Quantum structures are ideal objects by which to discover and study new sensor mechanisms and implement advanced approaches in sensor analysis to develop innovative sensor devices. Among them, one of the most interesting representatives is the Yanson point contact. It allows the implementation of a simple technological chain to activate the quantum mechanisms of selective detection in gaseous and liquid media. In this work, a portable device for multipurpose research on dendritic Yanson point contacts and quantum sensing was developed and manufactured. The device allows one to create dendritic Yanson point contacts and study their quantum properties, which are clearly manifested in the process of the electrochemical cyclic switchover effect. The device tests demonstrated that it was possible to gather data on the compositions and characteristics of the synthesized substances, and on the electrochemical processes that influence the production of dendritic Yanson point contacts, as well as on the electrophysical processes that provide information on the quantum nature of the electrical conductance of dendritic Yanson point contacts. The small size of the device makes it simple to integrate into a micro-Raman spectrometer setup. The developed device may be used as a prototype for designing a quantum sensor that will serve as the foundation for cutting-edge sensor technologies, as well as be applied to research into atomic-scale junctions, single-atom transistors, and any relative subjects.
Studying the optical performance of carbon nanotubes (CNTs) filled with guest materials can reveal the fundamental photochemical nature of ultrathin one-dimensional (1D) nanosystems, which are attractive for applications including photocatalysis. Here, we report comprehensive spectroscopic studies of how infiltrated HgTe nanowires (NWs) alter the optical properties of small-diameter (d t < 1 nm) single-walled carbon nanotubes (SWCNTs) in different environments: isolated in solution, suspended in a gelatin matrix, and heavily bundled in network-like thin films. Temperature-dependent Raman and photoluminescence measurements revealed that the HgTe NW filling can alter the stiffness of SWCNTs and therefore modify their vibrational and optical modes. Results from optical absorption and X-ray photoelectron spectroscopy demonstrated that the semiconducting HgTe NWs did not provide substantial charge transfer to or from the SWCNTs. Transient absorption spectroscopy further highlighted that the filling-induced nanotube distortion can alter the temporal evolution of excitons and their transient spectra. In contrast to previous studies on functionalized CNTs, where electronic or chemical doping often drove changes to the optical spectra, we highlight structural distortion as playing an important role.
The common approach to modify the thermoelectric activity of oxides is based on the concept of selective metal substitution. Herein, we demonstrate an alternative approach based on the formation of multiphase composites, at which the individual components have distinctions in the electric and thermal conductivities. The proof-of-concept includes the formation of multiphase composites between well-defined thermoelectric Co-based oxides: Ni, Fe co-substituted perovskite, LaCo0.8Ni0.1Fe0.1O3 (LCO), and misfit layered Ca3Co4O9. The interfacial chemical and electrical properties of composites are probed with the means of SEM, PEEM/XAS, and XPS tools, as well as the magnetic susceptibility measurements. The thermoelectric power of the multiphase composites is evaluated by the dimensionless figure of merit, ZT, calculated from the independently measured electrical resistivity (ρ), Seebeck coefficient (S), and thermal conductivity (λ). It has been demonstrated that the magnitude's electric and thermal conductivities depend more significantly on the composite interfaces than the Seebeck coefficient values. As a result, the highest thermoelectric activity is observed at the composite richer on the perovskite (i.e., ZT = 0.34 at 298 K).
A cationic boron dipyrromethene (BODIPY) derivative (1+) has been successfully combined with two polyoxometalates (POMs), the Lindqvist-type [W6O19]2- and the ß-[Mo8O26]4- units, into three new supramolecular fluorescent materials (1)2[W6O19]·2CH3CN, (1)2[W6O19], and (1)4[Mo8O26]·DMF·H2O. The resulting hybrid compounds have been fully characterized by a combination of single-crystal X-ray diffraction, IR and UV-vis spectroscopies, and photoluminescence analyses. This self-assembly approach prevents any π-π stacking interactions not only between the BODIPY units, responsible for aggregation-caused quenching (ACQ) effects, but also between the BODIPY and the POMs, avoiding intermolecular charge-transfer effects. Noticeably, the POM units do not only act as bulky spacers, but their negative charge density drives the molecular arrangement of the 1+ luminophore, strongly modifying its fluorescence in the solid state. As a consequence, the 1+ cations are organized into dimers in (1)2[W6O19]·2CH3CN and (1)2[W6O19], which are weakly emissive at room temperature, and in a more compact layered assembly in (1)4[Mo8O26]·DMF·H2O, which exhibits a red-shifted and intense emission upon similar photoexcitation.
