruent crystallization of glass. We show that a small deviation from the stoichiometric composition as well as thermal treatment duration play a crucial role in the formation of charge carrier traps, leading to a strong influence on the scintillation yield. We demonstrate that when the traps are not entirely removed, X-ray irradiation allows them to be permanently filled in order to significantly enhance the scintillation output. Finally, the best sample obtained demonstrates performances able to compete with a commercially available scintillating material, CsI:Tl.

γ-Al2O3 nanoparticles synthesised by pulsed laser ablation in liquids: a plasma analysis.

Pulsed laser ablation has proved its reliability for the synthesis of nano-particles and nano-structured materials, including metastable phases and complex stoichiometries. The possible nucleation of the nanoparticles in the gas phase and their growth has been little investigated, due to the difficulty of following the gas composition as well as the thermodynamic parameters. We show that such information can be obtained from the optically active plasma during its short lifetime, only a few microseconds for each laser pulse, as a result of a quick quenching due to the liquid environment. For this purpose, we follow the laser ablation of an α-Al2O3 target (corindon) in water, which leads to the synthesis of nanoparticles of γ-Al2O3. The AlO blue-green emission and the Al(I) (2)P(0)-(2)S doublet emission provide the electron density, the density ratio between the Al atoms and AlO molecules, and the rotational and vibrational temperatures of the AlO molecules. These diagnostic considerations are discussed in the framework of theoretical studies from the literature (density functional theory). We have found that starting from a hot atomized gas, the nucleation cannot occur in the first microseconds. We also raise the question of the influence of water on the control of the stoichiometry.

The Nanoplasmonic Purcell Effect in Ultrafast and High-Light-Yield Perovskite Scintillators.

The development of X-ray scintillators with ultrahigh light yields and ultrafast response times is a long sought-after goal. In this work, a fundamental mechanism that pushes the frontiers of ultrafast X-ray scintillator performance is theoretically predicted and experimentally demonstrated: the use of nanoscale-confined surface plasmon polariton modes to tailor the scintillator response time via the Purcell effect. By incorporating nanoplasmonic materials in scintillator devices, this work predicts over tenfold enhancement in decay rate and 38% reduction in time resolution even with only a simple planar design. The nanoplasmonic Purcell effect is experimentally demonstrated using perovskite scintillators, enhancing the light yield by over 120% to 88 ± 11 ph/keV, and the decay rate by over 60% to 2.0 ± 0.2 ns for the average decay time, and 0.7 ± 0.1 ns for the ultrafast decay component, in good agreement with the predictions of our theoretical framework. Proof-of-concept X-ray imaging experiments are performed using nanoplasmonic scintillators, demonstrating 182% enhancement in the modulation transfer function at four line pairs per millimeter spatial frequency. This work highlights the enormous potential of nanoplasmonics in optimizing ultrafast scintillator devices for applications including time-of-flight X-ray imaging and photon-counting computed tomography.

A compact detector system for simultaneous measurements of the light yield non-linearity and timing properties of scintillators.

This work presents an outline of a detection system that employs the Compton spectrometer method to assess the non-linearity of scintillator light yield. A novel approach is introduced, leading to more accurate measurements through the separate determination of the intrinsic light output parameters and the non-linearity of the scintillators. Key features of this system include the use of a portable scintillation detector with three photomultiplier tubes for precise measurement of the average number of detected photoelectrons and the incorporation of recent advancements in correction techniques for accidental coincidences. The integration of digital acquisition, offline data analysis, and geometric adaptation reduces the time required to perform a measurement. The developed detector can simultaneously measure different timing properties, as well as the relative intensities following ionization excitation in a scintillator. The system's performance is demonstrated through measurements of the light yield dependence on the deposited energy for commercially available liquid, plastic, and inorganic scintillators. Such instrumentation serves as a valuable tool in the development of novel scintillating materials, including liquid or solid organic scintillators, inorganic scintillators, and composite scintillators for electron detection, in addition to traditional X-ray or γ -ray detection.

Low-Temperature Emission Dynamics of Methylammonium Lead Bromide Hybrid Perovskite Thin Films at the Sub-Micrometer Scale.

We study the low-temperature (T = 4.7 K) emission dynamics of a thin film of methylammonium lead bromide (MAPbBr3), prepared via the anti-solvent method. Using intensity-dependent (over 5 decades) hyperspectral microscopy under quasi-resonant (532 nm) continuous wave excitation, we revealed spatial inhomogeneities in the thin film emission. This was drastically different at the band-edge (∼550 nm, sharp peaks) than in the emission tail (∼568 nm, continuum of emission). We are able to observe regions of the film at the micrometer scale where emission is dominated by excitons, in between regions of trap emission. Varying the density of absorbed photons by the MAPbBr3 thin films, two-color fluorescence lifetime imaging microscopy unraveled the emission dynamics: a fast, resolution-limited (∼200 ps) monoexponential tangled with a stretched exponential decay. We associate the first to the relaxation of excitons and the latter to trap emission dynamics. The obtained stretching exponents can be interpreted as the result of a two-dimensional electron diffusion process: Förster resonant transfer mechanism. Furthermore, the non-vanishing fast monoexponential component even in the tail of the MAPbBr3 emission indicates the subsistence of localized excitons. Finally, we estimate the density of traps in MAPbBr3 thin films prepared using the anti-solvent method at n∼1017 cm-3.

