Matti Knaapila

Methods for Controlling Structure and Photophysical Properties in Polyfluorene Solutions and Gels

Knowledge of the phase behavior of polyfluorene solutions and gels has expanded tremendously in recent years. The relationship between the structure formation and photophysics is known at the quantitative level. The factors which we understand control these relationships include virtually all important materials parameters such as solvent quality, side chain branching, side chain length, molecular weight, thermal history and myriad functionalizations. This review describes advances in controlling structure and photophysical properties in polyfluorene solutions and gels. It discusses the demarcation lines between solutions, gels, and macrophase separation in conjugated polymers and reviews essential solid state properties needed for understanding of solutions. It gives an insight into polyfluorene and polyfluorene beta phase in solutions and gels and describes all the structural levels in solvent matrices, ranging from intramolecular structures to the diverse aggregate classes and network structures and agglomerates of these units. It goes on to describe the kinetics and thermodynamics of these structures. It details the manifold molecular parameters used in their control and continues with the molecular confinement and touches on permanently cross-linked networks. Particular focus is placed on the experimental results of archetypical polyfluorenes and solvent matrices and connection between structure and photonics. A connection is also made to the mean field type theories of hairy-rod like polymers. This altogether allows generalizations and provides a guideline for materials scientists, synthetic chemists and device engineers as well, for this important class of semiconductor, luminescent polymers.

A new small-angle X-ray scattering set-up on the crystallography beamline I711 at MAX-lab.

A small-angle X-ray scattering (SAXS) set-up has recently been developed at beamline I711 at the MAX II storage ring in Lund (Sweden). An overview of the required modifications is presented here together with a number of application examples. The accessible q range in a SAXS experiment is 0.009-0.3 A(-1) for the standard set-up but depends on the sample-to-detector distance, detector offset, beamstop size and wavelength. The SAXS camera has been designed to have a low background and has three collinear slit sets for collimating the incident beam. The standard beam size is about 0.37 mm x 0.37 mm (full width at half-maximum) at the sample position, with a flux of 4 x 10(10) photons s(-1) and lambda = 1.1 A. The vacuum is of the order of 0.05 mbar in the unbroken beam path from the first slits until the exit window in front of the detector. A large sample chamber with a number of lead-throughs allows different sample environments to be mounted. This station is used for measurements on weakly scattering proteins in solutions and also for colloids, polymers and other nanoscale structures. A special application supported by the beamline is the effort to establish a micro-fluidic sample environment for structural analysis of samples that are only available in limited quantities. Overall, this work demonstrates how a cost-effective SAXS station can be constructed on a multipurpose beamline.

All-conjugated polyelectrolyte block copolymers

Novel, all-conjugated polyelectrolyte block copolymers of the rod-rod type can be generated in a “grafting from” scheme and exhibit a preferred tendency to self-assemble into layered aggregates both in solution and the solid state. Here, the rigid-rod structure of the individual, complex macromolecules favours the formation of low-curvature vesicular and lamellar aggregates. Our poly(9,9-dialkylfluorene)-b-poly[3-(6-ammoniumhexyl)thiophene] (PF2/6-b-P3TMAHT and PFO-b-P3TMAHT, where PF2/6 and PFO denote 2-(ethyl)hexyl and linear octyl alkyl pendant groups, respectively), and poly(9,9-dialkylfluorene)-b-poly[3-(6-pyridylhexyl)thiophene] (PF2/6-b-P3PyHT and PFO-b-P3PyHT) polyelectrolyte diblock copolymers allow for simple and reliable control of the occurring self-organisation process and the resulting nano-scaled architectures. They are, therefore, promising candidates for application as the active layer in electronic devices or as functional membranes (e.g. for sensor applications). Moreover, the electronic properties of the materials (especially the excitation energy transfer between both blocks) strongly depend on the aggregation state present. Aggregation can be further controlled via addition of oppositely charged surfactants resulting in the formation of ordered polyelectrolyte/surfactant complexes.

Cationic polythiophene-surfactant self-assembly complexes: phase transitions, optical response, and sensing.

