Single molecule spectroscopy of conjugated polymer chains in an electric field-aligned liquid crystal

Using single molecule polarization spectroscopy, we investigated the alignment of a polymer solute with respect to the liquid crystal (LC) director in an LC device while applying an external electric field. The polymer solute is poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] (or MEH-PPV), and the LC solvent is 5CB. The electric field induces a change in the LC director orientation from a planar alignment (no electric field) to a perpendicular (homeotropic) alignment with an applied field of 5.5 x 103 V/cm. We find that the polymer chains align with the LC director in both planar and homeotropic alignment when measured in the bulk of the LC solution away from the device interface. Single molecule polarization distributions measured as a function of distance from the LC device interface reveal a continuous change of the MEH-PPV alignment from planar to homeotropic. The observed polarization distributions are modeled using a conventional elastic model that predicts the depth profile of the LC director orientation for the applied electric field. The excellent agreement between experiment and simulations shows that the alignment of MEH-PPV follows the LC director throughout the LC sample. Furthermore, our results suggest that conjugated polymers such as MEH-PPV can be used as sensitive local probes to explore complex (and unknown) structures in anisotropic media.     

Anisotropic diffusion of elongated and aligned polymer chains in a nematic solvent

The translational diffusion constant, D, of a polymer solute in a single-domain, nematic liquid crystal solvent (5CB) is measured in directions parallel and perpendicular to the nematic director using a fluorescence two-beam, cross-correlation technique. The solute under investigation is the stiff, conjugated polymer, MEH-PPV. The ratio D parallel/D perpendicular) of diffusion constants (parallel and perpendicular to the director) is observed to be 1.9 +/- 0.3. This is surprisingly small considering that MEH-PPV is known to be both elongated and highly aligned along the liquid crystal director of 5CB. We therefore argue that the structural order parameter of the solvent governs the anisotropy of the diffusion of the solute.     

Singlet-triplet and triplet-triplet interactions in conjugated polymer single molecules

Single molecule fluorescence correlation spectroscopy has been used to investigate the photodynamics of isolated single multichromophoric polymer chains of the conjugated polymers MEH-PPV and F8BT on the microsecond to millisecond time scale. The experimental results (and associated kinetic modeling) demonstrate that (i) triplet exciton pairs undergo efficient triplet-triplet annihilation on the <30 micros time scale, (ii) triplet-triplet annihilation is the dominant mechanism for triplet decay at incident excitation powers > or =50 W/cm(2), and (iii) singlet excitons are quenched by triplet excitons with an efficiency on the order of (1)/(2). The high efficiency of this latter process ensures that single molecule fluorescence spectroscopy can be effectively used to indirectly monitor triplet exciton population dynamics in conjugated polymers. Finally, correlation spectroscopy of MEH-PPV molecules in a multilayer device environment reveals that triplet excitons are efficiently quenched by hole polarons.     

Conformational fluctuations and large fluorescence spectral diffusion in conjugated polymer single chains at low temperatures

The fluorescence of single chains of the conductive polymer poly[2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylene vinylene] (MEH-PPV) was studied by means of single-molecule spectroscopy at 15 K. MEH-PPV was deposited onto a surface from a toluene solution and covered with a polymer cap layer of poly(vinyl alcohol) spin-coated from an aqueous solution for protection against air. Because MEH-PPV is insoluble in water, such sample preparation guarantees that MEH-PPV chains do not mix with the cap polymer. We found that this "host matrix free" environment results in substantially stronger fluorescence spectral diffusion than that observed for conjugated polymer single chains embedded into polymer matrices. The average spectral diffusion range was 500 cm(-1), and the maximum registered value reached 1100 cm(-1), which is approximately 6 times larger than the values reported before. We analyzed spectral diffusion by observation of temporal evolution of the fluorescence intensity, the position of the maximum, and the width of fluorescence spectra. We propose that the transition energy shifts are caused by the differences of the London dispersive forces in slightly different polymer chain conformations. Such conformational changes are possible even at low temperatures because the MEH-PPV single chains in our samples have more freedom for fluctuations than in the usual "in host" arrangement.     