Designing new single-phase white phosphors for solid-state lighting is a challenging trial-error process as it requires to navigate in a multidimensional space (composition of the host matrix/dopants, experimental conditions, etc.). Thus, no single-phase white phosphor has ever been reported to exhibit both a high color rendering index (CRI - degree to which objects appear natural under the white illumination) and a tunable correlated color temperature (CCT). In this article, a novel strategy consisting in iterating syntheses, characterizations, and machine learning (ML) models to design such white phosphors is demonstrated. With the guidance of ML models, a series of luminescent hybrid lead halides with ultra-high color rendering (above 92) mimicking the light of the sunrise/sunset (CCT = 3200 K), morning/afternoon (CCT = 4200 K), midday (CCT = 5500 K), full sun (CCT = 6500K), as well as an overcast sky (CCT = 7000 K) are precisely designed.
Near-UV-pumped white-light-emitting diodes with ultra-high color rendering and decreased blue-light emission is highly desirable. However, discovering a single-phase white light emitter with such characteristics remains challenging. Herein, we demonstrate that Mn doping as low as 0.027 % in the hybrid post-perovskite type (TDMP)PbBr4 (TDMP=trans-2,5-dimethylpiperaziniium) enables to achieve a bright pure white emission replicating the spectrum of the sun's rays. Thus, a white phosphor exhibiting an emission with CIE coordinates (0.330, 0.365), a high photoluminescence quantum yield of 60 % (new record for white light emission of hybrid lead halides), and an ultra-high color rendering index (CRI=96, R9=91.8), corresponding to the record value for a single phase emitter was obtained. The investigation of the photoluminescence properties revealed how free excitons, self-trapped excitons, and low amount of Mn dopants are coupled to give rise to such pure white emission.
This work highlights for the first time the photoluminescence (PL) properties of two new [Ln(Mo8O26)2]5- (Ln = Eu, Sm) lanthanide-containing polyoxometalates. Stable crystals of their tetrabutylammonium salts were synthesized, and their structures were confirmed by single-crystal X-ray diffraction. The robustness of the [Ln(Mo8O26)2]5- complexes in an acetonitrile solution has been evidenced by Fourier transform Raman and PL spectroscopies. The tetraphenylphosphonium derivatives were obtained by a salt metathesis reaction. The two series exhibit high thermal stability in air and are efficient phosphors at room temperature.
Nanostructuration and self-ordering of semiconducting organic materials are required to fabricate highly efficient photovoltaic and photoemissive devices. In this work, we investigated the combined effect of melt-assisted template processing and self-ordering of high purity regio-regular poly (3-hexylthiophene) (P3HT) to obtain nanofibers of P3HT and of P3HT-single-walled carbon nanotubes (SWNT) nanocomposites. An original ordering of the polymer and the carbon nanotubes within the nanofibers, as well as their surprising anisotropic photoluminescent properties were determined by vibrational and optical spectroscopy. It was attributed to the combined effect of the melt-assisted wetting confined within alumina nanopores, altogether with the self-organization of both P3HT chains on the one hand, and of the P3HT charged with SWNT on the other hand. It is proposed that the well-ordered regio-regular P3HT matrix orientation is promoted by the interaction with the alumina pore surface and the 1D confinement. For the composite case, the P3HT matrix imposes additionally a preferential orientation of the SWNT transversal to the nanofiber axis. This original organization is responsible for the unexpected polarization of the composite nanofibers photoluminescence. This work opens the way to alternative methods for tackling challenges of nanofabrication to obtain more efficient optoelectronic nanodevices.
Two new supramolecular fluorescent hybrid materials, combining for the first time [M6 O19 ]2- (M=Mo, W) polyoxometalates (POMs) and aggregation-induced emission (AIE)-active 1-methyl-1,2,3,4,5-pentaphenyl-phospholium (1+ ), were successfully synthesized. This novel molecular self-assembling strategy allows designing efficient solid-state emitters, such as (1)2 [W6 O19 ], by directing favorably the balance between the AIE and aggregation-caused quenching (ACQ) effects using both anion-π+ and H-bonding interactions in the solid state. Combined single-crystal X-ray diffraction, Raman, UV-vis and photoluminescence analyses highlighted that the nucleophilic oxygen-enriched POM surfaces strengthened the rigidity of the phospholium via strong C-Hâ â â O contacts, thereby exalting its solid-state luminescence. Besides, the bulky POM anions prevented π-π stacking interactions between the luminophores, blocking detrimental self-quenching effects.
