Two-Step Synthesis of Bismuth-Based Hybrid Halide Perovskite Thin-Films.

Lead halide perovskites have been revolutionary in the last decade in many optoelectronic sectors. Their bismuth-based counterparts have been considered a good alternative thanks to their composition of earth-abundant elements, good chemical stability, and low toxicity. Moreover, their electronic structure is in a quasi-zero-dimensional (0D) configuration, and they have recently been explored for use beyond optoelectronics. A significant limitation in applying thin-film technology is represented by the difficulty of synthesizing compact layers with easily scalable methods. Here, the engineering of a two-step synthesis in an air of methylammonium bismuth iodide compact thin films is reported. The critical steps of the process have been highlighted so that the procedure can be adapted to different substrates and application areas.

Bright and Efficient Sensitized Near-Infrared Photoluminescence from an Organic Neodymium-Containing Composite Material System.

Intense organic neodymium (Nd3+) emission is obtained with near-infrared (NIR) emission equivalent in intensity to that of an organic semiconductor emitting material. The advantage of Nd3+ emission is its narrow line width and NIR emission, which is enhanced by ∼3000 times at low excitation power through an efficient sensitization effect from a composite organic sensitizer. This performance is optimized at high concentrations of Nd3+ ions, and the organic perfluorinated system provides the ion excitations with a quantum efficiency of ∼40%. The material system is applicable to thin films that are compatible with integrated optics applications.

Manipulation of Molecular Vibrations on Condensing Er3+ State Densities for 1.5 µm Application.

Vibrational modes of chemical bonds in organic erbium (Er3+) materials play an important role in determining the efficiency of the 1.5 µm Er3+ emission. This work studies the energy coupling of the Er3+ intra-4f transitions and vibrational modes. The results demonstrate that the coupling introduces enormous nonradiative internal relaxation, which condenses the excited erbium population on to the 4I13/2 state. This suggests that vibrational modes can be advantageous for optimizing the branching ratio for the 1.5 µm transition in organic erbium materials. Through control of the quenching effect on to the 4I13/2 state and a reliable determination of intrinsic radiative rates, it is found that the pump power for population inversion can be reduced by an order of magnitude at high erbium concentrations compared to conventional inorganic erbium materials.

Fitting the magnetoresponses of the OLED using polaron pair model to obtain spin-pair dynamics and local hyperfine fields.

Organic light-emitting diode (OLED) displays a sign reversal magnetic field effect (MFE) when the applied magnetic field range is reduced to the sub-milliTesla range and the Polaron Pair Model has been successful in explaining the ultra-small MFE. Here, we obtained high resolution (~ 1 µT) magnetoconductance (MC) and magnetoelectroluminescence (MEL) of a tris-(8-hydroxyquinoline)aluminium-based (Alq3) OLED within the magnetic field range of ± 500 µT with the earth magnetic field components cancelled. A clear "W" shaped MC with a dip position of ± 250 µT and a monotonic MEL were observed. We demonstrate a fitting technique using the polaron pair model to the experimentally obtained MC and MEL. The fitting process extracts physically significant parameters within a working OLED: the local hyperfine fields for electron and hole in Alq3: Bhf1 = (0.63 ± 0.01) mT (electron), Bhf2 = (0.24 ± 0.01) mT (hole); the separation rates for singlet and triplet polaron pairs: kS,s = (44.59 ± 0.01) MHz, kT,s = (43.97 ± 0.01) MHz, and the recombination rate for singlet polaron pair kS,r = (88 ± 6) MHz. The yielded parameters are highly reproducible across different OLEDs and are in broad agreement with density functional theory (DFT) calculations and reported experimental observations. This demonstrates the feasibility of this fitting technique to approach any working OLED for obtaining significant microscopic parameters.

Experimental Studies on the Dynamic Memcapacitance Modulation of the ReO3@ReS2 Composite Material-Based Diode.

