Aggregates In Thin Films Research Articles

The Excited-State Lifetime of Poly(NDI2OD-T2) Is Intrinsically Short.

Conjugated polymers composed of alternating electron donor and acceptor segments have come to dominate the materials being considered for organic photoelectrodes and solar cells, in large part because of their favorable near-infrared absorption. The prototypical electron-transporting push-pull polymer poly(NDI2OD-T2) (N2200) is one such material. While reasonably efficient organic solar cells can be fabricated with N2200 as the acceptor, it generally fails to contribute as much photocurrent from its absorption bands as the donor with which it is paired. Moreover, transient absorption studies have shown N2200 to have a consistently short excited-state lifetime (∼100 ps) that is dominated by a ground-state recovery. In this paper, we investigate whether these characteristics are intrinsic to the backbone structure of this polymer or if these are extrinsic effects from ubiquitous solution-phase and thin-film aggregates. We compare the solution-phase photophysics of N2200 with those of a pair of model compounds composed of alternating bithiophene (T2) donor and naphthalene diimide (NDI) acceptor units, NDI-T2-NDI and T2-NDI-T2, in a dilute solution. We find that the model compounds have even faster ground-state recovery dynamics (τ = 45, 27 ps) than the polymer (τ = 133 ps), despite remaining molecularly isolated in solution. In these molecules, as in the case of the N2200 polymer, the lowest excited state has a T2 to NDI charge-transfer (CT) character. Electronic-structure calculations indicate that the short lifetime of this state is due to fast nonradiative decay to the ground state (GS) promoted by strong CT-GS electronic coupling and strong electron-vibrational coupling with high-frequency (quantum) normal modes.

Correlating Charge Transport Properties of Conjugated Polymers in Solution Aggregates and Thin-Film Aggregates.

The role of solution aggregates on the charge transport process of conjugated polymers in electronic devices has gained increasing attention; however, the correlation of the charge carrier mobilities between the solution aggregates and the solid-state films remains elusive. Herein, three polymers, FBDOPV-2T, FBDOPV-2F2T, and FBDOPV-4F2T, are designed and synthesized with distinct aggregation behavior in solution. By combining contact-free ultrafast terahertz (THz) spectroscopy and field-effect transistor measurements, we track the charge carrier mobility of the aggregates of these polymers from the solution to the thin-film state. Remarkably, the mobility of these three polymers is found to follow nearly the same trend (FBDOPV-2T>FBDOPV-2F2T≫FBDOPV-4F2T) in both solutions and thin-film states. The quantitative mobility correlation indicates that the charge transport properties of solution aggregates play a critical role in determining the thin-film charge transport properties and final device performance. Our results highlight the importance of investigating and controlling solution aggregation structures towards efficient organic electronic devices.

Thin Films of Tolane Aggregates for Faraday Rotation: Materials and Measurement

We present organic, diamagnetic materials based on structurally simple (hetero-)tolane derivatives. They form crystalline thin-film aggregates that are suitable for Faraday rotation (FR) spectroscopy. The resulting new materials are characterized appropriately by common spectroscopic (NMR, UV-Vis), microscopy (POM), and XRD techniques. The spectroscopic studies give extremely high FR activities, thus making these materials promising candidates for future practical applications. Other than a proper explanation, we insist on the complexity of designing efficient FR materials starting from single molecules.

Fullerene Aggregation in Thin Films of Polymer Blends for Solar Cell Applications.

We report on the effects of the film morphology on the fluorescence spectra for a thin film including a quinoxaline-based co-polymer (TQ1) and a fullerene derivative ([6,6]-phenyl-C71-butyric acid methyl ester—PC70BM). The ratio between the polymer and the fullerene derivative, as well as the processing solvent, were varied. Besides the main emission peak at 700 nm in the fluorescence spectra of thin films of this phase-separated blend, a broad emission band is observed with a maximum at 520–550 nm. The intensity of this emission band decreases with an increasing degree of mixing in the film and becomes most prominent in thicker films, films with high PC70BM content, and films that were spin-coated from solvents with lower PC70BM solubility. We assign this emission band to aggregated PC70BM.