An original concept for the property tuning of semiconductors is demonstrated by the synthesis of a p-type zinc oxide (ZnO)-like metal-organic framework (MOF), (ZnC2O3H2)n, which can be regarded as a possible alternative for ZnO, a natural n-type semiconductor. When small oxygen-rich organic linkers are introduced to the Zn-O system, oxygen vacancies and a deep valence-band maximum, the two obstacles for generating p-type behavior in ZnO, are restrained and raised, respectively. Further studies of this material on the doping and photoluminescence behaviors confirm its resemblance to metal oxides (MOs). This result answers the challenges of generating p-type behavior in an n-type-like system. This concept reveals that a new category of hybrid materials, with an embedded continuous metal-oxygen network, lies between the MOs and MOFs. It provides concrete support for the development of p-type hybrid semiconductors in the near future and, more importantly, the enrichment of tuning possibilities in inorganic semiconductors.
The present manuscript reports a thorough quantum investigation on the luminescence properties of three monoplatinum(II) complexes. First, the simulated bond lengths at the ground state are compared to the observed ones, and the simulated electronic transitions are compared to the reported ones in the literature in order to assess our methodology. In a second time we show that geometries from the first triplet excited state are similar to the ground state ones. Simulations of the phosphorescence spectra from the first triplet excited states have been performed taking into account the vibronic coupling effects together with mode-mixing (Dushinsky) and solvent effects. Our simulations are compared with the observed ones already reported in the literature and are in good agreement. The calculations demonstrate that the normal modes of low energy are of great importance on the phosphorescence signature. When temperature effects are taken into account, the simulated phosphorescence spectra are drastically improved. An analysis of the computational time shows that the vibronic coupling simulation is cost-effective and thus can be extended to treat large transition metal complexes. In addition to the intrinsic importance of the investigated targets, this work provides a robust method to simulate phosphorescence spectra and to increase the duality experiment-theory.
The structure, spectroscopic parameters and optical properties of stilbene have been investigated by a computational protocol including suitable treatment of anharmonic contributions together with new experimental results. A full reproduction of the 500-3500 cm(-1) IR spectrum has been possible using the VPT2 approach and new insights are provided in the 6000 cm(-1) region where typical signatures have been characterized as a set of overtones and combination bands. Vibrational contributions to electronic transitions have been taken into account to simulate the optical (absorption and emission) properties of stilbene. Spectra simulated by employing the state-of-the-art Adiabatic Hessian model coupled to global hybrid functionals are in remarkable agreement with their experimental counterparts and the inclusion of Herzberg-Teller contributions further improves the results with respect to those delivered by the basic Franck-Condon model.
This paper briefly describes how nanowires with diameters corresponding to 1 to 5 atoms can be produced by melting a range of inorganic solids in the presence of carbon nanotubes. These nanowires are extreme in the sense that they are the limit of miniaturization of nanowires and their behavior is not always a simple extrapolation of the behavior of larger nanowires as their diameter decreases. The paper then describes the methods required to obtain Raman spectra from extreme nanowires and the fact that due to the van Hove singularities that 1D systems exhibit in their optical density of states, that determining the correct choice of photon excitation energy is critical. It describes the techniques required to determine the photon energy dependence of the resonances observed in Raman spectroscopy of 1D systems and in particular how to obtain measurements of Raman cross-sections with better than 8% noise and measure the variation in the resonance as a function of sample temperature. The paper describes the importance of ensuring that the Raman scattering is linearly proportional to the intensity of the laser excitation intensity. It also describes how to use the polarization dependence of the Raman scattering to separate Raman scattering of the encapsulated 1D systems from those of other extraneous components in any sample.
Nanowires/analysis , Spectrum Analysis, Raman/methods , Light , Nanotubes, Carbon , Vibration
Owing to its high technological importance for optoelectronics, zinc oxide received much attention. In particular, the role of defects on its physical properties has been extensively studied as well as their thermodynamical stability. In particular, a large concentration of Zn vacancies in ZnO bulk materials is so far considered highly unstable. Here we report that the thermal decomposition of zinc peroxide produces wurtzite-type ZnO nanoparticles with an extraordinary large amount of zinc vacancies (>15%). These Zn vacancies segregate at the surface of the nanoparticles, as confirmed by ab initio calculations, to form a pseudo core-shell structure made of a dense ZnO sphere coated by a Zn free oxo-hydroxide mono layer. In others terms, oxygen terminated surfaces are privileged over zinc-terminated surfaces for passivation reasons what accounts for the Zn off-stoichiometry observed in ultra-fine powdered samples. Such Zn-deficient Zn1-xO nanoparticles exhibit an unprecedented photoluminescence signature suggesting that the core-shell-like edifice drastically influences the electronic structure of ZnO. This nanostructuration could be at the origin of the recent stabilisation of p-type charge carriers in nitrogen-doped ZnO nanoparticles.
The mechanisms that control the photophysics of composite films made of a semiconducting conjugated polymer (poly(paraphenylene vinylene), PPV) mixed with single-walled carbon nanotubes (SWNT) up to a concentration of 64 wt % are determined by using photoexcitation techniques and density functional theory. Charge separation is confirmed experimentally by rapid quenching of PPV photoluminescence and changes in photocurrent starting at relatively low concentrations of SWNT. Calculations predict strong electronic interaction between the polymer and the SWNT network when nanotubes are semiconducting.
