In-Situ Template Synthesis of a Polymer/Semiconductor Nanohybrid Using Amphiphilic Conducting Block Copolymers

In this study, we synthesized organic/inorganic hybrid materials containing cadmium sulfide (CdS) nanoparticles using a novel amphiphilic conducting block copolymer as a synergistic structure-directing template and an efficient exciton quencher of the hybrid. The amphiphilic rod−coil block copolymer of polyphenylene-b-poly(2-vinyl pyridine) (PPH-PVP) was first prepared from its coil−coil precursor block copolymer of poly(1,3-cyclohexadiene)-b-poly(2-vinyl pyridine) (PCHD-PVP) by using sequential anionic polymerization followed by the aromatization reaction of converting the PCHD block to form conducting PPH. The synthesized PCHD-PVP block copolymers self-assembled into different bulk nanostructures of lamellae, cylinders, and spheres at a volume fraction similar to that of many coil−coil block copolymer systems. However, an enhanced chain-stiffness-induced morphological transformation was observed after the aromatization reaction. This is evidenced by the TEM observation in which both spherical and cylindrical structured PCHD-PVPs transform into lamellar structured PPH-PVPs after aromatization. In addition to the bulk-phase transformation, the rigid-rod characteristic of the conducting PPH block also affects the self-assembling property of the block copolymers in their solution state. CdS nanoparticles were synthesized in situ in a selective solvent of THF using PCHD-PVP and PPH-PVP micelles as nanoreactors. The PPH-PVP/Cd ion in THF exhibits a new ringlike structure of uniform size (∼50 nm) with PPH in the inner rim and complexed PVP/Cd ions in the outer rim as a result of the effects of strong intermolecular forces between PPH segments and the solvophobic interaction. CdS nanoclusters were subsequently synthesized in situ from the PPH-PVP/Cd2+ ring structure, forming a nanohybrid with intimate contact between the PPH domain and CdS nanoparticles. In particular, we found that there is an efficient energy/electron transfer between the conducting PPH domain and CdS nanoparticles in the hybrid, resulting in an enhanced PL quenching effect. The novel nanohybrid shows the potential to be used for optoelectronic applications

Facile Synthesis of Well-Defined Block Copolymers Containing Regioregular Poly(3-hexyl thiophene) via Anionic Macroinitiation Method and Their Self-Assembly Behavior

P3HT-P2VP block copolymers were synthesized using anionic macroinitiation of a vinyl end-functionalized P3HT. With different block ratio of P2VP to P3HT, the block copolymers exhibit sphere, cylinder, lamellae, and nanofiber nanostructures

Synthesis and Self-Assembly of Poly(diethylhexyloxy-<i>p</i>-phenylenevinylene)-<i>b</i>-poly(methyl methacrylate) Rod−Coil Block Copolymers

A series of poly(diethylhexyloxy-p-phenylenevinylene-b-methyl methacrylate) (DEH-PPV-b-PMMA) polymers with narrow polydispersity (PDI 1H nuclear magnetic resonance (1H NMR) and gel permeation chromatography (GPC). Transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) studies reveal the details of copolymer morphology. The DEH-PPV-b-PMMA system presented here has higher block segregation strength than many previously studied rod−coil block copolymers yet still shows experimentally accessible phase transitions with respect to temperature. As a result, this molecule offers new insight into the competition between rod−rod and rod−coil interactions that occurs in the system. The DEH-PPV rods are organized as a monolayer that is inclined with the lamellar normal (smectic C) for the copolymers containing low volume fraction of PMMA coil (<54%). However, as the coil fraction increases, the strips containing DEH-PPV pack into hexagonal lattice. In contrast to previous work which demonstrated similar morphologies, the sequence of reversible liquid crystalline and microphase phase transitions is altered as a result of the increased block segregation. Upon heating, the low coil fraction copolymers exhibit a series of clear transitions of smectic−lamellar to amorphous−lamellar to disordered structures. In high coil fraction copolymers, the transitions between smectic−hexagonal to amorphous−hexagonal and smectic−hexagonal to disorder structures could not be clearly differentiated. The order-to-disorder temperature (ODT) decreases slowly with increasing coil fraction while the smectic-to-isotropic transition (SI) temperature stays relatively unchanged. The steady SI temperature suggests that the strong rod−rod interaction keeps the liquid crystalline rod in the nanodomain structure regardless of the amount of coil segment in the copolymers

