A hierarchical self-assembly route to three-dimensional polymer-quantum dot photonic arrays

We demonstrate a new hierarchical self-assembly strategy for the formation of photonic arrays containing quantum dots (QDs), in which sequential self-assembly steps introduce organization on progressively longer length scales, ranging from the nanoscale to the microscale regimes. The first step in this approach is the self-assembly of diblock copolymers to form block ionomer reverse micelles (SA1); within each micelle core, a single CdS QD is synthesized to yield the hybrid building block BC-QD. Once SA1 is completed, the hydrophobic BD-QD building blocks are blended with amphiphilic block copolymer stabilizing chains in an organic solvent; water addition induces secondary self-assembly (SA2) to form quantum dot compound micelles (QDCMs). Finally, aqueous dispersions of QDCMs are slowly evaporated to induce the formation of three-dimensional (3D) close-packed arrays in a tertiary self-assembly step (SA3). The resulting hierarchical assemblies, consisting of a periodic array of hybrid spheres each containing multiple CdS QDs, exhibit the collective property of a photonic stop band, along with photoluminescence arising from the constituent QDs. A high degree of structural control is possible at each level of organization by judicious selection of experimental variables, allowing various parameters governing the collective optical properties, including QD size, nanoparticle spacing, and mesocale periodicity, to be independently tuned. The resulting control over optical properties via successive self-assembly steps should provide new opportunities for hierarchical materials for QD lasers and all-optical switching.     

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.     

Highly luminescent CdSe/Cd(x)Zn(1-x)S quantum dots coated with thickness-controlled SiO2 shell through silanization

A silanization technique of hydrophobic quantum dots (QDs) was applied to SiO(2)-coated CdSe/Cd(x)Zn(1-x)S QDs to precisely control the SiO(2) shell thickness and retain the original high photoluminescence (PL) properties of the QDs. Hydrophobic CdSe/Cd(x)Zn(1-x)S core-shell QDs with PL peak wavelengths of 600 and 652 nm were prepared by a facile organic route by using oleic acid (OA) as a capping agent. The QDs were silanized by using partially hydrolyzed tetraethyl orthosilicate by replacing surface OA. These silanized QDs were subsequently encapsulated in a SiO(2) shell by a reverse micelles synthesis. The silanization plays an important role for the QDs to be coated with a homogeneous SiO(2) shell and retain a high PL efficiency in water. Transmission electron microscopy observation shows that the shells are 1-9 nm with final particle sizes of 10-25 nm, depending on the initial QD size. In the case of short reaction time (6 h), the QDs were coated with a very thin SiO(2) layer because no visible SiO(2) shell was observed but transferred into the water phase. The silica coating does not change the PL peak wavelength of the QDs. The full width at half-maximum of PL was decreased 4 nm after coating for QDs emitting at both 600 and 652 nm. The PL efficiency of the SiO(2)-coated is up to 40%, mainly determined by the initial PL efficiency of the underlying CdSe/Cd(x)Zn(1-x)S QDs.     

Copolymer nanosphere encapsulated CdS quantum dots prepared by RAFT copolymerization: synthesis,characterization and mechanism of formation

Cadmium sulfide (CdS) quantum dots (QDs) encapsulated in block copolymer spheres were synthesized by an aqueous emulsion polymerization process. First, stable dispersions of CdS QDs in water were prepared using a polymer dispersant, either poly(acrylic acid) or a random copolymer having an average of ten acrylic acid and five butyl acrylate units. These polymer dispersants were prepared by reversible addition-fragmentation chain transfer polymerization. Then, the CdS QDs dispersed in water were encapsulated in a polystyrene shell using an emulsion polymerization process. Spectroscopic and microscopic techniques were used to characterize the resulting nanocomposites. Optical properties of QDs in polymer microspheres were investigated by UV-vis and fluorescence spectroscopic studies. Particle sizes of all CdS QD samples were calculated from absorption edges using Henglein's empirical curve. Transmission electron microscopy was used to determine the size and morphology of CdS QD samples. These observations were used to elucidate the mechanism of formation of the resulting well-defined polymer-encapsulated CdS nanoparticles.     

