Shailesh N. Sharma

Effect of surface passivating ligand on structural and optoelectronic properties of polymer : CdSe quantum dot composites

We demonstrate the effect of surface passivation of cadmium selenide quantum dots (CdSe QDs) (~5–7 nm) by tri-n-octylphosphene-oxide (TOPO) and oleic acid (OA) on the structural and optoelectronic properties of their respective polymer : CdSe composites by dispersing them in poly(2-methoxy-5(2-ethylhexyloxy)-1,4-phenylinevinylene) and poly(3-hexylthiophene) polymers. It has been found that OA passivated-QDs (~7 nm), as compared with TOPO passivated CdSe QDs (~5 nm), are of (i) high quality that provide better steric stability against coagulation, homogeneity and photostability to their respective polymer : CdSe composites, (ii) show low value of Stern–Volmer quenching constant (KSV) calculated from photoluminescence quenching measurements. These effects have been attributed to (i) CdSe(OA) (~7 nm) particles having relatively smaller surface energies compared with CdSe(TOPO) (~5 nm) particles thus showing lesser quenching capabilities (ii) dominance of respective processes of photoinduced Forster energy transfer between host polymer (donors) and guest CdSe nanocrystals (acceptors) in polymer : CdSe(OA) composites and charge transfer in polymer : CdSe(TOPO) composites.

Effect of CdSe quantum dots on hole transport in poly(3-hexylthiophene) thin films

This letter demonstrates the effect of cadmium selenide (CdSe) quantum dots on hole transport in poly(3-hexylthiophene) (P3HT) thin films. Current-voltage characteristics of P3HT and P3HT:CdSe thin films have been studied in the temperature range of 288–85K, in hole only device configurations, i.e., indium tin oxide (ITO)/poly(ethylene-dioxthiophene):polystyrenesulphonate (PEDOT:PSS)/P3HT/Au and ITO/PEDOT:PSS/P3HT:CdSe∕Au. The incorporation of CdSe quantum dots in P3HT results in the enhancement in hole current and switches the transport from dual conduction mechanism, viz., trap and mobility models to only trap model. This is attributed to the reduction in characteristic trap energy from 60to32meV and trap density from 2.5×1018to1.7×1018cm−3.

Formation of water-soluble and biocompatible TOPO-capped CdSe quantum dots with efficient photoluminescence

In this work, polysorbate surfactants with same functional groups but with varying molecular masses (Tween-80, Tween-40 and Tween-20) in different concentrations (0.1% to 20% w/w) were used to study the effect of the length of the surfactant chain on the luminescence of the entrapped TOPO-capped CdSe nanocrystals. Various phospholipids with different functional headgroups such as ethylene glycol (-PEG) and amine (-NH2) were used to improve biocompatibility and provide sites for bioconjugation respectively. It is understood that that the hydrophobic ends of the surfactant binds with the water repelling groups of the cap layer, thus modifying the CdSe cap layer and making it soluble in aqueous media. It was observed that the PL emission intensity of CdSe increases with increase in concentration of Tween-series surfactant unlike in the case of thiol-coated CdSe nanoparticles. However, higher PL intensity was obtained in the case of stoichiometric CdSe with Tween-40 corresponding to 20% w/w. The efficient PL sustainability of water-soluble CdSe QD’s can be attributed to the simpler chain structure of Tween-40 surfactant resulting in better passivation of the micelle.

Nanostructured porous silicon as functionalized material for biosensor application

In this work by means of PL, FTIR and XPS techniques, state-of-the-art porous silicon (PS) films with good mechanical and optical properties have been effectively utilized for the biofunctionalization purpose for its possible application in immunosensors. The functionalization of the PS surface has been achieved by silanization process using aminopropyltriethoxysilane (APTS) as a precursor. The presence of reactive amino groups on the PS surface along with glutaraldehyde as a linker aids in the covalent binding of the antibody (Human IgG) onto the PS surface. Different antigen concentrations can be detected with a good reproducibility with this technique which opens a huge possibility of using this biofunctionalized material for future biosensors.

