Role of surface modification of colloidal CdSe quantum dots on the properties of hybrid organic–inorganic nanocomposites

In this work, tri-octyl phosphine/tri-octyl phosphine oxide (TOPO)-capped cadmium selenide (CdSe) quantum dots (QDs) of varied sizes (5–9 nm), prepared by varying the input Cd:Se precursor ratio using chemical route, were dispersed in conducting polymer matrices viz. poly[2-methoxy, 5-(2-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) and poly(3-hexylthiophene) (P3HT). By using a binary solvent mixture (pyridine–chloroform), homogeneous dispersion of CdSe nanocrystals in polymers (MEH-PPV, P3HT) could be realized. The properties of the resulting dispersions could be tailored by the composition and concentration of QDs in polymer. The emission and structural properties of polymer–CdSe nanocomposites are found to be dependent on the crystallite size and morphology of CdSe nanocrystallites. An effective quenching of photoluminescence emission in the polymer nanocomposite was observed for smaller CdSe quantum dots (size ∼6 nm) as compared to larger CdSe quantum dots (size ∼9 nm), thus ensuring efficient charge transfer process across the polymer–CdSe interface in the former case. The incomplete quenching, particularly for MEH-PPV:CdSe nanocomposites, could be as a result of insufficient coverage of polymers on the surface of CdSe nanocrystallites, mainly due to phase segregation for TOPO-stripped CdSe nanocrystallites. The superior morphology and optical properties of polymer nanocomposite (P3HT:CdSe QDs) could play a pivotal role for the realization of effective charge separation and transport in hybrid solar cells.     

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.     

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.     

Fortification of CdSe quantum dots with graphene oxide. Excited state interactions and light energy conversion

Graphene based 2-D carbon nanostructures provide new opportunities to fortify semiconductor based light harvesting assemblies. Electron and energy transfer rates from photoexcited CdSe colloidal quantum dots (QDs) to graphene oxide (GO) and reduced graphene oxide (RGO) were isolated by analysis of excited state deactivation lifetimes as a function of degree of oxidation and charging in (R)GO. Apparent rate constants for energy and electron transfer determined for CdSe-GO composites were 5.5 × 10(8) and 6.7 × 10(8) s(-1), respectively. Additionally, incorporation of GO in colloidal CdSe QD films deposited on conducting glass electrodes was found to enhance the charge separation and electron conduction through the QD film, thus allowing three-dimensional sensitization. Photoanodes assembled from CdSe-graphene composites in quantum dot sensitized solar cells display improved photocurrent response (~150%) over those prepared without GO.     

Interface effects and relaxation processes in nanocomposites based on CdSe/ZnS semiconductor quantum dots and porphyrin molecules

Controllable self-assembly and properties of nanocomposites based on CdSe/ZnS semiconductor quantum dots (QDs) and tetrapyridylporphyrin molecules (H₂P) as well as the dynamics of relaxation processes in these systems were studied for solutions and single nanoobjects in the temperature range of 77–295 K. It was proved that the formation of surface states of different nature is crucial to nonradiative relaxation of exciton excitation in QDs. The efficiency of QD→Н₂Р energy transfer was shown to be at most 10–15%. Regularities of photoluminescence (PL) quenching for QDs in nanocomposites in solutions of different polarity correlate with the dependences of PL blinking for single QDs. A scheme was proposed of excited states and main relaxation channels of exciton excitation energy in semiconductor QDs and QD–Н₂Р nanocomposites.     

Stamping transfer of a quantum dot interlayer for organic photovoltaic cells

An organophilic cadmium selenide (CdSe) quantum dot (QD) interlayer was prepared on the active layer in organic solar cells by a stamping transfer method. The mother substrate composed of a UV-cured film on a polycarbonate film with strong solvent resistance makes it possible to spin-coat QDs on it and dry transfer onto an active layer without damaging the active layer. The QD interlayers have been optimized by controlling the concentration of the QD solution. The coverage of QD particles on the active layer was verified by TEM analysis and fluorescence images. After insertion of the QD interlayer between the active layer and metal cathode, the photovoltaic performances of the organic solar cell were clearly enhanced. By ultraviolet photoelectron spectroscopy of CdSe QDs, it can be anticipated that the CdSe QD interlayer reduces charge recombination by blocking the holes moving to the cathode from the active layer and facilitating efficient collection of the electrons from the active layer to the cathode.     