In this study, both memcapacitive and memristive characteristics in the composite material based on the rhenium disulfide (ReS2) rich in rhenium (VI) oxide (ReO3) surface overlayer (ReO3@ReS2) and in the indium tin oxide (ITO)/ReO3@ReS2/aluminum (Al) device configuration is presented. Comprehensive experimental analysis of the ReO3@ReS2 material properties' dependence on the memcapacitor electrical characteristics was carried out by standard as well as frequency-dependent current-voltage, capacitance-voltage, and conductance-voltage studies. Furthermore, determination of the charge carrier conduction model, charge carrier mobility, density of the trap states, density of the available charge carrier, free-carrier concentration, effective density of states in the conduction band, activation energy of the carrier transport, as well as ion hopping was successfully conducted for the ReO3@ReS2 based on the experimental data. The ITO/ReO3@ReS2/Al charge carrier conduction was found to rely on the mixed electronic-ionic processes, involving electrochemical metallization and lattice oxygen atoms migration in response to the externally modulated electric field strength. The chemical potential generated by the electronic-ionic ITO/ReO3@ReS2/Al resistive memory cell non-equlibrium processes leads to the occurrence of the nanobattery effect. This finding supports the possibility of a nonvolatile memory cell with a new operation principle based on the potential read function.

Enhanced 1.54-µm photo- and electroluminescence based on a perfluorinated Er(III) complex utilizing an iridium(III) complex as a sensitizer.

Advanced 1.5-µm emitting materials that can be used to fabricate electrically driven light-emitting devices have the potential for developing cost-effective light sources for integrated silicon photonics. Sensitized erbium (Er3+) in organic materials can give bright 1.5-µm luminescence and provide a route for realizing 1.5-µm organic light emitting diodes (OLEDs). However, the Er3+ electroluminescence (EL) intensity needs to be further improved for device applications. Herein, an efficient 1.5-µm OLED made from a sensitized organic Er3+ co-doped system is realized, where a "traditional" organic phosphorescent molecule with minimal triplet-triplet annihilation is used as a chromophore sensitizer. The chromophore provides efficient sensitization to a co-doped organic Er3+ complex with a perfluorinated-ligand shell. The large volume can protect the Er3+ 1.5-µm luminescence from vibrational quenching. The average lifetime of the sensitized Er3+ 1.5-µm luminescence reaches ~0.86 ms, with a lifetime component of 2.65 ms, which is by far the longest Er3+ lifetime in a hydrogen-abundant organic environment and can even compete with that obtained in the fully fluorinated organic Er3+ system. The optimal sensitization enhances the Er3+ luminescence by a factor of 1600 even with a high concentration of the phosphorescent molecule, and bright 1.5-µm OLEDs are obtained.

Modelling and fitting the Polaron Pair Magnetoconductance model to obtain a realistic local hyperfine field in Tris-(8-hydroxyquinoline)aluminium based diodes.

The Polaron Pair (PP) model has been successfully applied to magnetoconductance (MC) in organic semiconductor devices under ultra-small magnetic fields (USMFE). We report µT resolution MC measurements carried out with high sensitivity (better than 10-6) on the common organic semiconductor tris-(8-hydroxyquinoline)aluminium in the range ±500 µT displaying clear minima at ~±240 µT. Unlike traditional approaches, where device MC is simply evaluated using the PP model using nominal parameters for microscopic quantities such as the local hyperfine magnetic field, we have carried out actual fitting of the PP MC model to the experimentally obtained data. The fitting procedure yields physically realistic values for the polaron pair decay rate, local hyperfine magnetic field and triplet contribution to dissociation namely: [Formula: see text] = 28.6 ± 9.7 MHz, [Formula: see text] = 0.34 ± 0.04 mT and [Formula: see text] = 0.99 ± 0.01 respectively. The local hyperfine field obtained by fitting is in excellent agreement with independently calculated values for this system and is reproducible across different devices and independent of drive conditions. This demonstrates the applicability of the fitting approach to any organic USMFE MC data for obtaining microscopic parameter values.

Continuous Tuning of Organic Phosphorescence by Diluting Triplet Diffusion at the Molecular Level.

Organic long-persistent phosphorescent materials are advantageous due to the cost-effectiveness and easy processability. The organic phosphorescence is achieved by the long-lived triplet excitons, and the challenges are recognized regarding the various nonradiative pathways to quench the emission lifetime. Taming long-lived phosphorescence is generally engaged with the charge-transfer or exciton diffusion in molecular stacking to stabilize triplet excitons or form a photoinduced ionized state. Herein, we elucidate that the triplet-diffusion can cause a significant quenching that is not thermally activated by using a system of perfluorinated organic complexes. Hence, we suggest a coevaporation technique to dilute a single phosphorescence-emitting molecule with another optically inactive molecule to suppress the diffusion-induced quenching, tuning the phosphorescence lifetime and spectral features continuously. The work successfully suggests a general semitheoretical method of quantifying the population equilibrium to elucidate the loss mechanisms for organic phosphorescence.