Luminescence properties of the solvothermally synthesized blue light emitting Mn doped Cu2O nanoparticles

The Cu2O nanoparticles having average crystallite diameters ∼8–16 nm were synthesized by a simple solvothermal method. The Mn was doped in the Cu2O sample of crystallite size ∼8 nm. The effects of the size and doping concentration on the crystal structures of the nanoparticles were investigated. The x-ray photoelectron spectroscopy studies clearly showed that the Mn was incorporated into the Cu2O lattice as Mn2+ due to the substitution of the Cu+ ions by Mn2+ ions. The quantum confinement effects were observed in the nanoparticles. The multiple emissions from the Cu2O were quenched in the Mn doped nanoparticles and only blue light emitting Cu2O nanoparticles were obtained due to the transition T42→A61 of Mn. The effects of the doping concentration and the particle size on the relaxations dynamics of the Cu2O nanoparticles were mainly investigated using photoluminescence decay.

An insight into the mechanism of charge-transfer of hybrid polymer:ternary/quaternary chalcopyrite colloidal nanocrystals.

Summary In this work, we have demonstrated the structural and optoelectronic properties of the surface of ternary/quaternary (CISe/CIGSe/CZTSe) chalcopyrite nanocrystallites passivated by tri-n-octylphosphine-oxide (TOPO) and tri-n-octylphosphine (TOP) and compared their charge transfer characteristics in the respective polymer: chalcopyrite nanocomposites by dispersing them in poly(3-hexylthiophene) polymer. It has been found that CZTSe nanocrystallites due to their high crystallinity and well-ordered 3-dimensional network in its pristine form exhibit a higher steric- and photo-stability, resistance against coagulation and homogeneity compared to the CISe and CIGSe counterparts. Moreover, CZTSe nanocrystallites display efficient photoluminescence quenching as evident from the high value of the Stern–Volmer quenching constant (K SV) and eventually higher charge transfer efficiency in their respective polymer P3HT:CZTSe composites. We modelled the dependency of the charge transfer from the donor and the charge separation mechanism across the donor–acceptor interface from the extent of crystallinity of the chalcopyrite semiconductors (CISe/CIGSe/CZTSe). Quaternary CZTSe chalcopyrites with their high crystallinity and controlled morphology in conjunction with regioregular P3HT polymer is an attractive candidate for hybrid solar cells applications.

Constraints in post-synthesis ligand exchange for hybrid organic (MEH-PPV)–inorganic (CdSe) nanocomposites

For an optimum charge/energy transfer performance of hybrid organic–inorganic colloidal nanocrystals for applications such as photonic devices and solar cells, the determining factors are the distance between the nanocrystal and polymer which greatly depends upon nanocrystal size/nanocrystal ligands. Short chain ligands are preferred to ensure a close contact between the donor and acceptor as a result of the tunnelling probability of the charges and the insulating nature of long alkyl chain molecules. Short distances increase the probability for tunnelling to occur as compared to long distances induced by long alkyl chains of bulky ligands which inhibit tunnelling altogether. The ligands on the as-synthesized nanocrystals can be exchanged for various other ligands to achieve desirable charge/energy transfer properties depending on the bond strength of the ligand on the nanocrystal compared to the replacement ligand. In this work, the constraints involved in post-synthesis ligand exchange process have been evaluated, and these factors have been tuned via wet chemistry to tailor the hybrid material properties via appropriate selection of the nanocrystal capping ligands. It has been found that both oleic acid and oleylamine (OLA)-capped cadmium selenide (CdSe) quantum dots (QDs) as compared with trioctylphosphine oxide (TOPO)-passivated CdSe QDs are of high quality, and they provide better steric stability against coagulation, homogeneity, and photostability to their respective polymer:CdSe nanocomposites. CdSe QDs particularly with OLA capping have relatively smaller surface energies, and thus, lesser quenching capabilities show dominance of photoinduced Forster energy transfer between donors (polymer) and acceptors (CdSe nanocrystals) as compared to charge transfer mechanism as observed in polymer:CdSe (TOPO) composites. It is conjectured that size quantization effects, stereochemical compatibility of ligands (TOPO, oleic acid, and oleyl amine), and polymer MEH-PPV stability greatly influence the photophysics and photochemistry of hybrid polymer–semiconductor nanocomposites.