Effect of TiO₂ Nanoparticles on Self-Assembly Behaviors and Optical and Photovoltaic Properties of the P3HT-<i>b</i>-P2VP Block Copolymer

An ordered nanostructure can be created from the hybrid materials of self-assembly poly(3-hexyl thiophene-b-2-vinyl pyridine) and nicotinic acid-modified titanium dioxide nanoparticles (P3HT-b-P2VP/TiO2). TEM and XRD analyses reveal that the TiO2 nanoparticles (NPs) are preferentially confined in the P2VP domain of P3HT-b-P2VP whereas TiO2 NPs interact with either pure P3HT or a blend of P3HT and P2VP to produce microsized phase segregation. The morphologies of lamellar and cylindrical structures are disturbed when the loading of TiO2 NPs is 40 wt % or higher. Cylindrical P3HT-b-P2VP/TiO2 exhibits a small blue shift in absorption and photoluminescence spectra with increasing TiO2 loading as compared to P3HT/TiO2. The NPs cause a slightly misaligned P3HT domain in the copolymer. Furthermore, the PL quenching of P3HT-b-P2VP/TiO2 becomes very large as a result of efficient charge separation in the ordered nanodomain at 16 nm. Solar cells fabricated from self-assembly P3HT-b-P2VP/TiO2 hybrid materials exhibit a >30 fold improvement in power conversion efficiency as compared to the corresponding 0.3P3HT-0.7P2VP/TiO2 polymer blend hybrid. This study paves the way for the further development of high-efficiency polymer−inorganic nanoparticle hybrid solar cells using a self-assembled block copolymer

In Situ Fabrication of Poly(3-hexylthiophene)/ZnO Hybrid Nanowires with D/A Parallel-Lane Structure and Their Application in Photovoltaic Devices

In this study, we demonstrate a facile in situ synthetic strategy to fabricate self-assembled organic/inorganic hybrid nanowires, wherein a “pre-crystallization” approach was first utilized to co-organize P3HT molecules and zinc precursors into highly elongated nanowires, followed by a thermal oxidation treatment to directly grow ZnO nanocrystals on the existing nanofibrillar template. By further thermal annealing the ZnO embossed hybrid nanowires, a unique superhighway-like architecture which composed of alternating parallel channels of P3HT nanofibrils and ZnO nanocrystals could be further obtained. This donor/acceptor (D/A) parallel-channel structure gave access to the improvements in the exciton dissociation and charge transport, thereby enhancing photoluminescence quenching, charge transport, and device performance. The photovoltaic devices with the D/A parallel-lane structure gave a high PCE of 0.61% as compared to only 0.07% from a conventional P3HT/ZnO bulk heterojuction solar cell. Our approach offers a versatile route to coassemble inorganic nanocrystals with π-conjugated polymer hosts, forming uniform one-dimensional hybrid nanochannels potentially useful in optoelectronic applications

Reaching Nearly 100% Quantum Efficiencies in Thin Solid Films of Semiconducting Polymers via Molecular Confinements under Large Segmental Stresses

Quantum efficiencies remain a critical issue for general applications of semiconducting polymers in optoelectronics and others. In this work, we demonstrate that nearly 100% quantum efficiencies (η’s) in thin solid films can be reached when the polymer molecules are mechanically stretched into molecular confinement. We selected three conjugated polymers of varied backbone stiffness and interchain coupling, prepared in both diluted and pristine states. All of the polymers when highly diluted (c = 0.1 wt %) exhibited massive η increases after stretching to very large strains (∼300–500%) via micronecking, with the rigid polyfluorene (PFO) and semirigid MEH-PPV both manifesting η ≈ 90%, while the most flexible yet regioregular polythiophene (P3HT-rr) exhibited a 10-fold increase to ∼21%. In the pristine state, molecular aggregation and interchain coupling curtail development of the molecular confinement, but the large-strain deformation still enhances η’s significantly, to ∼90% (PFO) and ∼55% (MEH-PPV) despite no increases for the crystalline P3HT-rr. Moreover, upon substitution by a bulkier side-group to reduce interchain coupling, the pristine films of polythiophene (P3EHT) exhibited a ∼3-fold increase of η after the stretching. The nearly 100% of η’s in fully stretched molecules indicates that the in situ self-trapping occurring via sub-picosecond backbone interactions can be mostly responsible for energy dissipations and quite suppressible by segmental stress control. The mechanical confinement effects also indicate the fundamental role of molecular mechanics during stabilization and migration of photoexcited charges

