Assemblies of conjugated polymers: Intermolecular and intramolecular effects on the photophysical properties of conjugated polymers

Conjugated polymers are emerging materials for electronic applications due to the tunability of their properties through variation of their chemical structure. Their applications, which currently include light-emitting diodes (LEDs), field effect transistors (FETs), plastic lasers, batteries, and sensors, are expanding to many new areas. The two critical parameters that determine the function of conjugated polymer-based devices are chemical structure and nanostructure of a conjugated polymer in the solid state. While the physical properties of isolated polymers are primarily controlled by their chemical structure, these properties are drastically altered in the solid state due to electronic coupling between polymer chains as determined by their interpolymer packing and conformation. However, the development of effective and precise methods for controlling the nanostructure of polymers in the solid state has been limited because polymers often fail to assemble into organized structures due to their amorphous character and large molecular weight. In this review, recent developments of organizing methods of conjugated polymers and the conformation and interpolymer interaction effects on the photophysical properties of conjugated polymers are summarized

Directed self-assembly of nanogold using a chemically modified nanopatterned surface

Electron-beam lithography (EBL) was used to define an aminosilane nanopatterned surface in order to electrostatically self-assemble gold nanoparticles (Au NPs). The chemically modified nanopatterned surfaces were immersed into a Au NP solution to allow the Au NPs to self-assemble. Equilibrium self-assembly was achieved in only 20 min. The number of Au NPs that self-assembled on an aminosilane dot was controlled by manipulating the diameters of both the Au NPs and the dots. Adding salt to the Au NP solution enabled the Au NPs to self-assemble in greater numbers on the same sized dot. However, the preparation of the Au NP solution containing salt was sensitive to spikes in the salt concentration. These spikes led to aggregation of the Au NPs and non-specific deposition of Au NPs on the substrate. The Au NP patterned surfaces were immersed in a sodium hydroxide solution in order to lift-off the patterned Au NPs, but no lift-off was observed without adequate physical agitation. The van der Waals forces are too strong to allow for lift-off despite the absence of electrostatic forces.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/98607/1/0957-4484_23_4_045602.pd

Assemblies of conjugated polymers: Intermolecular and intramolecular effects on the photophysical properties of conjugated polymers

Conjugated polymers are emerging materials for electronic applications due to the tunability of their properties through variation of their chemical structure. Their applications, which currently include light-emitting diodes (LEDs), field effect transistors (FETs), plastic lasers, batteries, and sensors, are expanding to many new areas. The two critical parameters that determine the function of conjugated polymer-based devices are chemical structure and nanostructure of a conjugated polymer in the solid state. While the physical properties of isolated polymers are primarily controlled by their chemical structure, these properties are drastically altered in the solid state due to electronic coupling between polymer chains as determined by their interpolymer packing and conformation. However, the development of effective and precise methods for controlling the nanostructure of polymers in the solid state has been limited because polymers often fail to assemble into organized structures due to their amorphous character and large molecular weight. In this review, recent developments of organizing methods of conjugated polymers and the conformation and interpolymer interaction effects on the photophysical properties of conjugated polymers are summarized

Supramolecular assemblies of conjugated sensory polymers and the optimization of transport properties

Thesis (Ph.D.)--Massachusetts Institute of Technology, Dept. of Materials Science and Engineering, 2001.Includes bibliographical references.(cont.) The vectorial energy transfer design of sensory films to harvest and direct energy to the surface detection layer toward ultimate signal amplification has been discussed. Third, the role of chemical structure of a sensory polymer in the selectivity of a conjugated polymer-based fluorescent sensor has been examined. In two different sensory systems for the detection of potassium ions and a nitroaromatic explosive TNT, respectively, key chemical design parameters governing their selectivity have been rationalized. Finally, the combination of the conclusions of this thesis provided an idealized structure of a fluorescent conjugated polymer-based sensory film with optimized sensitivity and selectivity.A sensor is one of the many important applications of conjugated polymers. Poly(p-phenylene ethynylene)s (PPEs) have been studied for fluorescence-based sensor applications. The chemical structure and nano-structure of a polymer in the solid-state are two critical parameters that determine sensitivity and selectivity of a conjugated polymer-based sensor. In this thesis, both parameters have been systematically investigated. First, the Langmuir-Blodgett method was used to control the nano-structure of PPEs in the solid-state. Rational design of surfactant PPEs made it possible to control the conformation of a single polymer strand and interpolymer spatial arrangement at the air-water interface. In situ UV-Vis and fluorescence spectroscopy on the Langmuir film in controlled nano-structures revealed the effects of conformation and spatial arrangement of conjugated polymers on their intrinsic optical properties. Since the controlled structure of a monolayer at the air-water interface can be transferred to a solid substrate, structurally well-defined multilayer LB films of PPEs with confined optical properties were fabricated. This made it possible to study the role of interpolymer aggregation in the photophysical properties of conjugated polymer films. The results provided a general design principle to make a highly emissive conjugated polymer film. Second, an ideal thickness of a sensory film for optimizing sensitivity was determined by experimental and theoretical analysis of energy transport phenomena in multilayer PPE films.y Jinsang Kim.Ph.D

