Ultraprecise control over the photophysical properties of novel amino acid functionalized CdTeS quantum dots and their effect on the emission of yellow-emissive carbon dots.

Cadmium-based quantum dots (QDs) are amongst the most studied nanomaterials due to their excellent photophysical properties, which can be controlled by controlling the size and/or composition of the nanocrystal. However, the ultraprecise control over size and photophysical properties of Cd-based quantum dots and developing user-friendly techniques to synthesize amino acid-functionalized cadmium-based QDs are still the on-going challenges. In this study, we modified a traditional two-phase synthesis method to synthesize cadmium telluride sulfide (CdTeS) QDs. CdTeS QDs were grown with an extremely slow growth-rate (growth saturation of about 3 days), which allowed us to have an ultraprecise control over size, and as a consequence, the photophysical properties. Also, the composition of CdTeS could be controlled by controlling the precursor ratios. The CdTeS QDs were successfully functionalized with a water-soluble amino acid, L-cysteine, and an amino acid derivative, N-acetyl-L-cysteine. Red-emissive L-cysteine-functionalized CdTeS QDs interacted with yellow-emissive carbon dots. The fluorescence intensity of carbon dots increased upon interaction with CdTeS QDs. This study proposes a mild method that allows to grow QDs with an ultraprecise control over the photophysical properties and shows the implementation of Cd-based QDs to enhance the fluorescence intensity of different fluorophores with fluorescence wavelength at higher energy bands.

Development of Highly Luminescent Water-Insoluble Carbon Dots by Using Calix[4]pyrrole as the Carbon Precursor and Their Potential Application in Organic Solar Cells.

Carbon dots (CDs) are carbon-based fluorescent nanomaterials that are of interest in different research areas due to their low cost production and low toxicity. Considering their unique photophysical properties, hydrophobic/amphiphilic CDs are powerful alternatives to metal-based quantum dots in LED and photovoltaic cell designs. On the other hand, CDs possess a considerably high amount of surface defects that give rise to two significant drawbacks: (1) causing decrease in quantum yield (QY), a crucial drawback that limits their utilization in LEDs, and (2) affecting the efficiency of charge transfer, a significant factor that limits the use of CDs in photovoltaic cells. In this study, we synthesized highly luminescent, water-insoluble, slightly amphiphilic CDs by using a macrocyclic compound, calix[4]pyrrole, for the first time in the literature. Calix[4]pyrrole-derived CDs (CP-DOTs) were highly luminescent with a QY of over 60% and size of around 4-10 nm with graphitic structure. The high quantum yield of CP-DOTs indicated that they had less amount of surface defects. Furthermore, CP-DOTs were used as an additive in the active layer of organic solar cells (OSC). The photovoltaic parameters of OSCs improved upon addition of CDs. Our results indicated that calix[4]pyrrole is an excellent carbon precursor to synthesize highly luminescent and water-insoluble carbon dots, and CDs derived from calix[4]pyrrole are excellent candidates to improve optoelectronic devices.

Fabrication of mesoporous metal chalcogenide nanoflake silica thin films and spongy mesoporous CdS and CdSe.

Mesoporous silica metal oxide (ZnO and CdO) thin films have been used as metal ion precursors to produce the first examples of mesoporous silica metal sulfide (meso-SiO(2) @ZnS, meso-SiO(2) @CdS) or silica metal selenide (meso-SiO(2) @ZnSe, meso-SiO(2) @CdSe) thin films, in which the pore walls are made up of silica and metal sulfide or metal selenide nanoflakes, respectively. A gentle chemical etching with a dilute HF solution of the meso-SiO(2) @CdS (or meso-SiO(2) @CdSe) produces mesoporous cadmium sulfide (meso-CdS) (or cadmium selenide, meso-CdSe). Surface modified meso-CdS displays bright blue photoluminescence upon excitation with a UV light. The mesoporous silica metal oxides are formed as metal oxide nanoislands over the silica walls through a self-assembly process of a mixture of metal nitrate salt-two surfactants-silica source followed by calcination step. The reactions, between the H(2) S (or H(2) Se) gas and solid precursors, have been carried out at room temperature and monitored using spectroscopy and microscopy techniques. It has been found that these reactions are: 1) taking place through the diffusion of sulfur or selenium species from the top metal oxide layer to the silica metal oxide interface and 2) slow and can be stopped at any stage to obtain mesoporous silica metal oxide metal sulfide or silica metal oxide metal selenide intermediate thin films.

Synthesis of stable mesostructured coupled semiconductor thin films: meso-CdS-TiO(2) and meso-CdSe-TiO(2).

Cd(II) ions can be incorporated into the channels of mesostructured titania films, using the evaporation-induced self-assembly (EISA) approach, up to a record high Cd/Ti mole ratio of 25%. The film samples were obtained by spin or dip coating from a mixture of 1-butanol, [Cd(H(2)O)(4)](NO(3))(2), HNO(3), and Ti(OC(4)H(9))(4) and then aging the samples under 50% humidity at 30 degrees C (denoted as meso-xCd(II)-yTiO(2)). The nitrate ions, from nitric acid and cadmium nitrate, play important roles in the assembly process by coordinating as bidentate and bridged ligands to Cd(II) and Ti(IV) sites, respectively, in the mesostructured titania films. The film samples can be reacted under a H(2)S (or H(2)Se) gas atmosphere to produce CdS (or CdSe) on the channel surface and/or pore walls. However, the presence of such a large number of nitrate ions in the film samples also yields an extensive amount of nitric acid upon H(2)S (or H(2)Se) reaction, where the nanoparticles are not stable (they undergo decomposition back to metal ion and H(2)S or H(2)Se gas). However, this problem can be overcome by further aging the samples at 130 degrees C for a few hours before H(2)S (or H(2)Se) reaction. This step removes about 90% of the nitrate ions, eliminates the nitric acid production step, and stabilizes the CdS nanoparticles on the surface and/or walls of the pores of the coupled semiconductor films, denoted as meso-xCdS-yTiO(2). However, the H(2)Se reaction, additionally, needs to be carried at lower H(2)Se pressures in an N(2) atmosphere to produce stable CdSe nanoparticles on the surface and/or walls of the pores of the films, denoted as meso-xCdSe-yTiO(2). Otherwise, an excessive number of Se(8) particles form in the film samples.