Single chromophore spectroscopy of MEH-PPV: homing-in on the elementary emissive species in conjugated polymers.

Low-temperature, single-molecule spectroscopy can provide unparalleled access to the primary emissive species of conjugated polymers. We demonstrate this with the example of one of the most commonly studied polymers, poly(2-methoxy-5-(2'-ethylhexoxy)-1,4-phenylenevinylene), MEH-PPV, which is shown to exhibit sharp fluorescence signatures over one hundred times narrower than the ensemble. These unprecedented narrow emission features can be assigned to single chromophores on the polymer chain, which are selectively addressed by the narrow band excitation. As with organic dye systems, the emission from single chromophores is not static with time, but shows a substantial spectral fluctuation. We find that, for single chromophores, this spectral fluctuation always follows a universal Gaussian statistical distribution. High-resolution spectroscopy provides unique insight into low-energy vibrational modes in the polymer emission, which are generally inaccessible with conventional spectroscopic methods such as site-selective fluorescence or Raman spectroscopy. Interchromophoric coupling can also occur owing to the flexible nature of the polymer backbone. This leads to substantial spectral broadening and a loss of resolution in the vibronic progression. We observe reversible switching within one single molecule between narrow and broad emission, which directly correlates with a discrete switching in emission intensity. We conclude that one and the same single molecule can support aggregated and nonaggregated emission, that is, emission from isolated and aggregated chromophores in one single molecule, rather than the tendency for aggregate emission being intrinsic to the molecule.     

Molecular weight dependence of emission intensity and emitting sites distribution within single conjugated polymer molecules

We investigated exciton migration, trapping and emission processes occurring within a single conjugated polymer molecule by means of superresolution fluorescence localization microscopy. This methodology allowed us to locate the spatial distribution of emitting sites within single chains with nanometre precision. The study was done on individual poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) molecules with average molecular weights ranging from 215,000 to 1,440,000 and with narrow weight distributions. We found that the mean emission intensity increases proportionally to the polymer molecular weight. The localization experiments suggest that the emitting sites are distributed nearly uniformly within a single chain and that the sites are on average 10 nm apart, irrespective of the molecular weight of the polymer. Furthermore, spatial contours formed by all the combined emitting sites within one chain show elongated shapes, in agreement with a rod-like structure of MEH-PPV in a collapsed state.     

2H-N.M.R. studies of flexibility and orientational order in nematic liquid crystals

Deuteron magnetic resonance spectroscopy (²H-N.M.R.) has been used to investigate the effect of the nematic environment on the flexibility and orientational order of two perdeuteriated cyanobiphenyl homologues: 4-methyl-4'-cyanobiphenyl (1CB-d₁₁) and 4-n-pentyl-4'-cyanobiphenyl (5CB-d₁₉). The systems studied were low concentrations of 1CB-d₁₁ and 5CB-d₁₉ dissolved in the nematic phases of 5CB, N-(-4-ethoxybenzylidene)-4'-n-butylaniline (EBBA), Merck ZLI-1132 (1132) and a 55wt% mixture of 1132: EBBA. The spectra are dramatically different in these environments. Previous studies on small solutes have suggested that in the 55wt% 1132: EBBA mixture (at 301.4 K) the dominant orienting mechanism depends on the size and shape of the molecule which suggests that it is a short range repulsive interaction. This interaction has been modelled by treating the liquid crystal as an elastic continuum and the solute as a collection of van der Waals spheres which stretch the liquid crystal in the two dimensions perpendicular to the director. The distortion of the liquid crystal depends on the dimensions of the solute, and the elastic energy is described in terms of a Hooke's law force constant, k. The model is extended to include flexible liquid crystal molecules and quadrupolar couplings are calculated for each conformation of the 5CB chain. Statistical averaging over all conformations gives an excellent fit to the experimental spectrum. The results for 1CB and 5CB show that in the other nematic phases contributions from additional mechanisms must be included. Previous studies of ²H₂ and other solutes indicate that the additional mechanism is the interaction between the solute molecular quadrupole moment and the mean electric field gradient of the liquid crystal.     

