Chemically synthesized carbon dots (CDs) have attracted a lot of attention as an eco-friendly and cost-efficient light-emitting material, and functionalization of CD surfaces with additives of different natures is a useful way to control their properties. In this study, we show how a post-synthetic treatment of CDs with citric acid, benzoic acid, urea and o-phenylenediamine changes their chemical composition and optical properties. In particular, it results in the formation of carboxyl/imide/carbonyl groups at the CD surface, leading to the appearance of additional blue (or for CDs treated with phenylenediamine, blue and green) emissive optical centers on top of the remaining emission from the original CDs. Most importantly, the increased oxidation degree alongside a decreased relative amount of carbon and nitrogen in such treated CDs decreases their highest occupied molecular orbital (HOMO) energy level by up to 0.9 eV (the maximal value was observed for CDs treated with o-phenylenediamine). Moreover, the Fermi energy level shifted above the lowest unoccupied molecular orbital (LUMO) energy level for some of the treated CD samples. Thus, the energy structure of CDs can be tuned and optimized for further applications through the functionalization of their surface with organic additives.
In recent years, there has been rapid progress in the development of photonic devices based on lead halide perovskite nanocrystals since they possess a set of unique optical and charge transport properties. However, the main limiting factor for their subsequent application is poor stability against exposure to adverse environmental conditions. In this work, a study of a composite material based on perovskite CsPbBr3 nanocrystals embedded in porous silica microspheres is presented. We developed two different approaches to change the interface between nanocrystals and the surface of the microsphere pores: surface treatment of (i) nanocrystals or (ii) microspheres. The surface modification with tetraethylorthosilicate molecules not only increased stability but also improved the optical responses of the composite material. The position of the emission band remained almost unchanged, but its lifetime increased significantly compared to the initial value. The improvement of the optical performance via surface modification with tetraethylorthosilicate molecules also works for the lead-free Bi-doped Cs2AgInCl6 double perovskite nanocrystals leading to increased stability of their optical responses at ambient conditions. These results clearly demonstrate the advantage of a composite material that can be used in novel photonic devices with improved performance.
9 February 2024 in Journal of Materials Chemistry C
On-going development of carbon dots (CDs) for different applications calls for search of novel methods for their synthesis and surface functionalization. For fabrication of photonic devices, CDs should be soluble in non-polar solvents that are used for ink-printing of their functional layers, apart from the obvious requirement of bright luminescence. Herein, we introduce amphiphilic CDs synthesized from a mixture of benzoic acid and ethylenediamine in acetylacetone, which satisfy both above mentioned requirements. These CDs are quasi-spherical nanoparticles 20-50 nm in size, holding aliphatic, carbonyl, amide, imine, and carbamate groups at the surface which renders them amphiphilic and soluble in a variety of substances with relative polarity ranging from 0.002 to 1, such as toluene, chloroform, alcohols, and water. By variation of the molar ratio of benzoic acid and ethylenediamine, a highest quantum yield of 36 % in isopropanol is achieved for the amphiphilic CDs reported so far. As a demonstration of use of developed amphiphilic CDs in LEDs, green emitting charge-injection devices were fabricated with a broad emission band centered at 515 nm, maximal luminance of 1716 cd/m2, and ССT of 5627 K which is the first LED based on amphiphilic CDs. Furthermore, these CDs can be used as luminescent inks, and as active material for solar concentrators.
Today, the development of nanomaterials with sensing properties attracts much scientific interest because of the demand for low-cost nontoxic colloidal nanoprobes with high sensitivity and selectivity for various biomedical and environment-related applications. Carbon dots (CDs) are promising candidates for these applications as they demonstrate unique optical properties with intense emissions, biocompatibility, and ease of fabrication. Herein, we developed synthesis protocols to obtain CDs based on o-phenylenediamine with a variety of optical responses depending on additional precursors and changes in the reaction media. The obtained CDs are N-doped (N,S-doped in case of thiourea addition) less than 10 nm spherical particles with emissions observed in the 300–600 nm spectral region depending on their chemical composition. These CDs may act simultaneously as absorptive/fluorescent sensing probes for solvent polarity with up to 85, for from 0.099 to 1.0 and for pH values in the range of 3.0–8.0, thus opening an opportunity to check the pH in non-pure water or a mixture of solvents. Moreover, CDs preserve their optical properties when embedded in cellulose strips that can be used as sensing probes for fast and easy pH checks. We believe that the resulting dual-purpose sensing nano probes based on CDs will have high demand in various sensing applications.