A Facile Synthetic Route to Ether Diols Derived from 1,1-Cyclopentylenylbisphenol for Robust Cardo-Type Polyurethanes

An efficient scheme for the synthesis of 1,1-cyclopentylenyl­bisphenol (bisphenol CP) has been developed starting from dicyclopentadiene, a C5 byproduct from the petroleum cracking process. The synthetic steps leading to bisphenol CP consist of mostly isomerization and addition reactions, which are higher in their atom-economy efficiencies than those based upon condensation reactions. In addition, alkoxylation by cyclic carbonates converted bisphenol CP into ethoxylated and propoxylated ether diols. The transformation of hydroxyl functional groups from bisphenols to alkoxylated alcohols increased the reactivity of their hydroxyl groups toward isocyanates, as evidenced by achieving >3 times higher molecular weights of the segmented polyurethanes (PUs) in GPC analysis using alkoxylated diols as chain extenders instead of bisphenols. In addition, the incorporation of five-membered cardo-type groups onto the PU side chains through alkoxyl diols of bisphenol CP also significantly enhances the phase mixing of the resulting hard and soft segments, leading to a series of robust PUs

Self-Assembled All-Conjugated Block Copolymer as an Effective Hole Conductor for Solid-State Dye-Sensitized Solar Cells

An all-conjugated diblock copolymer, poly(2,5-dihexyloxy-p-phenylene)-b-poly(3-hexylthiophene) (PPP-b-P3HT), was synthesized and applied as a hole transport material (HTM) for the fabrication of solid-state dye-sensitized solar cells (ss-DSCs). This copolymer is characterized by an enhanced crystallinity, enabling its P3HT component to self-organize into interpenetrated and long-range-ordered crystalline fibrils upon spin-drying and ultimately endowing itself to have a faster hole mobility than that of the parent P3HT homopolymer. Transient photovoltage measurements indicate that the photovoltaic cell based on PPP-b-P3HT as the HTM has a longer electron lifetime than that of the reference device based on P3HT homopolymer. Moreover, comparing the two ss-DSCs in terms of the electrochemical impedance spectra reveals that the electron density in the TiO2 conduction band is substantially higher in the PPP-b-P3HT device than in the P3HT cell. Above observations suggest that the PPP block facilitates an intimate contact between the copolymer and dye molecules absorbed on the nanoporous TiO2 layer, which significantly enhances the performance of the resulting device. Consequently, the PPP-b-P3HT ss-DSC exhibits a promising power conversion efficiency of 4.65%. This study demonstrates that conjugated block copolymers can function as superior HTMs of highly efficient ss-DSCs

Detection of K⁺ Efflux from Stimulated Cortical Neurons by an Aptamer-Modified Silicon Nanowire Field-Effect Transistor

The concentration gradient of K⁺ across the cell membrane of a neuron determines its resting potential and cell excitability. During neurotransmission, the efflux of K⁺ from the cell via various channels will not only decrease the intracellular K⁺ content but also elevate the extracellular K⁺ concentration. However, it is not clear to what extent this change could be. In this study, we developed a multiple-parallel-connected silicon nanowire field-effect transistor (SiNW-FET) modified with K⁺-specific DNA-aptamers (aptamer/SiNW-FET) for the real-time detection of the K⁺ efflux from cultured cortical neurons. The aptamer/SiNW-FET showed an association constant of (2.18 ± 0.44) × 10⁶ M^–1 against K⁺ and an either less or negligible response to other alkali metal ions. The α-amino-3-hydroxy-5-methyl-4-isoxazolepropionic acid (AMPA) stimulation induced an outward current and hyperpolarized the membrane potential in a whole-cell patched neuron under a Na⁺/K⁺-free buffer. When neurons were placed atop the aptamer/SiNW-FET in a Na⁺/K⁺-free buffer, AMPA (13 μM) stimulation elevated the extracellular K⁺ concentration to ∼800 nM, which is greatly reduced by 6,7-dinitroquinoxaline-2,3-dione, an AMPA receptor antagonist. The EC₅₀ of AMPA in elevating the extracellular K⁺ concentration was 10.3 μM. By stimulating the neurons with AMPA under a normal physiological buffer, the K⁺ concentration in the isolated cytosolic fraction was decreased by 75%. These experiments demonstrate that the aptamer/SiNW-FET is sensitive for detecting cations and the K⁺ concentrations inside and outside the neurons could be greatly changed to modulate the neuron excitability