Solid-state optical properties of self-assembling amyloid-like peptides with different charged states at the terminal ends

The self-assembling of small peptides not only leads to the formation of intriguing nanoarchitectures, but also generates materials with unexpected functional properties. Oligopeptides can form amyloid-like cross-β assemblies that are able to emit intrinsic photoluminescence (PL), over the whole near-UV/visible range, whose origin is still largely debated. As proton transfer between the peptide chain termini within the assembly is one of the invoked interpretations of this phenomenon, we here evaluated the solid state PL properties of a series of self-assembled hexaphenylalanine peptides characterized by a different terminal charge state. Overall, our data indicate that the charge state of these peptides has a marginal role in the PL emission as all systems exhibit very similar multicolour PL associated with a violation of the Kasha’s rule. On the other hand, charged/uncharged ends occasionally produce differences in the quantum yields. The generality of these observations has been proven by extending these analyses to the Aβ16–21 peptide. Collectively, the present findings provide useful information for deciphering the code that links the spectroscopic properties of these assemblies to their structural/electronic features.

Effect of a Rubidium Chloride Carrier Confinement Layer on the Characteristics of CsPbBr3 Perovskite Light-Emitting Diodes

This work describes the effect of a rubidium chloride (RbCl) interlayer in CsPbBr3 perovskite light-emitting diode (LED) structures. RbCl crystallites exhibited polyhedral structures and lattice parameters similar to those of CsPbBr3 perovskite crystallites. The lattice mismatch between the RbCl interlayer and CsPbBr3 active layer was only approximately 2%. The devices exhibited the best quality and performance when RbCl was used as the nucleation and carrier confinement layer. The crystallite sizes of CsPbBr3 with 0.2-, 0.5-, and 1-nm-thick RbCl bottom layers were 55.1, 65.4, and 55.1 nm, respectively. The full width at half maximum (FWHM) of the photoluminescence (PL) emission peak for CsPbBr3 with the RbCl bottom layer was 0.096 eV.

Preparation and Fluorescent Wavelength Control of Multi-Color Nitrogen-Doped Carbon Nano-Dots

It is known that, by taking advantage of heteroatom doping, the electronic states and transition channels in carbon nano-dots (CNDs) can be effectively modulated. Thus, the photoluminescence (PL) properties of CNDs can be changed. For potential applications of CNDs as advanced materials for optoelectronic devices, it is important and significant to develop the practical techniques for doping heteroatoms into CNDs. In this work, we synthesize the multi-color fluorescent by using a fast and effective microwave method where the CNDs are nitrogen-doped. We examine the influence of different ratios of the raw materials on the structure and optical properties of N-CNDs. The results show that the prepared N-CNDs can generate blue (445 nm), green (546 nm), and orange (617 nm) fluorescence or PL with the mass ratio of the raw materials at 1:1, 1:2 and 1:3, respectively. We find that the N content in N-CNDs leads to different surface/edge states in n−π∗ domain. Thus, the wavelength of the PL emission from N-CNDs can be tuned via controlling the N concentration doped into the CNDs. Moreover, it is shown that the intensity of the PL from N-CNDs is mainly positively related to the content of C-O groups attached on the surface/edges of the N-CNDs. This study provides an effective experimental method and technical way to improve the fluorescent emission, and to modulate the color of the PL emission from CNDs.

Low-temperature luminescence in organic-inorganic lead iodide perovskite single crystals

