II-VI core/shell quantum dots and doping with transition metal ions as a means of tuning the magnetoelectronic properties of CdS/ZnS core/shell QDs: A DFT study.

This paper examines the alterations in the properties of II-VI Quantum Dots (QDs) when these are coated with a shell made of another material of the same family and investigates the structural, electronic and magnetic properties of doped CdS/ZnS core/shell QDs. The core/shell QDs have been constructed by building the shell over the bare core QD and it is found that this construction of a shell over the bare QD can bring about dramatic changes in its optical properties. On changing the shell by varying either the cation or the anion, substantial variations are brought about in the band gap and electrophilicity. The trend of Fermi energies is more negative for core/shell QDs than for the QDs without a shell, and the value is almost the same for core/shell QDs with the same core. Swapping of the core and the shell materials brings greater stability in the case of shells of the wider band gap materials. Binding energy data demonstrates that the CdS/ZnS, CdSe/ZnSe, CdSe/CdS core/shell systems are more stable than ZnS/CdS, ZnSe/CdSe, CdS/CdSe core/shell systems, respectively. An augmentation in the properties is found on doping the QD with transition metal ions. The binding energies are found to be functions of the kind of dopant as well as the spin multiplicity and account for the stability of one spin state over the other at a specific site of the QD. The most fascinating property that plays a decisive role in the extant work is the introduction of magnetism in core/shell QDs as a result of the entry of unpaired electrons within the CdS/ZnS QDs on doping with transition metal ions. The deviation of the observed magnetic moments from the expected values increases as the dopant is varied from Mn2+ to Fe2+ to Co2+ to Ni2+ to Cu2+. Hirshfeld charge analysis shows that the doped ion accepts negative charge from the sulfide ions in the core, with the smallest charge transfer seen in the case of Hg2+ ions. As we move from Mn2+ to Hg2+, the trend followed for the Hirshfeld charges indicates that the overall charge on the core is lower and that on the shell is higher for all the doped cases in comparison to the undoped CdS/ZnS core/shell QD. The band gap values reveal that the Fe2+ doped CdS/ZnS core/shell structures have the smallest band gaps. Hence, we expect that this paper will help researchers to develop a strategy to produce QDs of the anticipated properties for various applications, and transition metal ions can be successfully employed for modification of various magnetoelectronic properties of the host semiconductor for future applications in nanotechnology.

Malik P ，Thareja R ，Singh J ，Kakkar R ... -  《-》

Hydrothermal synthesis of water-soluble Mn- and Cu-doped CdSe quantum dots with multi-shell structures and their photoluminescence properties.

Optical properties of semiconductor quantum dots (QDs) can be tuned by doping with transition metal ions. In this study, water-soluble CdSe/ZnS:Mn/ZnS QDs with the core/shell/shell structure were synthesized through a hydrothermal method, in which the surface of the CdSe core was coated with a ZnS:Mn shell and ZnS capping shell. Herein, the CdSe core QDs were prepared first and then doped with Mn2+; therefore, the QD size and doping level could be controlled independently and interference from the self-purifying effect could be avoided. When CdSe cores with diameters less than 1.9 nm were used, Mn-related photoluminescence (PL) was observed as the main PL band, whereas the band-edge PL was mainly observed when larger CdSe cores were used. Furthermore, using ZnS:Cu as the doping shell layer, CdSe/ZnS:Cu/ZnS and ZnSe/ZnS:Cu/ZnS nanoparticles were successfully synthesized, and Cu-related PL was clearly observed. These results indicate that the core/shell/shell QD structure with doping in the shell layer is a versatile method for synthesizing doped QDs.

Nishimura H ，Enomoto K ，Pu YJ ，Kim D ... -  《RSC Advances》

Bandgap- and Radial-Position-Dependent Mn-Doped Zn-Cu-In-S/ZnS Core/Shell Nanocrystals.