Fluorescence blinking, exciton dynamics, and energy transfer domains in single conjugated polymer chains

In order to understand exciton migration and fluorescence intensity fluctuation mechanisms in conjugated polymer single molecules, we studied fluorescence decay dynamics at "on" and "off" fluorescence intensity levels with 20 ps time resolution using MEH-PPV [poly(2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene] dispersed in PMMA. Two types of intensity fluctuations were distinguished for single chains of conjugated polymers. Abrupt intensity fluctuations (blinking) were found to be always accompanied by corresponding changes in fluorescence lifetime. On the contrary, during "smooth" intensity fluctuations no lifetime change was observed. Time-resolved data in combination with data on fluorescence emission and excitation anisotropy lead to a picture where a single polymer molecule is seen as consisting of several energy transfer domains. Exciton migration is efficient within a domain and not efficient between domains. Each domain can have several emitting low-energy sites over which the exciton continuously migrates until it decays. Emission of individual domains is often highly polarized. Fluorescence from a domain can be strongly quenched by Forster energy transfer to a quencher (hole polaron) if the domain overlaps with the quenching sphere.     

Transient excited-state absorption of the liquid crystal CB15 [4-(2-methylbutyl)-4-cyanobiphenyl] in its isotropic phase

Liquid crystals are known to possess large electronic optical non-linearities. Transient photoinduced absorption is not commonly applied to liquid crystals, but it is a powerful technique by which to examine the excited-state absorption (ESA) and hence the non-linear absorption of molecular systems. We show that measurements of this kind can give an insight into the dominant mechanisms of picosecond non-linear optical response in liquid crystals, and together with semi-empirical quantum chemical calculations appropriate assignments of the absorptions can be made. In particular, we report measurements of the transient ESA of the liquid crystal CB15 [4-(2-methylbutyl)-4-cyanobiphenyl] in its isotropic phase using femtosecond pump-probe spectroscopy in the wavelength range from 400 to 1000 nm. By pumping directly into the first excited state (S₁) we identify at least four transient ESAs which contribute to the non-linear response up to a time of 1 ns after excitation. These features show a linear dependence with pump intensity. There also exists weak two-photon absorption (TPA) into S₁ at 650 nm, giving a similar ESA. Furthermore, we show that a semi-empirical quantum-chemical treatment of a single molecular unit of CB15 using the AMI Hamiltonian gives good agreement with the observed spectra, and implies that the dominant ESA in the picosecond regime can be attributed principally to singlet-singlet transitions from monomer units; but there is also a possible contribution to the ESAs by excimer absorption. On the time scale of our experiment we see no evidence of triplet-triplet absorptions, and we have also measured a fluorescence quantum yield of 20%.     

Photochemistry and kinetics of single organic nanoparticles in the presence of charge carriers

This paper describes a preliminary experimental study on charge injection in MEH-PPV polymer nanoparticles incorporated in an OLED type device. The nanoparticles have been investigated with single molecule fluorescence spectroscopy recorded simultaneously with charging and discharging of the particles. Structure and dynamics of an anion/MEH-PPV complex, proposed to be responsible for discrete photobleaching in conjugated polymers, have been investigated with this technique. Device physics and kinetics have been elucidated by using the fluorescent conjugated polymer nanoparticles as probes for detecting the presence of hole polarons, and have been related to the electrically induced oxidation and reduction of the anion/MEH-PPV complex.     

