Role of Core-Shell Formation in Exciton Confinement Relaxation in Dithiocarbamate-Capped CdSe QDs.

The possibility of exciton delocalization in alkyldithiocarbamate (ATC)-capped CdSe has been investigated for several alkyl groups and compared with phenyldithiocarbamates (PTCs). We find a bathochromic shift for ATC similar to the one obtained for PTC. Our computational studies show reduction in HOMO-LUMO gaps in both PTC and ATC, albeit with a lower shift. However, TDDFT studies revealed that ATC-capped CdSe is more of a localized HOMO state as compared with partly delocalized HOMO in PTC-capped CdSe, hinting at a difference in electronic interaction between the two binding groups. We hypothesized the formation of sulfide layer over the CdSe QDs as the possible reason for the observed bathochromic shift, as verified by absorption spectra of S2- ligand exchange samples. The formation of CdS shell leads to substantial electron delocalization because CdSe CB is in close resonance with CdS, which is exactly the opposite of what was previously concluded in the literature.

Density functional investigation and some optical experiments on dye-sensitized quantum dots.

Dye-sensitized quantum dots (QDs) are promising candidates for dye-sensitized solar cells (DSSCs). Here, we report steady state (absorption and photoluminescence) optical measurements on several sizes of CdS QDs ligated with Coumarin 343 dye (C-343) and two different solvents, viz., chloroform and toluene. We further report detailed first principles density functional theory and time-dependent density functional theory studies of the geometric, electronic and optical (absorption and emission) properties of three different sized capped QDs, ligated with C-343 dye. The absorption spectrum shows a QD-size-independent peak, and another peak which shifts to blue with decrease in QD size. The first peak is found to arise from the dye molecule and the second one from the QD. Charge transfer using natural transition orbitals (NTOs) is found to occur from dye-to-QDs and is solvent-dependent. In the emission spectra, the luminescence intensity of the dye is quenched by the addition of the QD indicating a strong interaction between the QD and the dye.

Synthesis, steady-state, and femtosecond transient absorption studies of resorcinol bound ruthenium(II)- and osmium(II)-polypyridyl complexes on nano-TiO2 surface in water.

The synthesis of two new ruthenium(II)- and osmium(II)-polypyridyl complexes 3 and 4, respectively, with resorcinol as the enediol anchoring moiety, is described. Steady-state photochemical and electrochemical studies of the two sensitizer dyes confirm strong binding of the dyes to TiO2 in water. Femtosecond transient absorption studies have been carried out on the dye-TiO2 systems in water to reveal <120 fs and 1.5 ps electron injection times along with 30% slower back electron transfer time for the ruthenium complex 3. However, the corresponding osmium complex 4 shows strikingly different behavior for which only a <120 fs ultrafast injection is observed. Most remarkably, the back electron transfer is faster as compared to the corresponding catechol analogue of the dye. The origin and the consequences of such profound effects on the ultrafast interfacial dynamics are discussed. This Article on the electron transfer dynamics of the aforesaid systems reinforces the possibility of resorcinol being explored and developed as an extremely efficient binding moiety for use in dye-sensitized solar cells.

Surface-state-mediated charge-transfer dynamics in CdTe/CdSe core-shell quantum dots.

Herein, we report the synthesis of aqueous CdTe/CdSe type-II core-shell quantum dots (QDs) in which 3-mercaptopropionic acid is used as the capping agent. The CdTe QDs and CdTe/CdSe core-shell QDs are characterized by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HR-TEM), steady-state absorption, and emission spectroscopy. A red shift in the steady-state absorption and emission bands is observed with increasing CdSe shell thickness over CdTe QDs. The XRD pattern indicates that the peaks are shifted to higher angles after growth of the CdSe shell on the CdTe QDs. HR-TEM images of both CdTe and CdTe/CdSe QDs indicate that the particles are spherical, with a good shape homogeneity, and that the particle size increases by about 2 nm after shell formation. In the time-resolved emission studies, we observe that the average emission lifetime (τ(av)) increases to 23.5 ns for CdTe/CdSe (for the thickest shell) as compared to CdTe QDs (τ(av) =12 ns). The twofold increment in the average emission lifetime indicates an efficient charge separation in type-II CdTe/CdSe core-shell QDs. Transient absorption studies suggest that both the carrier cooling and the charge-transfer dynamics are affected by the presence of traps in the CdTe QDs and CdTe/CdSe core-shell QDs. Carrier quenching experiments indicate that hole traps strongly affect the carrier cooling dynamics in CdTe/CdSe core-shell QDs.

Charge carrier dynamics in thiol capped CdTe quantum dots.

We report the ultrafast charge carrier relaxation dynamics of mercaptopropionic acid capped CdTe quantum dot (QD) using femtosecond transient absorption spectroscopy by exciting the particles with 400 nm laser light and monitoring the transients in the visible to near IR region. Cooling dynamics and population dynamics in different quantized states of the charge carriers were monitored by following the growth kinetics of the bleach at different excitonic positions. The cooling time second and first excitonic states were found to be 150 fs and 500 fs, respectively, which increases non-linearly with its size. Defect states of QD surface play an important role in the cooling dynamics of the charge carriers. Quenching studies have been carried out to find out cooling and trapping dynamics of the individual charge carriers. Electron and hole cooling time were measured to be 700 fs and 150 fs for the first excitonic state using quenchers. Trapping dynamics of electron and hole have been determined by monitoring transient signal at 1000 nm and by using hole and electron quencher, respectively. Electron and hole trapping times have been found to be 700 fs and 1 ps, respectively, in CdTe QD.

Interfacial electron transfer dynamics in quinizarin sensitized ZnS nanoparticles: monitoring charge transfer emission.

Water soluble cubic ZnS nanoparticles (NPs) have been synthesized at room temperature by using 3-mercaptopropionic acid (MPA) as a modifier molecule and characterized by X-ray diffraction (XRD), steady-state absorption, and emission spectroscopy. Electron transfer (ET) dynamics have been carried out in ZnS semiconductor nanoparticles and quinizarin (Qz) molecules as studied by picosecond time-resolved fluorescence spectroscopy. We have proposed that electron injection takes place from photoexcited Qz molecules into the surface states of wide band gap ZnS NPs. We have revealed that the formation of a charge transfer complex between the Qz molecule and ZnS nanoparticles facilitates electron injection into the surface states of nanoparticles. In the present investigation, we have detected charge transfer (CT) emission in the Qz-ZnS system as the injected electrons from surface states return back to the parent Qz cation radical. We have determined back ET rates by monitoring the CT emission.