Highly Emissive Self-assembled Organic Nanoparticles having Dual Color Capacity for Targeted Immunofluorescence Labeling

No Abstract.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/58079/1/1117_ftp.pd

Conjugated Polymers Combined with a Molecular Beacon for Label-Free and Self-Signal-Amplifying DNA Microarrays

A conjugated polymer (CP) and molecular-beacon-based solid-state DNA sensing system is developed to achieve sensitive, label-free detection. A novel conjugated poly(oxadiazole) derivative exhibiting amine and thiol functional groups ( POX-SH ) is developed for unique chemical and photochemical stability and convenient solid-state on-chip DNA synthesis. POX-SH is soluble in most nonpolar organic solvents and exhibits intense blue fluorescence. POX-SH is covalently immobilized onto a maleimido-functionalized glass slide by means of its thiol group. Molecular beacons having a fluorescent dye or quencher molecule as the fluorescence resonance energy transfer (FRET) acceptor are synthesized on the immobilized POX-SH layer through direct on-chip oligonucleotide synthesis using the amine side chain of POX-SH . Selective hybridization of the molecular beacon probes with the target DNA sequence opens up the molecular beacon probes and affects the FRET between POX-SH and the dye or quencher, producing a sensitive and label-free fluorescence sensory signal. Various molecular design parameters, such as the size of the stem and loop of the molecular beacon, the choice of dye, and the number of quencher molecules are systematically controlled, and their effects on the sensitivity and selectivity are investigated.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/64307/1/3317_ftp.pd

Random Copolymers Outperform Gradient and Block Copolymers in Stabilizing Organic Photovoltaics

Recent advances have led to conjugated polymer‐based photovoltaic devices with efficiencies rivaling amorphous silicon. Nevertheless, these devices become less efficient over time due to changes in active layer morphology, thereby hindering their commercialization. Copolymer additives are a promising approach toward stabilizing blend morphologies; however, little is known about the impact of copolymer sequence, composition, and concentration. Herein, the impact of these parameters is determined by synthesizing random, block, and gradient copolymers with a poly(3‐hexylthiophene) (P3HT) backbone and side‐chain fullerenes (phenyl‐C61‐butyric acid methyl ester (PC61BM)). These copolymers are evaluated as compatibilizers in photovoltaic devices with P3HT:PC61BM as the active layer. The random copolymer with 20 mol% fullerene side chains and at 8 wt% concentration in the blend gives the most stable morphologies. Devices containing the random copolymer also exhibit higher and more stable power conversion efficiencies than the control device. Combined, these studies point to the random copolymer as a promising new scaffold for stabilizing bulk heterojunction photovoltaics.Photovoltaic devices made from conjugated polymers now exhibit efficiencies rivaling amorphous silicon; however, the poor longevity of these devices continues to stymie their commercial impact. Copolymer additives represent a promising solution, yet little is known about how the copolymer sequence, composition, and concentration influence their compatibilizing abilities. Herein, random copolymer additives lead to higher efficiency and longer‐lasting photovoltaic devices.Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/150505/1/adfm201900467.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/150505/2/adfm201900467_am.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/150505/3/adfm201900467-sup-0001-S1.pd

Molecular Design Approach Managing Molecular Orbital Superposition for High Efficiency without Color Shift in Thermally Activated Delayed Fluorescent Organic Lightâ Emitting Diodes

Molecular design principles of thermally activated delayed fluorescent (TADF) emitters having a high quantum efficiency and a color tuning capability was investigated by synthesizing three TADF emitters with donors at different positions of a benzonitrile acceptor. The position rendering a large overlap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) enhances the quantum efficiency of the TADF emitter. Regarding the orbital overlap, donor attachments at 2â and 6â positions of the benzonitrile were more beneficial than 3â and 5â substitutions. Moreover, an additional attachment of a weak donor at the 4â position further increased the quantum efficiency without decreasing the emission energy. Therefore, the molecular design strategy of substituting strong donors at the positions allowing a large molecular orbital overlap and an extra weak donor is a good approach to achieve both high quantum efficiency and a slightly increased emission energy.Overlap to emit: The substitution of strong donors at the positions rendering a large HOMOâ LUMO overlap and the addition of a weak donor constitute an effective design approach to realize TADF emitters having high efficiency.Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/147817/1/chem201805616-sup-0001-misc_information.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/147817/2/chem201805616.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/147817/3/chem201805616_am.pd