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Ligand induced switching of the band alignment in aqueous synthesized CdTe/CdS core/shell nanocrystals.

ABSTRACT: CdTe/CdS core/shell quantum dots (QDs) are formed in aqueous synthesis via the partial decomposition of hydrophilic thiols, used as surface ligands. In this work, we investigate the influence of the chemical nature (functional group and chain length) of the used surface ligands on the shell formation. Four different surface ligands are compared: 3-mercaptopropionic acid, MPA, thioglycolic acid, TGA, sodium 3-mercaptopropanesulfonate, MPS, and sodium 2-mercaptoethanesulfonate, MES. The QD growth rate increases when the ligand aliphatic chain length decreases due to steric reasons. At the same time, the QDs stabilized with carboxylate ligands grow faster and achieve higher photoluminescence quantum yields compared to those containing sulfonate ligands. The average PL lifetime of TGA and MPA capped QDs is similar (?20?ns) while in the case of MPS shorter (?15?ns) and for MES significantly longer (?30?ns) values are measured. A detailed structural analysis combining powder X-ray diffraction, and X-ray photoelectron spectroscopy (XPS) indicates the existence of two novel regimes of band alignment: in the case of the mercaptocarboxylate ligands the classic type I band alignment between the core and shell materials is predominant, while the mercaptosulfonate ligands induce a quasi-type II alignment (MES) or an inverted type I alignment (MPS). Finally, the effect of the pH value on the optical properties was evaluated: using a ligand excess in solution allows achieving better stability of the QDs while maintaining high photoluminescence intensity at low pH.

SUBMITTER: Vale BRC

PROVIDER: S-EPMC6554334 | biostudies-literature | 2019 Jun

REPOSITORIES: biostudies-literature

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Ligand induced switching of the band alignment in aqueous synthesized CdTe/CdS core/shell nanocrystals.

Vale Brener R C BRC Mourão Rafael S RS Bettini Jefferson J Sousa José C L JCL Ferrari Jefferson L JL Reiss Peter P Aldakov Dmitry D Schiavon Marco A MA

Scientific reports 20190606 1

CdTe/CdS core/shell quantum dots (QDs) are formed in aqueous synthesis via the partial decomposition of hydrophilic thiols, used as surface ligands. In this work, we investigate the influence of the chemical nature (functional group and chain length) of the used surface ligands on the shell formation. Four different surface ligands are compared: 3-mercaptopropionic acid, MPA, thioglycolic acid, TGA, sodium 3-mercaptopropanesulfonate, MPS, and sodium 2-mercaptoethanesulfonate, MES. The QD growth ...[more]

PMID: 31171820

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Project description:To study the influence of the chemical and crystalline composition of core/shell NCs on their photoluminescence (PL) the mean structural profile of a large ensemble of NCs has to be retrieved in atomic resolution. This can be achieved by retrieving the chemical profile of core/shell NCs using anomalous small angle x-ray scattering (ASAXS) in combination with the analysis of powder diffraction data recorded by wide angle x-ray scattering (WAXS). In the current synchrotron based study, we investigate CdSe/CdS core/shell NCs with different core dimensions by recording simultaneously ASAXS and WAXS spectra. The CdS shells are grown epitaxial on nominal spherical CdSe cores with core diameters from around 3.5-5.5 nm. Three different CdSe shell thicknesses are realized by depositing around 4, 6, and 8 monolayers (MLs) of CdSe. We reveal that the epitaxial core/shell structure depicts a chemical sharp interface, even after a post growth annealing step. With increasing NC diameter, however, the CdSe/CdS NCs deviate significantly from a spherical shape. Instead an elliptical particle shape with pronounced surface facets for the larger core/shell NCs is found. In combination with the powder diffraction data we could relate this anisotropic shape to a mixture of crystal phases within the CdSe core. The smallest CdSe cores exhibit a pure hexagonal wurtzite crystal structure, whereas the larger ones also possess a cubic zincblende phase fraction. This mixed crystal phase fractions lead to a non-spherical shell growth with different thicknesses along specific crystallographic directions: The long axes are terminated by basal crystal faces parallel either to the a- or c-axis, the short axes by "tilted" pyramidal planes. By combining these structural data with the measured PL quantum yield values, we can clearly connect the optical output of the NCs to their shape and to their shell thickness. Above 6 ML CdS shell-thickness no further increase of the PL can be observed, but for large aspect ratio values the PL is significantly decreased. The gained understanding of the internal crystal structure on CdSe/CdS NCs is general applicable for a precise tuning of the optical properties of crystalline core/shell NCs.

Dataset Information

Ligand induced switching of the band alignment in aqueous synthesized CdTe/CdS core/shell nanocrystals.

Publications

Ligand induced switching of the band alignment in aqueous synthesized CdTe/CdS core/shell nanocrystals.

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