Trans-membrane Fluorescence Enhancement by Carbon Dots: Ionic Interactions and Energy Transfer.

We report on trans-membrane interactions between blue-emitting carbon dots (CDs) and fluorescein. Hydrophobic CDs with a positive surface charge are embedded as-synthesized in the lipophilic sheet of the bilayer membrane of large synthetic phospholipid vesicles. The vesicles are prepared by mixing DOPC phospholipids and lipid molecules that contain anionic fluorescein attached to their hydrophilic head. Due to attractive electrostatic interactions, the CDs and fluorescein conjoin within the vesicle membrane, which leads to photoluminescence enhancement of fluorescein and facilitates trans-membrane energy transfer between the CDs and the dye.

Tracking the Source of Carbon Dot Photoluminescence: Aromatic Domains versus Molecular Fluorophores.

Carbon dots (CDs) are an intriguing fluorescent material; however, due to a plethora of synthesis techniques and precursor materials, there is still significant debate on their structure and the origin of their optical properties. The two most prevalent mechanisms to explain them are based on polycyclic aromatic hydrocarbon domains and small molecular fluorophores, for instance, citrazinic acid. Yet, how these form and whether they can exist simultaneously is still under study. To address this, we vary the hydrothermal synthesis time of CDs obtained from citric acid and ethylenediamine and show that in the initial phase molecular fluorophores, likely 2-pyridone derivatives, account for the blue luminescence of the dots. However, over time, while the overall size of the CDs does not change, aromatic domains form and grow, resulting in a second, faster decay channel at similar wavelengths and also creating additional lower energetic states. Electrophoresis provides further evidence that the ensemble of CDs consists of several subsets with different internal structure and surface charge. The understanding of the formation mechanism enables a control of the chemical origin of these emitters and the ensuing optical properties of the CDs through synthetic means.

Effect of nitrogen atom positioning on the trade-off between emissive and photocatalytic properties of carbon dots.

Carbon dots (CDs) are a versatile nanomaterial with attractive photoluminescent and photocatalytic properties. Here we show that these two functionalities can be easily tuned through a simple synthetic means, using a microwave irradiation, with citric acid and varying concentrations of nitrogen-containing branched polyethyleneimine (BPEI) as precursors. The amount of BPEI determines the degree of nitrogen incorporation and the different inclusion modes within the CDs. At intermediate levels of BPEI, domains grow containing mainly graphitic nitrogen, producing a high photoluminescence yield. For very high (and very low) BPEI content, the nitrogen atoms are located primarily at the edge sites of the aromatic domains. Accordingly, they attract photogenerated electrons, enabling efficient charge separation and enhanced photocatalytic hydrogen generation from water. The ensuing ability to switch between emissive and photocatalytic behavior of CDs is expected to bring substantial improvements on their efficiency for on-demand light emission or energy conversion applications.

Dilution-Induced Formation of Hybrid Perovskite Nanoplatelets.

Perovskite nanocrystals (NCs) are an important extension to the fascinating field of hybrid halide perovskites. Showing significantly enhanced photoluminescence (PL) efficiency and emission wavelengths tunable through halide content and size, they hold great promise for light-emitting applications. Despite the rapid advancement in this field, the physical nature and size-dependent excitonic properties have not been well investigated due to the challenges associated with their preparation. Herein we report the spontaneous formation of highly luminescent, quasi-2D organic-inorganic hybrid perovskite nanoplatelets (NPls) upon dilution of a dispersion of bulk-like NCs. The fragmentation of the large NCs is attributed to osmotic swelling induced by the added solvent. An excess of organic ligands in the solvent quickly passivates the newly formed surfaces, stabilizing the NPls in the process. The thickness of the NPls can be controlled both by the dilution level and by the ligand concentration. Such colloidal NPls and their thin films were found to be extremely stable under continuous UV light irradiation. Full tunability of the NPl emission wavelength is achieved by varying the halide ion used (bromide, iodide). Additionally, time-resolved PL measurements reveal an increasing radiative decay rate with decreasing thickness of the NPls, likely due to an increasing exciton binding energy. Similarly, measurements on iodide-containing NPls show a transformation from biexponential to monoexponential PL decay with decreasing thickness, likely due to an increasing fraction of excitonic recombination. This interesting phenomenon of change in fluorescence upon dilution is a result of the intricate nature of the perovskite material itself and is uncommon in inorganic materials. Our findings enable the synthesis of halide perovskite NCs with high quantum efficiency and good stability as well as a tuning of both their optical and morphological properties.

Tuning the Optical Properties of Perovskite Nanoplatelets through Composition and Thickness by Ligand-Assisted Exfoliation.

High-quality hybrid halide perovskite nanocrystals are fabricated through a simple, versatile, and efficient two-step process involving a dry step followed by a ligand-assisted liquid-phase exfoliation step. The emission wavelength of the resulting nanocrystals can be tuned either through composition by varying the halide content or by reducing their thickness.

Carbon Dots: A Unique Fluorescent Cocktail of Polycyclic Aromatic Hydrocarbons.

Carbon dots (CDs) have attracted rapidly growing interest in recent years due to their unique and tunable optical properties, the low cost of fabrication, and their widespread uses. However, due to the complex structure of CDs, both the molecular ingredients and the intrinsic mechanisms governing photoluminescence of CDs are poorly understood. Among other features, a large Stokes shift of over 100 nm and a photoluminescence spectrally dependent on the excitation wavelength have so far not been adequately explained. In this Letter we investigate CDs and develop a model system to mimic their optical properties. This system comprised three types of polycyclic aromatic hydrocarbon (PAH) molecules with fine-tuned concentrations embedded in a polymer matrix. The model suggests that the Stokes shift in CDs is due to the self-trapping of an exciton in the PAH network. The width and the excitation dependence of the emission comes from a selective excitation of PAHs with slightly different energy gaps and from energy transfer between them. These insights will help to tailor the optical properties of CDs and help their implementation into applications, e.g., light-emitting devices and biomarkers. This could also lead to "artificial" tunable carbon dots by locally modifying the composition and consequently the optical properties of composite PAH films.