This paper presents a mechanistic study on the doping of Zn-Cu-In-S/ZnS core/shell quantum dots (QDs) with Mn by changing the Zn-Cu-In-S QD bandgap and dopant position inside the samples (Zn-Cu-In-S core and ZnS shell). Results show that for the Mn:Zn-Cu-In-S/ZnS system, a Mn-doped emission can be obtained when the bandgap value of the QDs is larger than the energy of Mn-doped emission. Conversely, a bandgap emission is only observed for the doped system when the bandgap value of QDs is smaller than the energy gap of the Mn-doped emission. In the Zn-Cu-In-S/Mn:ZnS systems, doped QDs show dual emissions, consisting of bandgap and Mn dopant emissions, instead of one emission band when the value of the host bandgap is larger than the energy of the Mn-doped emission. These findings indicate that the emission from Mn-doped Zn-Cu-In-S/ZnS core/shell QDs depends on the bandgap of the QDs and the dopant position inside the core/shell material. The critical bandgap of the host materials is estimated to have the same value as the energy of the Mn d-d transition. Subsequently, the mechanism of photoluminescence properties of the Mn:Zn-Cu-In-S/ZnS and Zn-Cu-In-S/Mn:ZnS core/shell QD systems is proposed. Control experiments are then carried out by preparing Mn-doped Zn(Cu)-In-S QDs with various bandgaps, and the results confirm the reliability of the suggested mechanism. Therefore, the proposed mechanism can aid the design and synthesis of novel host materials in fabricating doped QDs.

Peng L ，Huang K ，Zhang Z ，Zhang Y ，Shi Z ，Xie R ，Yang W ... -  《-》

Sensitization enhancement of europium in ZnSe/ZnS core/shell quantum dots induced by efficient energy transfer.

Eu-doped ZnSe:/ZnS quantum dots (formed as ZnSe:Eu/ZnS QDs) were successfully synthesized by a two-step wet chemical method: nucleation doping and epitaxial shell growing. The sensitization characteristics of Eu-doped ZnSe and ZnSe/ZnS core/shell QD are studied in detail using photoluminescence (PL), PL excitation spectra (PLE) and time-resolved PL spectroscopy. The emission intensity of Eu ions is enhanced and that of ZnSe QDs is decreased, implying that energy was transferred from the excited ZnSe host materials (the donor) to the doped Eu ions (the acceptor). PLE reveals that the ZnSe QDs act as an antenna for the sensitization of Eu ions through an energy transfer process. The dynamics of ZnSe:Eu/ZnS core/shell quantum dots with different shell thicknesses and doping concentrations are studied via PL spectra and fluorescence lifetime spectra. The maximum phosphorescence efficiency is obtained when the doping concentration of Eu is approximately 6% and the sample showed strong white light under ultraviolet lamp illumination. By surface modification with ZnS shell layer, the intensity of Eu-related PL emission is increased approximately three times compared with that of pure ZnSe:Eu QDs. The emission intensity and wavelength of ZnSe:Eu/ZnS core/shell quantum dots can be modulated by different shell thickness and doping concentration. The results provide a valuable insight into the doping control for practical applications in laser, light-emitting diodes and in the field of biotechnology.

Liu N ，Xu L ，Wang H ，Xu J ，Su W ，Ma Z ，Chen K ... -  《-》

Deposition of CdS, CdS/ZnSe and CdS/ZnSe/ZnS shells around CdSeTe alloyed core quantum dots: effects on optical properties.

In this work, we synthesized water-soluble L-cysteine-capped alloyed CdSeTe core quantum dots (QDs) and investigated the structural and optical properties of deposition of each of CdS, CdS/ZnSe and CdS/ZnSe/ZnS shell layers. Photophysical results showed that the overcoating of a CdS shell around the alloyed CdSeTe core [quantum yield (QY) = 8.4%] resulted in effective confinement of the radiative exciton with an improved QY value of 93.5%. Subsequent deposition of a ZnSe shell around the CdSeTe/CdS surface decreased the QY value to 24.7%, but an increase in the QY value of up to 49.5% was observed when a ZnS shell was overcoated around the CdSeTe/CdS/ZnSe surface. QDs with shell layers showed improved stability relative to the core. Data obtained from time-resolved fluorescence measurements provided useful insight into variations in the photophysical properties of the QDs upon the formation of each shell layer. Our study suggests that the formation of CdSeTe/CdS core/shell QDs meets the requirements of quality QDs in terms of high photoluminescence QY and stability, hence further deposition of additional shells are not necessary in improving the optical properties of the core/shell QDs.

Adegoke O ，Nyokong T ，Forbes PB 《-》