This paper presents a resonance Raman spectroscopy study of â¼1 nm diameter HgTe nanowires formed inside single walled carbon nanotubes by melt infiltration. Raman spectra have been measured for ensembles of bundled filled tubes, produced using tubes from two separate sources, for excitation photon energies in the ranges 3.39-2.61 and 1.82-1.26 eV for Raman shifts down to â¼25 cm(-1). We also present HRTEM characterization of the tubes and the results of DFT calculations of the phonon and electronic dispersion relations, and the optical absorption spectrum based upon the observed structure of the HgTe nanowires. All of the evidence supports the hypothesis that the observed Raman features are not attributable to single walled carbon nanotubes, i.e., peaks due to radial breathing mode phonons, but are due to the HgTe nanowires. The observed additional features are due to four distinct phonons, with energies 47, 51, 94, and 115 cm(-1), respectively, plus their overtones and combinations. All of these modes have strong photon energy resonances that maximize at around 1.76 eV energy with respect to incident laser.
We report a general and simple approach to take control of the color of light-emitting two-luminophore hybrid nanowires (NWs). Our strategy is based on the spatial control at the nanoscale (coaxial geometry) and the spectral selection of the two kinds of luminophores in order to restrict complex charge and energy transfers. Thus, it is possible to control the color of the photoluminescence (PL) as an interpolation of the CIE (Commission Internationale de l'Eclairage) coordinates of each luminophore. For this purpose, we selected a green-emitting semiconducting polymer and a red-emitting hexanuclear metal cluster compound, (n-Bu4N)2Mo6Br8F6, dispersed in a poly(methyl-methacrylate) (PMMA) matrix. The great potential and the versatility of this strategy have been demonstrated for two configurations. First, a yellow PL with a continuous change along the nanowire has been evidenced when the proportion of the PPV shell versus the nanocomposite core, that is, the green/red volumic ratio, progressively shifts from 1:2 to 1:5. Second, an extremely abrupt change in the PL color with red-green-yellow segments has been achieved. A simple model corroborates the effectiveness of this strategy. PL excitation and time-resolved experiments also confirm that no significant charge and energy transfers are involved. The two-luminophore hybrid nanowires may find widespread nanophotonic applications in multicolor emitting sources, lasers and chemical and biological sensors.
Color , Luminescent Measurements/methods , Models, Chemical , Nanostructures/chemistry , Nanostructures/ultrastructure , Computer Simulation , Light , Materials Testing , Particle Size , Scattering, Radiation
Low-voltage aberration-corrected transmission electron microscopy (AC-TEM) of discrete Lindqvist [W(6)O(19)](2-) polyoxometalate ions inserted from an ethanolic solution of [NBu(4)](2)[W(6)O(19)] into double walled carbon nanotubes (DWNTs) allows a higher precision structural study to be performed than previously reported. W atom column separations within the constituent W(6) tungsten cage can now be visualized with sufficient clarity that reliable correlation with structural predictions from density functional theory (DFT) can be achieved. Calculations performed on [W(6)O(19)](2-) anions encapsulated in carbon nanotubes show good agreement with measured separations between pairs of W(2) atom columns imaged within equatorial WO(6) polyhedral pairs and also single W atom positions located within individual axial WO(6) octahedra. Structural data from the tilted chiral encapsulating DWNT were also determined simultaneously with the anion structural measurements, allowing the influence of the conformation of the encapsulating tubule to be included in the DFT calculation and compared against that of other candidate encapsulating nanotubes. Additional DFT calculations performed using Li(+) cations as a model for the [NBu(4)](+) counterions indicate that the latter may help to induce charge transfer between the DWNT and the [W(6)O(19)](2-) ion and this may help to constrain the motion of the ion in situ.
An optical approach for structural characterization of the modified surface layer in ion-implanted polymers is proposed. The mid-infrared reflectivity from the implanted surface is analyzed in terms of an oscillator dispersion model combined with the theory of differential reflection spectroscopy. The degree of destruction of a specific chemical bond is determined by the relative drop of the oscillator strengths associated with the corresponding vibrational modes. As an example, this methodology is applied to poly(methylmethacrylate) (PMMA) implanted with 50 keV silicon ions at fluences in the range 3 x 10(14) to 1 x 10(17) ions/cm(2). The scission rates for the C=O, C-O-C, and C-H bonds, as well as the static dielectric constant of the ion-modified material, are calculated as a function of the ion fluence. Further, a lower-limit estimate of 120 nm for the thickness of the ion-modified layer is obtained.