Facile synthesis of fluorescent quantum dot‐polymer nanocomposites via frontal polymerization

We report an available approach for quickly fabricating CdS QD‐polymer nanocomposites via frontal polymerization (FP). First, we synthesized (3‐mercaptopropyl)‐1‐trimethoxysilane (MPS)‐capped CdS quantum dots (QDs). With these MPS‐capped CdS QDs containing mercapto groups, MPS‐capped CdS QDs can be easily incorporated into a poly(N‐methylolacrylamide) (PNMA) matrix via FP. A variety of features for preparing QD‐polymer nanocomposites, such as initiator concentration and CdS concentration, were thoroughly investigated. The fluorescence properties of QD‐polymer nanocomposites prepared via FP are comparatively investigated on the basis of ultraviolet–visible (UV–vis) spectra and photoluminescence (PL) spectra. Results show that the PL intensity of QD‐polymer nanocomposites prepared via the FP method is superior to that obtained by the traditional batch polymerization (BP) method. In addition, by measuring the changes of PL intensity of the samples immersed in different concentrations of copper acetate solution, we found the QD‐polymer nanocomposites can be ultrasensitive to copper ions. This FP process can be exploited as a facile and rapid way for synthesis QD‐polymer nanocomposites on a large scale, avoiding the fluorescence quenching of nanocrystals during incorporation nanocrystals into polymer matrices. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2170–2177, 2010     

Triggered aggregation of PbS nanocrystal dispersions; towards directing the morphology of hybrid polymer films using a removable bilinker ligand

Hybrid polymer films consist of quantum dots (QDs) dispersed in a polymer matrix. A key fundamental challenge that is hindering their optimisation in optoelectronic devices such as hybrid solar cells is overcoming uncontrolled aggregation of the QDs. In an effort to direct aggregation, and trigger self-assembly, we added a bilinker ligand (1,2-ethanedithiol) to dispersed PbS QDs in polymer solutions prior to film deposition by spin casting. Turbidity studies of the PbS QD/1,2-ethanedithiol dispersions enabled a relationship to be established between the extent of 1,2-ethanedithiol-triggered QD aggregation and the nominal fractional coverage of the QDs by 1,2-ethanedithiol. The extent of aggregation (and self-assembly) increased with nominal fraction coverage. Above a value of about 1.0 QD aggregation increased substantially. TEM images showed that at low 1,2-ethanedithiol concentrations triggered assembly of network-like QD structures occurred. At high 1,2-ethanedithiol concentrations the QDs self-assembled into more-ordered micrometre-sized crystals. The results suggest that 1,2-ethanedithiol decreases the inter-QD separation in dispersion as a result of rapid ligand exchange and this process results in QD aggregation as well as self-assembly. The assembled QD structures were successfully trapped within polymer films by spin casting of PbS QD/1,2-ethanedithiol dispersions containing added polystyrene or polytriarylamine.     

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%.     

高性能量子点编码磁性微球的制备

基于改进的层层组装法,以氯仿/正丁醇混合溶液作为反应溶剂,将油溶性CdSSe/ZnS量子点装载到表面氨基修饰的磁性聚苯乙烯微球(MS)表面,通过调节量子点浓度,制备出高性能CdSSe/ZnS量子点编码磁性微球(CdSSe/ZnS-MBs).研究了氯仿和氯仿/正丁醇混合溶液对CdSSe/ZnS-MBs制备效果的影响.结果表明,氯仿/正丁醇混合溶液不仅能避免氯仿等量子点良溶剂对聚合物微球的形貌破坏,同时能促进CdSSe/ZnS量子点高效地装载到磁性微球表面.所制备的CdSSe/ZnS-MBs在水相具有较好的分散性,荧光强度变异系数(CV)小,形貌均一.该方法为简单、精确可控地制备高编码容量的量子点编码微球提供了新思路.     

Langmuir-Blodgett thin films of quantum dots: synthesis, surface modification, and fluorescence resonance energy transfer (FRET) studies

We describe herein studies on as-prepared hydrophobic ZnS-CdSe quantum dots (QDs) at the air-water interface. Surface pressure-area (pi-A) isotherms have been used to study the monolayer behavior. Uniform, lamellar multilayer thin films of QDs were deposited by the Langmuir-Blodgett (LB) technique. The role of two different surfactant systems commonly employed in the synthesis of these QDs (trioctylphosphine oxide-octadecylamine (TOPO-ODA) system and trioctylphosphine oxide-tetradecylphosphonic acid (TOPO-TDPA) system) on the monolayer behavior and the quality of thin films produced has been investigated. The thin films were characterized by quartz crystal microgravimetry (QCM), contact angle measurements, fluorescence spectroscopy, and transmission electron microscopy (TEM). These QD films were further modified by an amphiphilic polymer, poly(maleic anhydride-alt-1-tetradecene) (PMA). The hydrophobic interaction between the polymers and the surfactants attached to the QDs drove the self-assembly process. The carboxylic acid functional groups in the polymer were also used to immobilize avidin. We have demonstrated a proof of concept for the biosensing strategy wherein the avidin-coated QD films attracted biotinylated gold nanoparticles, resulting in fluorescence resonance energy transfer (FRET) quenching of the thin films.     