We present temperature and laser-power dependent photoluminescence (PL) study of methylammonium lead iodide (CH3NH3PbI3) single crystals in the orthorhombic phase. At temperatures below 140 K, we revealed the multi-component PL emission. In addition to a free exciton with an energy of 1.65 eV, we found emission bands with peaks approximately equal to 1.6 eV, 1.52 eV, and 1.48 eV. Analysis of the thermal evolution of the intensities, peak positions, and linewidths of all the PL bands allowed one to determine their origin. We attributed the PL peak with the energy of 1.6 eV to a bound exciton, while the free exciton-bound exciton splitting energy is 50-60 meV. The PL emission with an energy of 1.52 eV can be explained by the donor-acceptor pair (DAP) recombination, where donor and acceptor defects have a depth of about 12 meV and 120 meV, respectively. MA (CH3NH3) interstitials (MA+i ) and lead vacancies (V2-Pb) are the most suitable for the DAP transition to occur in CH3NH3PbI3 crystals. The 1.48 eV PL emission is consistent with the recombination of self-trapped excitons, and interstitial iodine is likely to be an active trap source. We found the variation of the self-trapped depth from 15 meV (at T<80 K) to 53 meV (at T>80 K) with increasing the temperature. Although the multi-component PL emission in CH3NH3PbI3 single crystals appears at low temperatures, defects and excitonic traps that cause this emission can affect the photophysics of hybrid perovskites at higher temperatures.

Effect of the Graded Silicon Content in SRN/SRO Multilayer Structures on the Si Nanocrystals and Si Nanopyramids Formation and Their Photoluminescence Response

Two multilayer (ML) structures, composed of five layers of silicon-rich oxide (SRO) with different Si contents and a sixth layer of silicon-rich nitride (SRN), were deposited by low pressure chemical vapor deposition. These SRN/SRO MLs were thermally annealed at 1100 °C for 180 min in ambient N2 to induce the formation of Si nanostructures. For the first ML structure (MLA), the excess Si in each SRO layer was about 10.7 ± 0.6, 9.1 ± 0.4, 8.0 ± 0.2, 9.1 ± 0.3 and 9.7 ± 0.4 at.%, respectively. For the second ML structure (MLB), the excess Si was about 8.3 ± 0.2, 10.8 ± 0.4, 13.6 ± 1.2, 9.8 ± 0.4 and 8.7 ± 0.1 at.%, respectively. Si nanopyramids (Si-NPs) were formed in the SRO/Si substrate interface when the SRO layer with the highest excess silicon (10.7 at.%) was deposited next to the MLA substrate. The height, base and density of the Si-NPs was about 2–8 nm, 8–26 nm and ~6 × 1011 cm−2, respectively. In addition, Si nanocrystals (Si-ncs) with a mean size of between 3.95 ± 0.20 nm and 2.86 ± 0.81 nm were observed for the subsequent SRO layers. Meanwhile, Si-NPs were not observed when the excess Si in the SRO film next to the Si-substrate decreased to 8.3 ± 0.2 at.% (MLB), indicating that there existed a specific amount of excess Si for their formation. Si-ncs with mean size of 2.87 ± 0.73 nm and 3.72 ± 1.03 nm were observed for MLB, depending on the amount of excess Si in the SRO film. An enhanced photoluminescence (PL) emission (eight-fold more) was observed in MLA as compared to MLB due to the presence of the Si-NPs. Therefore, the influence of graded silicon content in SRN/SRO multilayer structures on the formation of Si-NPs and Si-ncs, and their relation to the PL emission, was analyzed.

Toward white light emission from plasmonic-luminescent hybrid nanostructures

We study the light emission of plasmonic-luminescent hybrid nanostructures consisting of Ag nanoparticles (NPs) embedded in europium oxide (EuOX). The Ag NPs present a bidimensional organization in the nanostructures and they optically behave as oblate spheroids. The photoluminescence (PL) spectral response of the nanostructures evolves from a narrow red emission characteristic of Eu3+ ions in absence of Ag NPs to a broad blue-green emission band associated with Eu2+ ions when the layer of Ag NPs is present. This behavior is not related to a change in the Eu2+/Eu3+ ratio, which is verified by compositional analysis. Instead, a detailed investigation of the PL emission of the nanostructures suggests that the coupling of the Ag NPs to the Eu2+ ions present in the EuOX layer, which manifests itself in an efficient sensitization of these ions, enhances their broad visible emission. In particular, the longitudinal mode of the Ag NPs surface plasmon is considered to be responsible for the efficient energy transfer for the non-normal incidence excitation PL configuration used. Finally, the use of a capping amorphous Al2O3 layer allows improving the robustness of hybrid nanostructures and further enhances their PL emission. These findings provide a new path to actively control the selective excitation of Eu2+ and Eu3+ ions via a controlled coupling with the surface plasmon resonance modes of the Ag NPs and points to these nanostructures as promising building blocks for the development of integrable white light sources.