Hot‐Hole Extraction from Quantum Dot to Molecular Adsorbate

Ultrafast thermalized and hot‐hole‐transfer processes have been investigated in CdSe quantum dot (QD)/catechol composite systems in which hole transfer from photoexcited QDs to the catechols is thermodynamically favorable. A series of catechol derivatives were selected with different electron‐donating and ‐withdrawing groups, and the effect of these groups on hole transfer and charge recombination (CR) dynamics has been investigated. The hole‐transfer time was determined using the fluorescence upconversion technique and found to be 2–10 ps depending on the molecular structure of the catechol derivatives. The hot‐hole‐transfer process was followed after monitoring 2S luminescence of CdSe QDs. Interestingly, hot‐hole extraction was observed only in the CdSe/3‐methoxycatechol (3‐OCH₃) composite system owing to the higher electron‐donating property of the 3‐methoxy group. To confirm the extraction of the hot hole and to monitor the CR reaction in CdSe QD/catechol composite systems, ultrafast transient absorption studies have been carried out. Ultrafast transient‐absorption studies show that the bleach recovery kinetics of CdSe QD at the 2S excitonic position is much faster in the presence of 3‐OCH₃. This faster bleach recovery at the 2S position in CdSe/3‐OCH₃ suggests hot‐hole transfer from CdSe QD to 3‐OCH₃. CR dynamics in CdSe QD/catechol composite systems was followed by monitoring the excitonic bleach at the 1S position and was found to decrease with free energy of the CR reaction.     

Controlled self-assembly of hydrophobic quantum dots through silanization

We demonstrate the formation of one-, two-, and three-dimensional nanocomposites through the self-assembly of silanized CdSe/ZnS quantum dots (QDs) by using a controlled sol-gel process. The self-assembly behavior of the QDs was created when partially hydrolyzed silicon alkoxide monomers replaced hydrophobic ligands on the QDs. We examined systematically self-assembly conditions such as solvent components and QD sizes in order to elucidate the formation mechanism of various QD nanocomposites. The QD nanocomposites were assembled in water phase or on the interface of water and oil phase in emulsions. The partially hydrolyzed silicon alkoxides act as intermolecules to assemble the QDs. The QD nanocomposites with well-defined solid or hollow spherical, fiber-like, sheet-like, and pearl-like morphologies were prepared by adjusting the experimental conditions. The high photoluminescence efficiency of the prepared QD nanocomposites suggests partially hydrolyzed silicon alkoxides reduced the surface deterioration of QDs during self-assembly. These techniques are applicable to other hydrophobic QDs for fabricating complex QD nanocomposites.     

High efficiency hybrid solar cells using post-deposition ligand exchange by monothiols

High-performance hybrid solar cells (HSCs) based on P3HT?:?CdSe QD blends are achieved through post-deposition ligand exchange by n-butanethiol (n-BT) with a high power conversion efficiency of 3.09%. The mechanism by which n-BT modifies the surface structures of CdSe QDs and thus improves the HSCs performance is investigated.     

Stepwise Self‐Assembly of P3HT/CdSe Hybrid Nanowires with Enhanced Photoconductivity

A facile approach to prepare poly(3‐hexylthiophene) (P3HT)/cadmium selenide quantum dot (CdSe QD) hybrid coaxial nanowires by a stepwise self‐assembly process is reported. P3HT nanowires of ≈20 nm diameter are first prepared by self‐assembly in a poor solvent such as cyclohexanone, and then as‐prepared CdSe QDs are deposited compactly onto the P3HT nanowires by non‐covalent interactions between P3HT and CdSe. When illuminated with white light, the hybrid nanowires show enhanced photoconductivity compared with the pristine P3HT nanowires and the blended nanocomposites.