Exploring Feasibility for Application of Luminescent CdTe Quantum Dots Prepared in Aqueous Phase to Live Cell Imaging

Due to the quantum confinement, semiconductor quantum dots (QDs) show some unique and fascinating optical properties, such as, sharp and symmetrical emission spectra, high quantum yield (QY), good chemical and photo-stability. These excellent optical prop…     

Characterization of quantum dot bioconjugates by capillary electrophoresis with laser-induced fluorescent detection

In this paper, we present a universal, highly efficient and sensitive method for the characterization of quantum dot (QD) bioconjugates based on capillary electrophoresis with laser-induced fluorescent (LIF) detection. We first prepared CdTe QDs in aqueous phase by a chemical route with mercaptopropionic acid as a ligand, and then were coupled to certain proteins using bifunctional linkage reagent or electrostatic attraction. The QD bioconjugates were characterized by capillary electrophoresis with LIF detection. We found that QD bioconjugates were efficiently separated with free QDs by the optimization of buffer pH. Furthermore, we found that ultrafiltration was an effective and simple approach to purify QD conjugates with bovine serum albumin (BSA). Due to their broad absorption spectra and size dependent emission wavelength tunability, QDs can be excited to emit different colour fluorescence using a single wavelength laser source, and therefore, we believe that CE with LIF detection will become a universal and efficient tool for the characterization of QD bioconjugates.     

Self-selective recovery of photoluminescence in amphiphilic polymer encapsulated PbS quantum dots

Self-selected recovery of the photoluminescence (PL) of amphiphilic polymer encapsulated PbS quantum dots (QDs) was observed in water for the first time and possible mechanisms were proposed based on investigations by means of transmission electron microscopy, X-ray photoelectron spectroscopy (XPS), X-ray diffraction and fluorescence spectroscopy. Water-soluble PbS QDs were synthesized by transferring monodispersed QDs capped with hydrophobic ligands of oleylamine from an organic solvent into water via amphiphilic polymers poly(maleic anhydride-alt-1-octadecene-co-poly(ethylene glycol)). The water transfer process leads to a double size distribution (5.6 ± 0.9 nm and 2.7 ± 0.4 nm), attributed to ligand etching together with Ostwald ripening, as well as the fast decay of PL. The automatic recovery of the PL in PbS QDs stored in water in the dark for 3 months was only observed for the subset of smaller QDs and is largely due to the removal of surface defects with aging, as evidenced by the decreased percentage of unpassivated surface atoms from XPS studies. In contrast, the PL of the subset of larger QDs in the same sample does not self-recover in water and can only be slightly recovered by transferring them into environments with less external quenches. The results strongly suggest that it is the surface defect in the larger QDs themselves, introduced during Ostwald ripening, that is primarily responsible for their non-emitting status or rather low PL intensity under different conditions. The increase of unpassivated Pb atoms in larger PbS QDs after the 3 month aging has been confirmed by XPS, which explains their non-recovery behavior in water. The PL-recovered QD sample in water is very stable and shows comparable photostability to the initial QDs dispersed in an organic phase.     

CsPbBr3 QD/AlOx Inorganic Nanocomposites with Exceptional Stability in Water,Light, and Heat

Herein, the assembly of CsPbBr₃ QD/AlO_x inorganic nanocomposites, by using atomic layer deposition (ALD) for the growth of the amorphous alumina matrix (AlO_x ), is described as a novel protection scheme for such QDs. The nucleation and growth of AlO_x on the QD surface was thoroughly investigated by miscellaneous techniques, which highlighted the importance of the interaction between the ALD precursors and the QD surface to uniformly coat the QDs while preserving the optoelectronic properties. These nanocomposites show exceptional stability towards exposure to air (for at least 45 days), irradiation under simulated solar spectrum conditions (for at least 8 h), and heat (up to 200 °C in air), and finally upon immersion in water. This method was extended to the assembly of CsPbBr_x I_3−x QD/AlO_x and CsPbI₃ QD/AlO_x nanocomposites, which were more stable than the pristine QD films.     