Ligand-exchange dependent properties of hybrid nanocomposites based on luminescent colloidal CdSe nanocrystals in P3HT matrix

In this work, a suitable ligand-exchange process has been proposed which elucidates the possibility to modulate charge/energy transfer rate between polymer and semiconductor quantum dots. The photoluminescence studies of CdSe emission as well as transient absorption measurements confirm mainly electron transfer for P3HT:CdSe (TOPO) and electron/energy transfer for P3HT:CdSe (OA) nanocomposites, respectively. The dominance of charge transfer for P3HT:CdSe (TOPO) as compared to P3HT:CdSe (OA) nanocomposites can be attributed to complete and partial removal of the surface ligands (TOPO, OA) upon ligand exchange with pyridine as elucidated from FTIR results. The various characterization techniques viz. Fourier transform infrared (FTIR), Raman, photoluminescence (PL), optical and transient absorption (UV-Vis and TA) spectroscopies used in this work provide an insight into the charge separation, charge accumulation and/or trapping of charge carriers for the better understanding of hybrid organic-inorganic photovoltaics. Composites of CdSe (OA) quantum dots in particular with P3HT polymer owing to its higher crystallinity and ordered morphology provide a new and promising direction toward developing effective light energy harvesting strategies in organic photovoltaics.

Single-Pot Rapid Synthesis of Colloidal Core/Core-Shell Quantum Dots: A Novel Polymer-Nanocrystal Hybrid Material

Colloidal core and core shell Quantum Dots (QD’s) are unique and important optoelectronic materials because properties of these QD’s can be tailored by configuring core and optimizing shell thickness. In this research work, lead selenide (PbSe) core and PbSe-CdSe (Core-shell) QD’s are synthesized using oleic acid as a capping ligand by colloidal route. This simpler, cost-effective and rapid single pot synthesis route for colloidal core-shell quantum dots unlike conventional double-pot approach like cation-exchange and SILAR process has been reported for the very first time. Phase formation of prepared quantum dots is confirmed by XRD analysis, capping ligand presence by IR spectroscopy and morphological information by Scanning electron microscopy respectively. These synthesized inorganic quantum dots are dispersed in Poly (3-hexyl thiophene) polymer for formation of their respective nanocomposites. From PL quenching studies, it was inferred that PbSe-CdSe core-shell quantum dots showed enhanced rate of PL quenching and hence higher value of Stern-Volmer constant (KSV) than PbSe Core QD’s. This confirms that CdSe shell formation on PbSe core significantly passivates the core-surface, increases the stability and enhances the charge transfer mechanism for its potential application in Hybrid Solar cells.

Demonstration of the Formation of Porous Silicon Films with Superior Properties Formed on Polished (100) Si with Screen-Printed Back Contacts

Porous silicon (PS) layers were formed by anodization on polished substrates of (1 0 0) Si at different current densities for a fixed anodization time of 30 mins. using different screenprinted/ evaporated back contacts (Ag, Al) respectively. The PS films has been characterized by high resolution X-ray diffraction (HRXRD), photoluminescence (PL), Scanning Electron Microscopy (SEM) and Fourier Transform Infrared (FTIR) techniques respectively. Porosity and thickness of PS layers were estimated by gravimetric analysis. The properties of PS formed using screen-printed Ag & Al as the back contacts (SP-(Ag/Al)) was found to be superior as compared to the corresponding films with evaporated back contacts (EV-(Ag/Al)). The PS formed with screenprinted Ag & Al-back contacts shows better crystalline perfection, higher stability, higher PL efficiency and negligible PL decay compared to that formed with evaporated Ag & Al- as the back contact for the same current density and time of anodization.