     

Studies of optical and structural properties of CdSe/polymer nanocomposites: evidence of charge transfer and photostability

In this work, the role of conducting [poly (p-phenylinevinylene) (PPV)] and nonconducting (polystyrene) polymers on the properties of their respective composites with CdSe quantum dots of varied sizes has been investigated. The emission and structural properties of polymer–CdSe composites are found to be dependent on the crystallite size and morphology of CdSe nanocrystallites. Smaller CdSe quantum dots (size, ∼5 nm) ensures efficient charge transfer process across polymer–CdSe interface as evident by almost complete quenching of photoluminescence (PL) emission as compared to larger CdSe quantum dots (size, ∼7 nm). Presence of residual trioctylphosphine (TOP)/ tri-n-octylphosphine-oxide (TOPO) species and agglomeration of particles act as a hindrance for quenching of emission and hence charge transfer for larger CdSe nanocrystallites. Emission studies indicated an increased conjugation length for PPV polymers in different solvents (toluene, pyridine) and in solid state. Nonconducting polymer polystyrene shows charge transfer across polymer–CdSe interface as well. However, polystyrene polymer has a shorter chain length, which ensures maximum coverage on the surface of CdSe nanocrystallites and provides better photostability to CdSe QDs within the polymer matrix as compared to that for PPV–CdSe nanocomposites.     

Intermittent electron transfer activity from single CdSe/ZnS quantum dots

Electron transfer activity from excited single CdSe/ZnS core/shell quantum dots (QDs) to adsorbed Fluorescein 27 was studied by single QD fluorescence spectroscopy. In comparison with QDs, the QD-acceptor complexes showed a shorter average and broader distribution of QD emission lifetimes due to electron transfer to adsorbates. Large fluctuation of lifetimes in single QD/dye complexes was observed, indicating intermittent electron transfer activity from QDs.     

Effect of linker on the photosensitization of ZnO layers with CdSe quantum dots

In this work, zinc oxide (ZnO) nanoparticles (size <10 nm) were formed via precipitation in ethanolic solution. The zinc acetate and lithium hydroxide solutions in ethanol were mixed at 273 K temperatures under vigorous stirring. To study the effect of quantum dot (QD) coverage, we have prepared a colloidal suspension of capped CdSe QDs (size ~5 nm) by chemical route and anchored them to a nanoporous ZnO layer either by direct adsorption or through linker. Here a bifunctional molecule (mercaptopropionic acid, MPA, and thioglycolic acid, TGA) was previously adsorbed on the ZnO surface, which acted as a molecular cable. From TEM/SEM studies, it was observed that direct adsorption of CdSe QDs onto ZnO surface was not efficient. However, the bifunctional linker molecules particularly MPA facilitates binding of CdSe QDs to ZnO; and consequently, interparticle electron transfer is thus facilitated. The use of MPA linker despite of its long carbon chain also aids in the quenching of photoluminescence of CdSe on addition of ZnO in a more systematic manner indicating efficient charge transfer from CdSe into ZnO as compared with the without linker and with linker TGA case, respectively. Due to higher PL quenching and reduction in lifetime values, higher values of Stern–Volmer quenching constants were thus obtained for CdSe–ZnO composites with MPA as compared with TGA linker and without linker case, respectively. Nonlinear Stern–Volmer plots as observed for samples without linker case indicated heterogeneous quenching due to insufficient binding between CdSe QDs and ZnO. By means of spectroscopic (PL, UV–VIS, FTIR) and microscopic (TEM, SEM) techniques, we have demonstrated linker-dependent photosensitization mechanism of ZnO layers with CdSe QDs. Our data thus illustrate that interfacial-electron transfer kinetics in QD–linker–ZnO assemblies are almost independent of the length of alkyl-containing molecular linkers.     