A2Bn-1PbnI3n+1 (A = BA, PEA; B = MA; n = 1, 2): Engineering Quantum-Well Crystals for High Mass Density and Fast Scintillators.

Quantum-well (QW) hybrid organic-inorganic perovskite (HOIP) crystals, e.g., A2PbX4 (A = BA, PEA; X = Br, I), demonstrated significant potentials as scintillating materials for wide energy radiation detection compared to their individual three-dimensional (3D) counterparts, e.g., BPbX3 (B = MA). Inserting 3D into QW structures resulted in new structures, namely A2BPb2X7 perovskite crystals, and they may have promising optical and scintillation properties toward higher mass density and fast timing scintillators. In this article, we investigate the crystal structure as well as optical and scintillation properties of iodide-based QW HOIP crystals, A2PbI4 and A2MAPb2I7. A2PbI4 crystals exhibit green and red emission with the fastest PL decay time <1 ns, while A2MAPb2I7 crystals exhibit a high mass density of >3.0 g/cm3 and tunable smaller bandgaps <2.1 eV resulting from quantum and dielectric confinement. We observe that A2PbI4 and PEA2MAPb2I7 show emission under X- and γ-ray excitations. We further observe that some QW HOIP iodide scintillators exhibit shorter radiation absorption lengths (∼3 cm at 511 keV) and faster scintillation decay time components (∼0.5 ns) compared to those of QW HOIP bromide scintillators. Finally, we investigate the light yields of iodide-based QW HOIP crystals at 10 K (∼10 photons/keV), while at room temperature they still show pulse height spectra with light yields between 1 and 2 photons/keV, which is still >5 times lower than those for bromides. The lower light yields can be the drawbacks of iodide-based QW HOIP scintillators, but the promising high mass density and decay time results of our study can provide the right pathway for further improvements toward fast-timing applications.

Local refractive index probed via the fluorescence decay of semiconductor quantum dots.

We present a novel approach for convenient tuning of the local refractive index around nanostructures. We apply this technique to study the influence of the local refractive index on the radiative decay time of CdSe/ZnS quantum dots with three distinct emission wavelengths. The dependence of the luminescence decay time on the environment is well described by an effective medium approach. A critical distance of about 80 nm is found for the determination of the effective local index of refraction. An estimation for the emitting-state quantum efficiency can be extracted.

Spectroscopic IR, EPR, and operando DRIFT insights into surface reaction pathways of selective reduction of NO by propene over the Co-BEA zeolite.

Interaction of a Co-BEA catalyst with individual components (NO, C(3)H(6), CO, O(2)) and mixtures simulating the real feed of the selective catalytic reduction (SCR) of nitric oxide in static and pulse experiments at variable temperatures was investigated by means of IR, EPR, and operando DRIFT spectroscopy coupled with QMS/GC analysis of the products. Speciation of cobalt active sites into Co(II), mono- and polynuclear oxo-cobalt species as well as CoO clusters was quantified by IR using CO and NO as probe molecules. The key intermediates, by-products, and final products of the SCR reaction were identified and their spectroscopic signatures ascertained. Based on the spectroscopic operando results, a concise mechanistic scheme of the selective catalytic reduction of nitric oxide by propene, triggered by a two-electron Co(II)/Co(0) redox couple, was developed. It consists of a complex network of the sequential/parallel selective reduction steps that are interlocked by the rival nonselective oxidation of the intermediates and their thermal decomposition. It has been shown that the SCR process is initiated by the chemoselective capture of NO from the reaction mixture by the cobalt active sites leading to the cobalt(II) dinitrosyls, which in the excess of oxygen are partially oxidized to surface nitrates and nitrites. N(2)O is produced by semi-decomposition of the dinitrosyl intermediates on the mononuclear centers, whereas NO(2)via NO oxidation on the polynuclear oxo-cobalt sites. Cyanide and isocyanate species, formed together with propene oxygenates in the course of the C=C bond scission, are the mechanistically pivotal reaction intermediates of C(3)H(6) interaction with the dinitrosyles and NO(3)(-)/NO(2)(-) surface species. Dinitrogen is produced by three main reaction routes involving oxidation of cyanides by NO/NO(2), reduction of dinitrosyls, nitrates, and nitrites by propene oxygenates (medium temperature range) or their reduction by carbon monoxide (high temperature range).

Doping MAPbBr3 hybrid perovskites with CdSe/CdZnS quantum dots: from emissive thin films to hybrid single-photon sources.