Room temperature synthesis of ReS2 through aqueous perrhenate sulfidation.

In this study, a direct sulfidation reaction of ammonium perrhenate (NH4ReO4) leading to a synthesis of rhenium disulfide (ReS2) is demonstrated. These findings reveal the first example of a simplistic bottom-up approach to the chemical synthesis of crystalline ReS2. The reaction presented here takes place at room temperature, in an ambient and solvent-free environment and without the necessity of a catalyst. The atomic composition and structure of the as-synthesized product were characterized using several analysis techniques including energy dispersive x-ray spectroscopy, x-ray photoelectron spectroscopy, x-ray diffraction, transmission electron microscopy, Raman spectroscopy, thermogravimetric analysis and differential scanning calorimetry. The results indicated the formation of a lower symmetry (1T') ReS2 with a low degree of layer stacking.

Sensitization, energy transfer and infra-red emission decay modulation in Yb3+-doped NaYF4 nanoparticles with visible light through a perfluoroanthraquinone chromophore.

Infra-red emission (980 nm) of sub 10 nm Yb3+-doped NaYF4 nanoparticles has been sensitized through the excitation of 2-hydroxyperfluoroanthraquinone chromophore (1,2,3,4,5,6,7-heptafluro-8-hydroxyanthracene-9,10-dione) functionalizing the nanoparticle surface. The sensitization is achieved with a broad range of visible light excitation (400-600 nm). The overall near infra-red (NIR) emission intensity of Yb3+ ions is increased by a factor 300 as a result of the broad and strong absorption of the chromophore compared with ytterbium's intrinsic absorption. Besides the Yb3+ NIR emission, the hybrid composite shows organic chromophore-based visible emission in the orange-red region of the spectrum. We observe the energy migration process from the sensitized Yb3+ ions at the surface to those in the core of the particle using time-resolved optical spectroscopy. This highlights that the local environments for emitting Yb3+ ions at the surface and center of the nanoparticle are not identical, which causes important differences in the NIR emission dynamics. Based on the understanding of these processes, we suggest a simple strategy to control and modulate the decay time of the functionalized Yb3+-doped nanoparticles over a relatively large range by changing physical or chemical parameters in this model system.

Carbon Nanotube-Quantum Dot Nanohybrids: Coupling with Single-Particle Control in Aqueous Solution.

A strategy is reported for the controlled assembly of organic-inorganic heterostructures consisting of individual single-walled carbon nanotubes (SWCNTs) selectively coupled to single semiconductor quantum dots (QDs). The assembly in aqueous solution was controlled towards the formation of monofunctionalized SWCNT-QD structures. Photoluminescence studies in solution, and on surfaces at the single nanohybrid level, showed evidence of electronic coupling between the two nanostructures. The ability to covalently couple heterostructures with single particle control is crucial for the design of novel QD-based optoelectronic and light-energy conversion devices.

Solution-Processable Carbon Nanoelectrodes for Single-Molecule Investigations.

Here we present a solution-based assembly method for producing molecular transport junctions employing metallic single-walled carbon nanotubes as nanoelectrodes. The molecular junction conductance of a series of oligophenyls was successfully measured, highlighting the potential of an all-carbon based approach for the fabrication of solution-processable single-molecule junctions for molecular electronics.

Synthesis, Characterization, and Application of Core-Shell Co0.16Fe2.84O4@NaYF4(Yb, Er) and Fe3O4@NaYF4(Yb, Tm) Nanoparticle as Trimodal (MRI, PET/SPECT, and Optical) Imaging Agents.

Multimodal nanoparticulate materials are described, offering magnetic, radionuclide, and fluorescent imaging capabilities to exploit the complementary advantages of magnetic resonance imaging (MRI), positron emission tomography/single-photon emission commuted tomography (PET/SPECT), and optical imaging. They comprise Fe3O4@NaYF4 core/shell nanoparticles (NPs) with different cation dopants in the shell or core, including Co0.16Fe2.84O4@NaYF4(Yb, Er) and Fe3O4@NaYF4(Yb, Tm). These NPs are stabilized by bisphosphonate polyethylene glycol conjugates (BP-PEG), and then show a high transverse relaxivity (r2) up to 326 mM(-1) s(-1) at 3T, a high affinity to [(18)F]-fluoride or radiometal-bisphosphonate conjugates (e.g., (64)Cu and (99m)Tc), and fluorescent emissions from 500 to 800 nm under excitation at 980 nm. The biodistribution of intravenously administered particles determined by PET/MR imaging suggests that negatively charged Co0.16Fe2.84O4@NaYF4(Yb, Er)-BP-PEG (10K) NPs cleared from the blood pool more slowly than positively charged NPs Fe3O4@NaYF4(Yb, Tm)-BP-PEG (2K). Preliminary results in sentinel lymph node imaging in mice indicate the advantages of multimodal imaging.