2H NMR Spectroscopic Investigation of para-Nitroazobenzene Liquid Crystals

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Ultrafast charge photogeneration dynamics in ground-state charge-transfer complexes based on conjugated polymers

The charge photogeneration and early recombination in MEH-PPV-based charge-transfer complexes (CTCs) and in MEH-PPV/PCBM blend as a reference are studied by ultrafast visible-pump-IR-probe spectroscopy. After excitation of the CTC band, an immediate (<100 fs) electron transfer is observed from the polymer chain to the acceptor with the same yield as in the MEH-PPV/PCBM blend. The forward charge transfer in the CTCs is followed by an efficient (approximately 95%) and fast (<30 ps) geminate recombination. For comparison, the recombination efficiency obtained in the MEH-PPV/PCBM blend does not exceed a mere 50%. Polarization-sensitive experiments demonstrate high (approximately 0.3) values of transient anisotropy for the CTCs polaron band. In contrast, in the MEH-PPV/PCBM blend the dipole moment orientation of the charge-induced transition is less correlated with the polarization of the excitation photon. According to these data, photogeneration and recombination of charges in the CTCs take place locally (i.e., within a single pair of a polymer conjugation segment and an acceptor) while in the MEH-PPV/PCBM blend exciton migration precedes the separation of charges. Results of the ultrafast experiments are supported by photocurrent measurements on the corresponding MEH-PPV/acceptor photodiodes.     

Effects of liquid crystal environment on the spectroscopic and photophysical properties of well-known reacting systems 2,3-dimethylindole (DMI) and 9-cyanoanthracene (9CNA)

Electrochemical and steady-state and time-resolved spectroscopic studies on a disubstituted indole, 2,3-dimethylindole (DMI), and well-known electron acceptor 9-cyanoanthracene (9CNA) in liquid crystal (LC) 4-(n- pentyl)-4'-cyanobiphenyl (5CB) environment demonstrate entirely different spectroscopic and photophysical behaviors from those observed earlier by our research group with the same reacting systems in isotropic media n-heptane and acetonitrile (ACN). From the UV-vis absorption spectral measurements of the donor DMI in the presence of the acceptor 9CNA in liquid crystal medium (in 5CB) in various temperatures above the nematic-isotropic phase transition from 308 to 313 K (pseudo-ordered domain), it was observed that the lower energy lying absorption band of DMI situates in a longer wavelength region than the corresponding band observed in isotropic medium n-heptane or ACN. The possibility of the photochromic effect is discussed. In this band, the degree of mixing of the two closely spaced electronic states (1)L(a) (S(2)) and (1)L(b) (S(1)) of DMI was very prominent in the ordered LC environment (5CB) whereas in isotropic medium the dominant contribution for the formation of the lower energy band system primarily originates from the (1)Lb (S(1)) state, as evidenced from the steady-state polarization measurements. Both steady-state fluorescence quenching and time-resolved fluorescence studies clearly demonstrate in favor of the presence of only the static mode in LC environment. The situation differs in isotropic media where the dynamic process possesses the key role in the quenching mechanism. Expectedly, the transient absorption measurements by the nanosecond laser flash photolysis technique show a lack of formation of transient ionic species in the pseudo-ordered domain of 5CB. On the contrary, in isotropic solvents n-heptane and ACN, the transient absorption spectra measured by the same nanosecond laser flash photolysis technique exhibit the broad band of 9CNA radical anion at around 560 nm (9CNA-) and the band of neutral radical of DMI at 540 nm. It is inferred that the charge-separation reactions occurring within the present intermolecular systems could be stopped significantly by changing the nature of the environment from the isotropic to the LC's pseudo-ordered domain which situates closely above the nematic (N)-isotropic (I) phase transition temperature. From the steady-state and time-resolved investigations, it is revealed that, due to the hysteresis phenomenon, the nematic phase properties persist over a wide temperature range well within pseudo-ordered domain to some extent into the isotropic phases. The investigations with the different donor-acceptor inter- and intramolecular systems in 5CB and some other LC's environment are underway.     