We report the first doping of crystalline methyl-ammonium lead bromide perovskite (MAPbBr3) films with CdSe/CdZnS core/shell quantum dots (QDs), using a soft-chemistry approach that preserves their high quantum yield and other remarkable luminescence properties. Our approach produces MAPbBr3 films of around 100 nm thickness, doped at volume ratios between 0.01 and 1% with colloidal CdSe/CdZnS QDs whose organic ligands were exchanged with halide ions to allow for close contact between the QDs and the perovskite matrix. Ensemble photoluminescence (PL) measurements demonstrate the retained emission of the QDs after incorporation into the MAPbBr3 matrix. Photoluminescence excitation (PLE) spectra exhibit signatures of wavelength-dependent coupling between the CdSe/CdZnS QDs and the MAPbBr3 matrix, i.e., a transfer of charges from matrix to QD, which increases the QD luminescence by up to 150%, or from QD to matrix. Spatially-resolved PL experiments reveal a strong correlation between the positions of QDs and an enhancement of the PL signal of the matrix. Lifetime imaging of the doped films furthermore shows that the emission lifetime of MAPbBr3 is slower in the vicinity of QDs, which, in combination with the increased PL signal of the matrix, suggests that QDs can act as local nucleation seeds that improve the crystallinity of MAPbBr3, thus boosting its emission quantum yield. Luminescence antibunching measurements provide clear evidence of single-photon emission from individual QDs in perovskite. Finally, the analysis of blinking statistics indicates an improvement of the photostability of individual QDs in perovskite as compared to bare CdSe/CdZnS QDs. At high CdSe/CdZnS QD doping levels, this work thus opens a route to hybrid solar concentrators for visible-light harvesting and hybrid-based LEDs, while a low degree of doping could yield hybrid single-photon sources than can be embedded in field-effect devices for single-charge control, which would allow the construction of nanophotonic devices via low-cost solution-processing techniques as an alternative to solid-state quantum dots.

Rare earth fluoride nanoparticles obtained using charge transfer complexes: a versatile and efficient route toward colloidal suspensions and monolithic transparent xerogels.

Crystalline rare earth fluoride nanoparticles were synthesized by reacting rare earth ions with charge-transfer complexes, in solution, under mild conditions. An infrared study showed that these intermediate complexes are made up of solvent molecules (amide: N,N-dimethylformamide, 1-methyl-2-pyrrolidinone, etc.) and fluoride ions coming from hydrofluoric acid. The size and shape of the particles can be controlled through the process parameters. The complete study of the particles obtained through this process is carried out in this document, especially for the YbF(3) system. However, the process can easily be extended to the whole series of rare earth elements. We also show the ability of these objects to be transferred from an aqueous medium to an organic phase thanks to their surface modification. Finally, transparent monolithic xerogels of rare earth fluoride have been developed starting from the prepared colloidal solutions.

Perspectives for CdSe/CdS spherical quantum wells as rapid-response nano-scintillators.

We explore the effect of the shell thickness on the time response of CdS/CdSe/CdS spherical quantum wells (SQWs) nanoscintillators under X-ray excitation. We first compare the spectral and timing properties under low and intense optical excitation, which allows us to identify the complex temporal and spectral response of the highly excited species. We find that a defect-induced delayed luminescence appears at large sizes. Under pulsed X-ray excitation, an analysis of the scintillation decay time reveals that multiexcitons are generated, similarly to the intense optical excitation and that the shell thickness does not change the fraction of fast component to a large extent. We performed a two-step simulation of the energy relaxation in the SQWs which reveals that large-size SQWs favor a very high number of excitations per particle, which, however, is counterbalanced by increased Auger quenching, rendering large SQWs less effective regarding the timing performance.

Stable and Bright Commercial CsPbBr3 Quantum Dot-Resin Layers for Apparent X-ray Imaging Screen.

CsPbBr3 quantum dots (QDs) have recently gained much interest due to their excellent optical and scintillation properties and their potential for X-ray imaging applications. In this study, we blended CsPbBr3 QDs with resin at different QD concentrations to achieve thick films and to protect the CsPbBr3 QDs from environmental moisture. Then, their scintillation properties are investigated and compared to the traditional commercial scintillators, CsI:Tl microcolumns, and Gadox layers. The CsPbBr3 QD-resin sheets show a high light yield of up to 21 500 photons/MeV at room temperature and a relatively small variation in light yield across a wide temperature range. In addition, the CsPbBr3 QD-resin sheets feature a small scintillation afterglow. The CsPbBr3 QD-resin sheets show a negligible trap density for the concentration below 50% weight, indicating that traps might arise from the aggregation of the QDs. The CsPbBr3 QD-resin sheets are also very stable at low irradiation intensities and relatively stable at higher intensities, with higher CsPbBr3 QD concentrations being more stable. Gamma-ray-excited-time-resolved emission measurements at 662 keV showed that the CsPbBr3 QD-resin sheets have an average scintillation decay time between 108 and 176 ns, which are still 10 000 and 6000 times faster than CsI:Tl and Gadox, respectively. Imaging tests show that the CsPbBr3 QD-resin sheets have a mean transfer function of 50% at 2 lp/mm and 20% at 4 lp/mm, comparable to that of commercial Gadox layers. This feature makes CsPbBr3 QD-resin sheets a good candidate for the low-cost, flexible X-ray imaging screens and γ-ray applications.