Bound-Ion Pair X-Type Ligation of Cadmium and Zinc Dithiocarbamates on Cadmium Selenide Quantum Belts.

Wurtzite CdSe quantum belts with L-type n-octylamine, L-type ammonia, or Z-type Cd(oleate)2 ligands are exchanged for several metal-dithiocarbamate ligands [M(S2CNR1R2)2]: Cd(S2CNPhMe)2, Cd(S2CNEt2)2, Zn(S2CNPhMe)2, and Zn(S2CNEt2)2. Successful ligand exchange with all M(S2CNR1R2)2 compounds occurs from {CdSe[Cd(oleate)2]0.19} quantum belts (QBs), which induce similar spectral shifts in the absorption spectra of the ligand-exchanged QBs. Spectroscopic data, experimentally determined lattice strains, and ligand exchanges with [Na][Et2NCS2] and [NH4][MePhNCS2] establish that the [M(S2CNR1R2)2] ligands bind as bound-ion-paired X-type ligands with (S2CNR1R2)- groups ligated directly to the QB surfaces and [M(S2CNR1R2)]+ groups serving as the charge-balancing ion-paired countercations. The X-type dithiocarbamate ligands do not impart any special electronic effects to the CdSe QBs.

Excitation Energy Dependence of Photoluminescence Quantum Yields in Semiconductor Nanomaterials with Varying Dimensionalities.

The excitation energy dependence (EED) of the photoluminescence quantum yield (ΦPL) of semiconductor nanoparticles with varying dimensionalities is reported. Specifically, the EEDs of CdSe quantum dots, CdSe quantum platelets, CdSe quantum belts, and CdTe quantum wires were determined via measurements of individual ΦPL values and photoluminescence efficiency (PLEff(E)) spectra. There is a general trend of overall decreasing efficiency for radiative recombination with increasing excitation energy. In addition, there are often local minima in the PLEff(E) spectra that are most often at energies between quantum-confinement transitions. The average PL lifetimes of the samples do not depend on the excitation energy, suggesting that the EED of ΦPL arises from charge carrier trapping that competes efficiently with intraband carrier relaxation to the band edge. The local minima in the PLEff(E) spectra are attributed to excitation into optically coupled states that results in the loss of carriers in the semiconductor. The EED data suggest that the PLEff(E) spectra depend on the sample synthesis, preparation, surface passivation, and environment.

Cadmium Bis(phenyldithiocarbamate) as a Nanocrystal Shell-Growth Precursor.

Cadmium bis(phenyldithiocarbamate) [Cd(PTC)2] is prepared and structurally characterized. The compound crystallizes in the monoclinic space group P21/n. A one-dimensional polymeric structure is adopted in the solid state, having bridging PTC ligands and 6-coordinate pseudo-octahedral Cd atoms. The compound is soluble in DMSO, THF, and DMF and insoluble in EtOH, MeOH, CHCl3, CH2Cl2, and toluene. {CdSe[n-octylamine]0.53} quantum belts and Cd(PTC)2 react to deposit epitaxial CdS shells on the nanocrystals. With an excess of Cd(PTC)2, the resulting thick shells contain spiny CdS nodules grown in the Stranski-Krastanov mode. Stoichiometric control affords smooth, monolayer CdS shells. A base-catalyzed reaction pathway is elucidated for the conversion of Cd(PTC)2 to CdS, which includes phenylisothiocyanate and aniline as intermediates, and 1,3-diphenylthiourea as a final product.