Influence of the remanent polarisation on the liquid crystal alignment in composite films of ferroelectric poly(vinylidene fluoride-trifluoroethylene) and a cyanobiphenyl-based liquid crystal

Polymer-dispersed liquid crystals (PDLCs) of ferroelectric poly(vinylidene fluoride-trifluoroethylene) and nematic 4-cyano-4?-n-hexylbiphenyl (6CB) or 4-cyano-4?-n-pentylbiphenyl (5CB) were prepared to study the effect of the remanent polarisation of the polymer on the liquid crystal alignment. We measured the macroscopic alignment of the liquid crystal molecules in the thickness direction by means of Infrared Transition-Moment Orientational Analysis. Electrical poling at 100 V/µm caused an increased order parameter up to 0.15. After subsequent annealing above the nematic-to-isotropic phase-transition temperature, the order parameter was reduced to 0.02. Nevertheless, the order parameter was still higher than for non-poled film indicating a slight orientation in thickness direction. Both values are lower than those expected from model calculations. In agreement with dielectric measurements, we attribute this result to the shielding effect of mobile charge carriers within the liquid crystal inclusions.     

Electrofluorescence of MEH-PPV and its oligomers: evidence for field-induced fluorescence quenching of single chains

Electrofluorescence (Stark) spectroscopy has been used to measure the trace of the change in polarizability (trDeltaalpha) and the absolute value of the change in dipole moment (|Deltamu|) of the electroluminescent polymer poly[2-methoxy,5-(2'-ethyl-hexoxy)-1,4-phenylene vinylene] (MEH-PPV) and several model oligomers in solvent glass matrixes. From electrofluorescence, the measured values of trDeltaalpha increase from 500 +/- 60 A(3) in OPPV-5 to 2000 +/- 200 A(3) in MEH-PPV. The good agreement found between these values and those measured by electroabsorption suggests the electronic properties do not differ strongly between absorption and emission, in contrast to earlier predictions. Evidence of electric-field-induced fluorescence quenching of MEH-PPV in dilute solvent glasses was found. When normalized to the square of the applied electric field, the magnitude of quench is comparable to that reported in the literature for thin films of MEH-PPV. In addition, fluorescence quenching was also observed in the oligomers with a magnitude that increases with increasing chain length. By using the values of trDeltaalpha measured by electrofluorescence, a model is developed to qualitatively explain the chain length dependence to the fluorescence quench observed in the oligomers as a function of exciton delocalization along the oligomer backbone. Various explanations for the origin of this quenching behavior and its chain length dependence are considered.     

Controlling chain conformation in conjugated polymers using defect inclusion strategies

The Horner method was used to synthesize random copolymers of poly(2-methoxy-5-(2'-ethylhexyloxy)-p-phenylene vinylene) (MEH-PPV) that incorporated different backbone-directing monomers. Single-molecule polarization absorption studies of these new polymers demonstrate that defects that preserve the linear backbone of PPV-type polymers assume the highly anisotropic configurations found in defect-free MEH-PPV. Rigid defects that are bent lower the anisotropy of the single chain, and saturated defects that provide rotational freedom for the chain backbone allow for a wide variety of possible configurations. Molecular dynamics simulations of model defect PPV oligomers in solution demonstrate that defect-free and linearly defected oligomers remain extended while the bent and saturated defects tend toward more folded, compact structures.     

Effect of the Side‐Chain‐Distribution Density on the Single‐Conjugated‐Polymer‐Chain Conformation