Tuning of the charge and energy transfer in ternary CdSe/poly(3-methylthiophene)/poly(3-hexylthiophene) nanocomposite system

Composite CdSe:poly(3-methylthiophene) (P3MT) nanoparticles have been synthesized via polymerization of 3-methylthiophene (3MT) in the presence of CdSe particles of nanorod or dot-like morphology and dispersed in the poly(3-hexylthiophene) (P3HT) matrix. The effect of the P3MT layer to mediate charge and energy transfer between CdSe and P3HT in the ternary nanocomposite system has been studied using electronic absorption, photoluminescence spectroscopy, and current–voltage measurements. The energy level diagram of the composite system has been deduced based on optical and electrochemical data of the separate components of the system. The contribution of the low- and high-molecular fractions of P3MT to control the charge transfer in order to optimize the intermediary role of P3MT is analyzed. Particularly, it was shown that excitation of the low-molecular P3MT leads to energy transfer to both CdSe and P3HT components, and it also serves as a barrier against recombination of electrons and holes separated at CdSe and P3HT, respectively. Thus, the role of the P3MT interlayer in assisting the charge separation and increasing an open-circuit voltage in the photovoltaic cell based on the ternary system is demonstrated.     

Role of the Polymer Matrix on the Photoluminescence of Embedded CdSe Quantum Dots

The photoluminescence (PL) of CdSe quantum dots (QDs) that form stable nanocomposites with polymer liquid crystals (LCs) as smectic C hydrogen‐bonded homopolymers from a family of poly[4‐(n‐acryloyloxyalkyloxy)benzoic acids] is reported. The matrix that results from the combination of these units with methoxyphenyl benzoate and cholesterol‐containing units has a cholesteric structure. The exciton PL band of QDs in the smectic matrix is redshifted with respect to QDs in solution, whereas a blueshift is observed with the cholesteric matrix. The PL lifetimes and quantum yield in cholesteric nanocomposites are higher than those in smectic ones. This is interpreted in terms of a higher order of the smectic matrix in comparison to the cholesteric one. CdSe QDs in the ordered smectic matrix demonstrate a splitting of the exciton PL band and an enhancement of the photoinduced differential transmission. These results reveal the effects of the structure of polymer LC matrices on the optical properties of embedded QDs, which offer new possibilities for photonic applications of QD–LC polymer nanocomposites.     

Super Sensitization: Grand Charge (Hole/Electron) Separation in ATC Dye Sensitized CdSe,CdSe/ZnS Type‐I,and CdSe/CdTe Type‐II Core–Shell Quantum Dots

Ultrafast charge‐transfer dynamics has been demonstrated in CdSe quantum dots (QD), CdSe/ZnS type‐I core–shell, and CdSe/CdTe type‐II core–shell nanocrystals after sensitizing the QD materials by aurin tricarboxylic acid (ATC), in which CdSe QD and ATC form a charge‐transfer complex. Energy level diagrams suggest that the conduction and valence band of CdSe lies below the LUMO and the HOMO level of ATC, respectively, thus signifying that the photoexcited hole in CdSe can be transferred to ATC and that photoexcited ATC can inject electrons into CdSe QD, which has been confirmed by steady state and time‐resolved luminescence studies and also by femtosecond time‐resolved absorption measurements. The effect of shell materials (for both type‐I and type‐II) on charge‐transfer processes has been demonstrated. Electron injection in all the systems were measured to be <150 fs. However, the hole transfer time varied from 900 fs to 6 ps depending on the type of materials. The hole‐transfer process was found to be most efficient in CdSe QD. On the other hand, it has been found to be facilitated in CdSe/CdTe type‐II and retarded in CdSe/ZnS type‐I core–shell materials. Interestingly, electron injection from photoexcited ATC to both CdSe/CdTe type‐II and CdSe/ZnS type‐I core–shell has been found to be more efficient as compared to pure CdSe QD. Our observation suggests the potential of quantum dot core–shell super sensitizers for developing more efficient quantum dot solar cells.     