Concentration dependence of the up- and down-conversion emission colours of Er(3+)-doped Y2O3: a time-resolved spectroscopy analysis.

In this paper, a series of Er(3+)-doped Y2O3 samples are systematically investigated, focusing on the effect of the doping concentration on the emission lifetime and spectrum under both 488 nm and 980 nm excitations. Decay times of the (4)S3/2 and (4)F9/2 emitting states under 488 nm and 980 nm excitations are found to be different and concentration dependent. We explain these variations in terms of the changes in the up-conversion routes caused by the predominance of energy exchanges that involve the lowest lying excited states.

Visible-Range Sensitization of Er(3+)-Based Infrared Emission from Perfluorinated 2-Acylphenoxide Complexes.

Five new fully fluorinated acylphenoxide ligands, which are aromatic analogues of ß-diketonates, provide visible photosensitization of the Er(3+4)I13/2 → (4)I15/2 emission at ∼1540 nm (of interest for telecommunications) via the "antenna effect", as observed in Cs[ErL4] compounds. Depending on the chemical functionalization, the excitation wavelength can be tuned in the 400-650 nm range. Decay times for the solids are in the range of 7-16 µs, proving that the complexes can be of interest for a number of optoelectronic and photonic applications.

Efficient sensitized emission in Yb(III) pentachlorotropolonate complexes.

New Yb(III) complexes based on the pentachlorotropolonate (pctrop) ligand show enhanced infrared emission when excited in the orange organic chromophore. Yb(pctrop)(3)(DMF-d(7))(2) presents the highest reported quantum yield for a nonfluorinated infrared-emitting organolanthanide complex.

Luminescent zinc(II) complexes of fluorinated benzothiazol-2-yl substituted phenoxide and enolate ligands.

Zn(II) complexes of the following new, fluorine-containing, benzothiazole-derived ligands have been synthesized and characterized crystallographically: 2-(3,3,3-trifluoro-2-oxopropyl)benzothiazole (3), 4,5,6,7-tetrafluoro-2-(3,3,3-trifluoro-2-oxopropyl)benzothiazole (4), 4,5,6,7-tetrafluoro-2-(2-hydroxyphenyl)benzothiazole (12), 2-(3,4,5,6-tetrafluoro-2-hydroxyphenyl)-4,5,6,7-tetrafluorobenzothiazole (13), and 2-(3,4,5,6-tetrafluoro-2-hydroxyphenyl)benzothiazole (16); the Cu(II) complex of ligand 4 is also reported. These are analogs of the important photo- and electroluminescent material [Zn(BTZ)(2)](2), where H-BTZ = 2-(2-hydroxyphenyl)benzothiazole. DFT calculations indicate that HOMO and LUMO energy levels in these materials are substantially lowered by fluorination. The fluorinated ZnL(2) complexes are mononuclear (in contrast to the dinuclear, nonfluorinated material [Zn(BTZ)(2)](2)). They easily sublime and show broad visible photoluminescence. A common crystallographic feature is the existence of pairs of fluorinated ZnL(2) molecules related by inversion centers, with their π systems facing one another.

A single-device universal logic gate based on a magnetically enhanced memristor.

Memristors are one of the most promising candidates for future information and communications technology (ICT) architectures. Two experimental proofs of concept are presented based on the intermixing of spintronic and memristive effects into a single device, a magnetically enhanced memristor (MEM). By exploiting the interaction between the memristance and the giant magnetoresistance (GMR), a universal implication (IMP) logic gate based on a single MEM device is realized.

Efficient white light emission by upconversion in Yb(3+)-, Er(3+)- and Tm(3+)-doped Y2BaZnO5.

We report efficient white upconversion luminescence in Yb(3+)-, Er(3+)- and Tm(3+)-doped monophasic and biphasic Y(2)BaZnO(5) phosphors under 977 nm near-infrared excitation and at low excitation power densities (down to ∼25 mW mm(-2)).