Morphology and photoluminescence properties of silicon nanoparticles deposited in helium-nitrogen mixtures maintained at low residual pressures

We elaborated a technique of pulsed laser ablation in gas mixtures (He-N2), maintained under residual pressures of 0.5–5 Torr to deposit silicon (Si)-based nanostructured films on a substrate. We show that the deposited films can exhibit strong photoluminescence (PL) emission with the position of peaks depending on the pressure of ambient gas and the ratio of gases in the mixture. Nanostructured films prepared in pure He gas exhibited a strong band in the infrared range (around 760 nm) and a weak band in the green range (550 nm), which were attributed to quantum-confined excitonic states in small Si nanocrystals and radiative transitions via the localized electronic states in silicon suboxide coating, respectively. In contrast, nanostructured films prepared in He-N2 mixtures exhibited more intense “green-yellow” PL band centered at 580 nm, which was attributed to a radiative recombination in amorphous oxynitride (a-SiNxOy) coating of Si nanocrystals. We also present a detailed analysis of morphology of nanostructures Si-based films prepared by laser ablation. Finally, we show that the nanocrystals can be removed from the substrate and milled by ultrasound to form aqueous solutions of colloidal Si nanopartiles. The fabricated Si-based nanocrystals present a promising object for theranostics, combining imaging functionality based on PL emission and a series of therapy functionalities (photo and radiofrequency hyperthermia, photodynamic therapy).

Synthesis and Electro-Optical Property of Green Fluorescent Emitter Based on Anthracene Core and Optimized Side Groups

New green emitter is designed and synthesized by selecting anthracene having high photoluminescence quantum yield (PLQY) and diphenylamine side group substituted methyl and t-butyl group: N9,N10-bis(5-(tert-butyl)-2-methylphenyl)-N9,N10-bis(2,4-dimethylphenyl)anthracene-9,10-diamine (3Me-1Bu-TPADA). Photophysical, electrochemical, and electroluminescent (EL) properties of 3Me-1Bu-TPADA were investigated. The maximum photoluminescence (PL) emission wavelengths of 3Me-1Bu-TPADA in solution and in a film were 528 nm and 531 nm, respectively. 3Me-1Bu-TPADA has excellent thermal properties with glass transition temperatures (Tg) of 110 °C, melting temperatures (Tm) of 217 °C of, and degradation temperature (Td) of 330 °C. 3Me-1Bu-TPADA was used as an emitting layer in non-doped devices: ITO/2-TNATA (60 nm)/NPB (15 nm)/3Me-1Bu-TPADA (30 nm)/Alq3 (30 nm)/LiF (1 nm)/Al (200 nm). The 3Me-1Bu-TPADA device showed luminance efficiency of 6.05 cd/A, EQE of 2.68% at 10 mA/cm2.

Towards Red Emissive Systems Based on Carbon Dots

Carbon dots (C-dots) represent an emerging class of nontoxic nanoemitters that show excitation wavelength-dependent photoluminescence (PL) with high quantum yield (QY) and minimal photobleaching. The vast majority of studies focus on C-dots that exhibit the strongest PL emissions in the blue/green region of the spectrum, while longer wavelength emissions are ideal for applications such as bioimaging, photothermal and photodynamic therapy and light-emitting diodes. Effective strategies to modulate the PL emission of C-dot-based systems towards the red end of the spectrum rely on extensive conjugation of sp2 domains, heteroatom doping, solvatochromism, surface functionalization and passivation. Those approaches are systematically presented in this review, while emphasis is given on important applications of red-emissive suspensions, nanopowders and polymer nanocomposites.