Impact of dendritic interface modifiers on phase behavior of polyvinylcarbazol-CdSe/ZnS nanocomposite films

The phase behavior of mixtures of poly(9-vinylcarbazol) (PVK) and CdSe/ZnS quantum dots (QDs) were studied depending on the nature of the surfactant used as QDs shell, namely, “native surfactant” (NS) originated from the QDs synthesis, and specially designed two-component interface modifiers comprising of dendritic phosphonic acids possessing alkyl- or cyano-terminal groups and hexyl phosphonic acid as a cosurfactant. It is shown, that the nature of interface modifier dramatically influence on distribution of QDs in the nanocomposite film. Thus, both the “native surfactant” and alkyl-containing dendritic interface modifiers favors to phase segregation of QDs in the resulting nanocomposites where two-dimensional aggregates are localized near-surface layer of the PVK film. In contrast, the cyano-containing dendritic interface modifier provides the homogeneous QDs distribution through the film thickness. We determined that the concentration quenching of QDs photoluminescence is observed for PVK/QD(NS) film. For PVK films containing QDs grafted with dendritic surfactants, the luminescent intensities increase vs QD concentration up to 80–85 wt%.     

Directed self-assembly in laponite/CdSe/polyaniline nanocomposites

Laponite films provide versatile inorganic scaffolds with materials architectures that direct the self-assembly of CdSe quantum dots (QDs or EviTags) and catalytic surfaces that promote the in situ polymerization of polyaniline (PANI) to yield novel nanocomposites for light emitting diodes (LEDs) and solar cell applications. Water-soluble CdSe EviTags with varying, overlapping emission wavelengths in the visible spectrum were incorporated using soft chemistry routes within Na-Laponite host film platforms to achieve broadband emission in the visible spectrum. QD concentrations, composition and synthesis approach were varied to optimize photophysical properties of the films and to mediate self-assembly, optical cascading and energy transfer. In addition, aniline tetramers coupled to CdSe (QD-AT) surfaces using a dithioate linker were embedded within Cu-Laponite nanoscaffolds and electronically coupled to PANI via vapor phase exposure. Nanotethering and specific host-guest and guest-guest interactions that mediate nanocomposite photophysical behavior were probed using electronic absorption and fluorescence spectroscopies, optical microscopy, AFM, SEM, powder XRD, NMR and ATR-FTIR. Morphology studies indicated that Lap/QD-AT films synthesized using mixed solvent, layer by layer (LbL) methods exhibited anisotropic supramolecular structures with unique mesoscopic ordering that affords bifunctional networks to optimize charge transport.     

Dynamic light-scattering analysis of the electrostatic interaction of hexahistidine-tagged cytochrome P450 enzyme with semiconductor quantum dots.

Currently, there is great interest in the development of methods suitable for determining the stoichiometry of biomolecules attached to nanoparticles. We describe the use of the dynamic light-scattering technique (DLS) to determine the stoichiometry of the protein cytochrome P450(BSbeta) attached to CdS and CdSe quantum dots (QDs). The enzyme-conjugated QDs have different diffusion characteristics compared to the QD and enzyme precursors, expressed in their size, scattering intensity as well as zeta-potential values. The significant enhancement of the scattering intensity of QDs observed upon conjugation with the P450(BSbeta) due to the refractive-index increment and the systematic variation in zeta potential resulting from charge neutralization of the anionic QDs by the cationic histidine-tagged P450(BSbeta) have been used for stoichiometry determination.     

CdSe Quantum Dots and N719‐Dye Decorated Hierarchical TiO2 Nanorods for the Construction of Efficient Co‐Sensitized Solar Cells

Three‐dimensional hierarchical TiO₂ nanorods (HTNs) decorated with the N719 dye and 3‐mercaptopropionic or oleic acid capped CdSe quantum dots (QDs) in photoanodes for the construction of TiO₂ nanorod‐based efficient co‐sensitized solar cells are reported. These HTN co‐sensitized solar cells showed a maximum power‐conversion efficiency of 3.93 %, and a higher open‐circuit voltage and fill factor for the photoanode with 3‐mercaptopropionic acid capped CdSe QDs due to the strong electronic interactions between CdSe QDs, N719 dye and HTNs, and the superior light‐harvesting features of the HTNs. An electrochemical impedance analysis indicated that the superior charge‐collection efficiency and electron diffusion length of the CdSe QD‐coated HTNs improved the photovoltaic performance of these HTN co‐sensitized solar cells.