The spatial arrangement of the side chains of conjugated polymer backbones has critical effects on the morphology and electronic and photophysical properties of the corresponding bulk films. The effect of the side‐chain‐distribution density on the conformation at the isolated single‐polymer‐chain level was investigated with regiorandom (rra‐) poly(3‐hexylthiophene) (P3HT) and poly(3‐hexyl‐2,5‐thienylene vinylene) (P3HTV). Although pure P3HTV films are known to have low fluorescence quantum efficiencies, we observed a considerable increase in fluorescence intensity by dispersing P3HTV in poly(methyl methacrylate) (PMMA), which enabled a single‐molecule spectroscopy investigation. With single‐molecule fluorescence excitation polarization spectroscopy, we found that rra‐P3HTV single molecules form highly ordered conformations. In contrast, rra‐P3HT single molecules, display a wide variety of different conformations from isotropic to highly ordered, were observed. The experimental results are supported by extensive molecular dynamics simulations, which reveal that the reduced side‐chain‐distribution density, that is, the spaced‐out side‐chain substitution pattern, in rra‐P3HTV favors more ordered conformations compared to rra‐P3HT. Our results demonstrate that the distribution of side chains strongly affects the polymer‐chain conformation, even at the single‐molecule level, an aspect that has important implications when interpreting the macroscopic interchain packing structure exhibited by bulk polymer films.     

2H-N.M.R. studies of flexibility and orientational order in nematic liquid crystals

Abstract

Deuteron magnetic resonance spectroscopy (²H-N.M.R.) has been used to investigate the effect of the nematic environment on the flexibility and orientational order of two perdeuteriated cyanobiphenyl homologues: 4-methyl-4′-cyanobiphenyl (1CB-d ₁₁) and 4-n-pentyl-4′-cyanobiphenyl (5CB-d ₁₉). The systems studied were low concentrations of 1CB-d ₁₁ and 5CB-d ₁₉ dissolved in the nematic phases of 5CB, N-(-4-ethoxybenzylidene)-4′-n-butylaniline (EBBA), Merck ZLI-1132 (1132) and a 55wt% mixture of 1132: EBBA. The spectra are dramatically different in these environments. Previous studies on small solutes have suggested that in the 55wt% 1132: EBBA mixture (at 301.4 K) the dominant orienting mechanism depends on the size and shape of the molecule which suggests that it is a short range repulsive interaction. This interaction has been modelled by treating the liquid crystal as an elastic continuum and the solute as a collection of van der Waals spheres which stretch the liquid crystal in the two dimensions perpendicular to the director. The distortion of the liquid crystal depends on the dimensions of the solute, and the elastic energy is described in terms of a Hooke's law force constant, k. The model is extended to include flexible liquid crystal molecules and quadrupolar couplings are calculated for each conformation of the 5CB chain. Statistical averaging over all conformations gives an excellent fit to the experimental spectrum. The results for 1CB and 5CB show that in the other nematic phases contributions from additional mechanisms must be included. Previous studies of ²H₂ and other solutes indicate that the additional mechanism is the interaction between the solute molecular quadrupole moment and the mean electric field gradient of the liquid crystal.     

Effect of metal nanoparticles on the optical properties of the solutions of porphyrinates and MEH-PPV polymer

The interactions of metal nanoparticles, which were synthesized in inverse micelles, with a number of porphyrinate molecules and a poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) polymer in solutions were examined by spectrophotometry in order to study the effects of various additives on the efficiency of sun energy absorption and conversion by photosensitive polymer layers. The optical absorption and luminescence spectra of the solutions of Ag, Pd, and Pt nanoparticles and the solutions of Pd(II) and Pt(II) meso-tetra(benzo-15-crown-5)porphyrinates and the MEH-PPV polymer were measured previously.     

Application of poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] for splitting of single-walled carbon nanotube bundles in polystyrene/SWCNT composite

Dispersions of single-walled carbon nanotubes (SWCNTs) in organic solutions containing poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) were studied by Raman spectroscopy, UV-vis-NIR spectroscopy, and electron microscopy. This polymer interacts with the nanotube resulting in the appearance of a new red-shifted absorption band in the electronic spectrum. This indicates the formation of a charge-transfer complex between MEH-PPV and SWCNTs. Additives of MEH-PPV make it possible to achieve stable suspensions of nanotubes in styrene. A polystyrene/SWCNT/MEH-PPV composite with a high degree of bundle splitting was obtained by polymerization. It was shown that the luminescence intensity of the nanotubes in the Raman spectrum can serve as a indicator for the estimation of the degree of splitting of SWCNT bundles in the composite.