Assembly kinetics of nanocrystals via peptide hybridization

The assembly kinetics of colloidal semiconductor quantum dots (QDs) on solid inorganic surfaces is of fundamental importance for implementation of their solid-state devices. Herein an inorganic binding peptide, silica binding QBP1, was utilized for the self-assembly of nanocrystal quantum dots on silica surface as a smart molecular linker. The QD binding kinetics was studied comparatively in three different cases: first, QD adsorption with no functionalization of substrate or QD surface; second, QD adsorption on QBP1-modified surface; and, finally, adsorption of QBP1-functionalized QD on silica surface. The surface modification of QDs with QBP1 enabled 79.3-fold enhancement in QD binding affinity, while modification of a silica surface with QBP1 led to only 3.3-fold enhancement. The fluorescence microscopy images also supported a coherent assembly with correspondingly increased binding affinity. Decoration of QDs with inorganic peptides was shown to increase the amount of surface-bound QDs dramatically compared to the conventional methods. These results offer new opportunities for the assembly of QDs on solid surfaces for future device applications.     

New insight in the role of modifying ligands in the sol-gel processing of metal alkoxide precursors: A possibility to approach new classes of materials

This paper summarizes recent literature data and presents new experimental data on the mechanisms of chemical modification, hydrolysis and polycondensation of the alkoxides and demonstrates possibilities to approach new classes of materials, exploiting these mechanisms. Low reactivity of silicon alkoxides is improved by either basic catalysis exploiting an S_N2 mechanism or acidic catalysis facilitating a proton-assisted S_N1 mechanism as well as by modification with chelating ligands. Metal alkoxides are much stronger Lewis bases compared to silicon alkoxides and the acidity of water is strong enough to achieve their rapid hydrolysis via proton-assisted S_N1 pathway even in the absence of additional catalysts. Introduction of the modifying chelating ligands is leading generally to increased charge distribution in the precursor molecules. Modifying chelating ligands are also appreciably smaller than the alkoxide ligands they replace. The modification with chelating ligands is thus facilitating the kinetics of hydrolysis and polycondensation. The size and shape of the primary particles formed in sol-gel treatment of metal alkoxides are defined not by kinetic factors in their hydrolysis and polycondensation but by the interactions on the phase boundary, which is in its turn directed by the ligand properties. The products of the fast hydrolysis and condensation sequence consist of micelles templated by self-assembly of ligands (mainly oxo-species). This concept provides explanations for commonly observed material properties and allows for the development of new strategies for the preparation of materials. We discuss the formation of inverted micelles, obtained by the appropriate choice of solvents, which allows for the formation of hollow spheres. The modifying β-diketonate ligands act as the surfactant and form an interface between the hollow sphere and the solvent. Retention of ligands inside the gel particles is possible only if ligands possessing both chelating and bridging properties are applied. Application of such ligands, for example, diethanolamine, permits to prepare new transition metal oxide based microporous membranes.     

CsPbBr3 QD/AlOx Inorganic Nanocomposites with Exceptional Stability in Water,Light, and Heat

Herein, the assembly of CsPbBr₃ QD/AlO_x inorganic nanocomposites, by using atomic layer deposition (ALD) for the growth of the amorphous alumina matrix (AlO_x ), is described as a novel protection scheme for such QDs. The nucleation and growth of AlO_x on the QD surface was thoroughly investigated by miscellaneous techniques, which highlighted the importance of the interaction between the ALD precursors and the QD surface to uniformly coat the QDs while preserving the optoelectronic properties. These nanocomposites show exceptional stability towards exposure to air (for at least 45 days), irradiation under simulated solar spectrum conditions (for at least 8 h), and heat (up to 200 °C in air), and finally upon immersion in water. This method was extended to the assembly of CsPbBr_x I_3−x QD/AlO_x and CsPbI₃ QD/AlO_x nanocomposites, which were more stable than the pristine QD films.     

Tuning Optical Properties of Si Quantum Dots by π‐Conjugated Capping Molecules

The absorption and photoluminescence (PL) properties of silicon quantum dots (QDs) are greatly influenced by their size and surface chemistry. Herein, we examined the optical properties of three Si QDs with increasing σ–π conjugation length: octyl‐, (trimethylsilyl)vinyl‐, and 2‐phenylvinyl‐capped Si QDs. The PL photon energy obtained from as‐prepared samples decreased by 0.1–0.3 eV, while the PL excitation (PLE) extended from 360 nm (octyl‐capped Si QDs) to 400 nm (2‐phenylvinyl‐capped Si QDs). A vibrational PL feature was observed in all samples with an energy separation of about 0.192±0.013 eV, which was explained based on electron–phonon coupling. After soft oxidization through drying, all samples showed blue PL with maxima at approximately 410 nm. A similar high‐energy peak was observed with the bare Si QD sample. The changes in the optical properties of Si QDs were mainly explained by the formation of additional states arising from the strong σ–π conjugation and QD oxidation.     