The absorption and photoluminescence spectra of the cationic conjugated polyelectrolyte poly[3-(6-trimethylammoniumhexyl)thiophene] (P3TMAHT) were observed to be dramatically altered in the presence of anionic surfactants due to self-assembly through ionic complex formation. Small-angle neutron scattering (SANS), UV/vis, and photoluminescence spectroscopy were used to probe the relationship between the supramolecular complex organization and the photophysical response of P3TMAHT in the presence of industrially important anionic surfactants. Subtle differences in the surfactant mole fraction and chemical structure (e.g., chain length, headgroup charge density, perfluorination) result in marked variations in the range and type of complexes formed, which can be directly correlated to a unique colorimetric and fluorimetric fingerprint. Our results show that P3TMAHT has potential as an optical sensor for anionic surfactants capable of selectively identifying distinct structural subgroups through dual mode detection.

Structure and "surfactochromic" properties of conjugated polyelectrolyte (CPE): Surfactant complexes between a cationic polythiophene and SDS in water

We report on the phase transitions, solution structure, and consequent effect on the photophysical properties of poly[3-(6-trimethylammoniumhexyl)thiophene] bromide (P3TMAHT) in aqueous sodium dodecylsulfate (SDS). Polythiophene was mixed with SDS or deuterated SDS to form P3TMAHT(SDS)(x) complex (x = the molar ratio of surfactant over monomer units) in D(2)O and studied by small-angle neutron and X-ray scattering (SANS/SAXS) and optical spectroscopy. At room temperature, P3TMAHT forms charged aggregates with interparticle order. The addition of SDS eliminates the interparticle order and leads to rod-like (x = 1/5) or sheet-like polymer-SDS aggregates (x = 1/2 to 1) containing rod-like (x = 1/5 to 1/2) or sheet-like (x = 1/2 to 1) polymer associations. Partial precipitation occurs at the charge compensation point (x = 1). Ellipsoidal particles without interparticle order, reminiscent of SDS micelles modified by separated polymer chains, occur for x = 2 to 5. Free SDS micelles dominate for x = 20. Structural transitions lead to a concomitant variation in the solution color from red (P3TMAHT) to violet (x = 1/5 to 1) to yellow (x > 2). The photoluminescence fingerprint changes progressively from a broad featureless band (x = 0) through the band narrowing and appearance of vibronic structure (x = 1/5 to 1) to the return to a blue-shifted broad emission band (x = 5). The polymer stiffness reaches a maximum for x = 1, which leads to minimization of the Stokes shift (0.08 eV). This work gives fundamental information upon how surfactant complexation can influence both the solution structure and photophysical properties of a water-soluble polythiophene.

Structure and Morphology of Polyfluorenes in Solutions and the Solid State

This account provides a state of the art overview of polyfluorene structure and phase behaviour in solutions and the solid state. This review covers key aspects of the hierarchical intra- and intermolecular self-assembly starting at the molecular level and extentding up to larger length scale structures. This includes crystallization, alignment on surfaces and texture. Many Central ideas are highlighted via structural archetypes. Recent theoretical treatments for understanding these structural properties are discussed and the implications for opto-electronics and photophysics are described.

Polarized luminescence from self-assembled, aligned, and cleaved supramolecules of highly ordered rodlike polymers

A hierarchical self-assembly in comb-shaped supramolecules of conjugated rodlike polymers is reported. The supramolecules consist of poly(2,5-pyridinediyl), acid dopants, and hydrogen bonded alkyl side chains. A thermotropic smectic state with an exceptionally large coherence length is formed without additional solvent. This allows facile overall alignment resulting in high dichroism and polarized photoluminescence. Solid films are formed by cleaving side groups from the supramolecules which retain the optical anisotropy together with the high photoluminescence quantum yield of pristine polymer.

Conductivity Enhancement in Carbon Nanocone Adhesive by Electric Field Induced Formation of Aligned Assemblies

We show how an alternating electric field can be used to assemble carbon nanocones (CNCs) and align these assemblies into microscopic wires in a commercial two-component adhesive. The wires form continuous pathways that may electrically connect the alignment electrodes, which leads to directional conductivity (∼10(-3) S/m) on a macroscopic scale. This procedure leads to conductivity enhancement of at least 2-3 orders of magnitude in the case where the CNC fraction (∼0.2 vol %) is 1 order of magnitude below the percolation threshold (∼2 vol %). The alignment and conductivity are maintained on curing that joins the alignment electrodes permanently together. If the aligned CNC wires are damaged before curing, they can be realigned by an extended alignment period. This concept has implications in areas such as electronic packaging technology.