Enhancing the stability and biological functionalities of quantum dots via compact multifunctional ligands

We have designed and synthesized a series of modular ligands based on poly(ethylene glycol) (PEG) coupled with functional terminal groups to promote water-solubility and biocompatibility of quantum dots (QDs). Each ligand is comprised of three modules: a PEG single chain to promote hydrophilicity, a dihydrolipoic acid (DHLA) unit connected to one end of the PEG chain for strong anchoring onto the QD surface, and a potential biological functional group (biotin, carboxyl, and amine) at the other end of the PEG. Water-soluble QDs capped with these functional ligands were prepared via cap exchange with the native hydrophobic caps. Homogeneous QD solutions that are stable over extended periods of time and over a broad pH range were prepared. Surface binding assays and cellular internalization and imaging showed that QDs capped with DHLA-PEG-biotin strongly interacted with either NeutrAvidin immobilized on surfaces or streptavidin coupled to proteins which were subsequently taken up by live cells. EDC coupling in aqueous buffer solutions was also demonstrated using resonance energy transfer between DHLA-PEG-COOH-functionalized QDs and an amine-terminated dye. The new functional surface ligands described here provide not only stable and highly water-soluble QDs but also simple and easy access to various biological entities.     

Sol–gel processing at increased temperatures: the formation of polyester nanocomposites

Polyester nanocomposites were prepared using sol–gel precursors, prehydrolyzed sols, or nanoparticles in polyester formulations. The different inorganic components were introduced in the early stages of the esterification reaction and a typical polymerization temperature program was applied leading to temperatures up to 240 °C at low pressures. The structural and physical properties of the final materials depend on the applied method for the introduction of the sol–gel materials. Silicon atoms were incorporated into the polyester chain if silicon tetraalkoxide was used as precursor. The silicon atoms represent branching points in the polymer structure. Prehydrolyzed sols that were prepared under acidic conditions were another source of silicon and formed larger inorganic aggregates in the polymer matrix. Nanoparticles prepared via the Stöber process were the third inorganic species in polyester formation. All three processing pathways produced different kinds of materials depending on the type of silica incorporated in the polyester networks but also with regard to the nanoscale structure of the materials. Both, composition and structure have a major influence on the final polyester nanocomposite properties. Model reactions between silicon tetraalkoxides and diols or diacids using the temperature program for the polyester formation showed that exchange reactions of the alkoxides and the alcohols or acids can occur and the obtained products can carry out side reactions in the polyester formation. The final materials show a homogeneous distribution of the silicon containing moieties in the polyester matrix. The viscosities and the branching degrees of the polymers changed dramatically compared to the pristine polymers by incorporation of the sol–gel precursors.     

Size control of mesoscale aqueous assemblies of quantum dots and block copolymers

Dropwise addition of water to blend solutions of block copolymer-stabilized quantum dots (QDs) and amphiphilic block copolymer stabilizing chains PS(665)-b-PAA(68) (PS = polystyrene, PAA = poly(acrylic acid)) in DMF induces self-assembly to form photoluminescent mesoscale QD/block copolymer colloids in water termed QD compound micelles (QDCMs). Here we demonstrate reproducible kinetic control of QDCM particle size and chain stretching within the external PAA stabilizing layer via changes in the initial polymer concentration and rate of water addition. By increasing the initial polymer concentration or decreasing the rate of water addition for a constant blend composition, larger QDCM particles are obtained. From a combination of transmission electron microscopy and dynamic light scattering, the thickness of the external PAA layer is determined for various QDCM sizes, showing that PAA stretching in the external brush layer increases with increasing particle size, reaching the limit of fully extended chains for sufficiently large particles. The photoluminescence spectra from QDCMs in pure water indicate that photoluminescence properties of the block copolymer-stabilized QD building blocks are retained during self-assembly. The demonstrated control of mesoscale particle size and conformation of the stabilizing PAA layer, among other related structural parameters, via simple variation of experimental conditions is a promising step toward the application of QDCM assemblies in photonics and biolabeling.