Solvent Dependent Assembly of a Polyfluorene−Polythiophene “Rod−Rod” Block Copolyelectrolyte: Influence on Photophysical Properties

We report the solvent-driven assembly of a polyelectrolytic polyfluorene-polythiophene diblock copolymer-poly[9,9-bis(2-ethylhexyl)fluorene]-b-poly[3-(6-trimethylammoniumhexyl)thiophene] (PF2/6-b-P3TMAHT)-in tetrahydrofuran (THF), water, their 1:1 mixture and in subsequently prepared thin films, as investigated using a combination of scattering, microscopic and photoluminescence techniques. In solution PF2/6-b-P3TMAHT forms large (>100 nm) aggregates which undergo a transition from objects with surface fractal interface (THF) to ones with a significant planar component due to the presence of the 2-dimensionally merged ribbon-like aggregates or fused walls of the observed vesicular aggregates [THF-water (1:1)]. In THF-water and water the blocks are loosely segregated into P3TMAHT and PF2/6 rich domains, with PF2/6 dominating the aggregate interior. Depending on solvent, the spun films contain either aggregates with a crystalline interior (THF) or large 200 nm-2 microm vesicular aggregates embedded in a featureless matrix (THF-water and water). Structural variations are concomitant with distinctive solvatochromic changes in the photophysical properties including a color change from deep red (THF) to pale orange (THF-water and water) in solution, a decrease in fluorescence quantum yield with increasing water content, and a shift from photoluminescence of individual PF2/6 blocks (THF) to efficient PF2/6 --> P3TMAHT energy transfer (THF-water and water).

Conjugated polyelectrolyte (CPE) poly[3-[6-(N-methylimidazolium)hexyl]-2,5-thiophene] complexed with aqueous sodium dodecylsulfate amphiphile: synthesis, solution structure and “surfactochromic” properties

We report on the synthesis, solution structure and photophysical properties of poly[3-[6-(N-methylimidazolium)hexyl]-2,5-thiophene] bromide (P3ImiHT) when complexed with sodium dodecylsulfate (SDS). Synthesis of P3ImiHT used a Grignard metathesis (GRIM)-type route developed by McCullough, followed by quaternisation of the bromohexyl side groups of poly[3-(6-bromohexyl)thiophene] with N-methylimidazole. P3ImiHT was mixed with either SDS or deuterated SDS to form the P3ImiHT(SDS)x complex, where x is the molar ratio of surfactant to polyelectrolyte repeat unit, in D2O and studied using small-angle neutron scattering (SANS) and optical spectroscopy. Marked differences in behaviour are observed upon interaction of P3ImiHT with SDS compared with the related poly[3-(6-trimethylammoniumhexyl)thiophene] bromide (P3TMAHT). At room temperature, P3ImiHT forms charged aggregates with electrostatic repulsion which are eliminated by the SDS addition. For x ≤ 1 P3ImiHT and SDS are molecularly mixed and form ellipsoidal (x = 1/5) or sheet-like (x = 1/2–1) P3ImiHT(SDS)x aggregates. No visible precipitation is observed around the nominal charge compensation point (x = 1). For x > 1, P3ImiHT(SDS)x aggregates coexist with SDS rich micelles which turn from thick rod-like (x = 3/2) to non-charged (x = 2) and charged ellipsoidal micelles (x = 5). This transition is driven by decreasing free ion fraction. For x = 5, P3ImiHT(SDS)x forms a lamellar phase with a periodicity of ∼270 A. The structural transitions are accompanied by an initial red-shift from 422 nm (x = 0) to 459 nm (x = 1), followed by a reverse blue-shift to 400 nm (x = 5) of the UV/vis absorption maxima. The photoexcitation spectra follow this trend but are ∼50 nm red-shifted, thus indicating energy transfer within the density of states after photoexcitation. The photoluminescence maximum is gradually blue-shifted from 643 nm to 597 nm on increasing x from 0 to 5, indicating a decrease in polymer–polymer interactions.