Progress in organic photocatalysts

Organic materials have advantages of diversity, ease of functionality, self-assembly, etc. The varied mechanistic pathways also make it conceivable to design an appropriate photocatalyst for an identical reaction. From this perspective, organic photocatalysts find wide applications in homogeneous, heterogeneous photocatalysis and photoelectrochemical (PEC) solar cells. In this review, the form of the employed organic photocatalysts ranging from molecules, supported molecules, to nanostructures or thin-film aggregates will be firstly discussed. Rational design strategies relating to each form are also provided, aiming to enhance the photoenergy conversion efficiency. Finally, the ongoing directions for future improvement of organic materials in high-quality optoelectronic devices are also proposed.

The Effect of H‐ and J‐Aggregation on the Photophysical and Photovoltaic Properties of Small Thiophene–Pyridine–DPP Molecules for Bulk‐Heterojunction Solar Cells

The performance of organic semiconductors in optoelectronic devices depends on the functional properties of the individual molecules and their mutual orientations when they are in the solid state. The effect of H‐ and J‐aggregation on the photophysical properties and photovoltaic behavior of four electronically identical but structurally different thiophene–pyridine–diketopyrrolopyrrole molecules is studied. By introducing and changing the position of two hexyl side chains on the two peripheral thiophene units of these molecules, their aggregation in thin films between H‐type and J‐type is effectively tuned, as evidenced from the characteristics of optical absorption, fluorescence, and excited state lifetime. The two derivatives that assemble into J‐type aggregates exhibit a significantly enhanced photovoltaic performance, up to an order of magnitude, compared to the two molecules that form H‐type aggregates. The reasons for this remarkably different behavior are discussed.

Multicolor photon emission from organic thin films on different substrates

Thin films of 1-pentyl-2/,3/-difluoro-3///-methyl-4////-octyl-p-quinquephenyl and 9,10-Bis (4-pentylphenylethynyl)antracene organic molecules were grown on optical glass, silicon and porous silicon substrates. First optical and luminescent properties of such hybrid composites are thoroughly studied using spectroscopic techniques. The strong decrease of aggregation in thin films of 1-pentyl-2/,3/-difluoro-3///-methyl-4////-octyl-p-quinquephenyl on porous silicon was observed. The possibility of simultaneous red, green and blue tunable photon emission from organic film/porous silicon hybrid structure is demonstrated.

Mitigation of Surface Aggregation in Modified Phthalocyanines as Potential Photo Sensitizers

ABSTRACTImportant to the development of dye-sensitized solar cells is the longevity and photo-conversion efficiency of the dye. To improve cost effectiveness, dyes of superior thermal and chemical stability are desirable to extend device performance. In this study, we examine a series of peripherally fluorinated Zinc-Phthalocyanines (FxZnPc). Introduction of chemically inert fluorine and isopropyl fluoroalkyl groups on the periphery of the Pc improve the dye stability and allow for tunable photo-physical properties. Additionally, introduction of the bulky isopropyl fluoroalkyl groups help mitigate molecular aggregation in thin films which is known to be detrimental to maintaining the desired photo-physical properties of the surface coating. Using molecular dynamics and first principles modeling, various substituent effects on surface adhesion and aggregation over TiO2 surfaces are characterized for both symmetric and asymmetric substitution.

High Intrachain Order Promotes Triplet Formation from Recombination of Long-Lived Polarons in Poly(3-hexylthiophene) J-Aggregate Nanofibers

Photoluminescence (PL) of single poly(3-hexylthiophene) (P3HT) J-aggregate nanofibers (NFs) exhibits strong quenching under intensity-modulated pulsed excitation. Initial PL intensities (I(0)) decay to steady-state levels (ISS) typically within ∼ 1-10 μs, and large quenching depths (I(0)/I(SS) >2) are observed for ∼ 70% of these NFs. Similar studies of polymorphic, H-aggregate type P3HT NFs show much smaller PL quenching depths (I(0)/I(SS) ≤ 1.2). P3HT chains in J-type NF π-stacks possess high intrachain order, which has been shown previously to promote the formation of long-lived, delocalized polarons. We propose that these species recombine nongeminately to triplets on time scales of >1 ns. The identity of triplets as the dominant PL quenchers was confirmed by subjecting NFs to oxygen, resulting in an instantaneous loss of triplet PL quenching (I(0)/I(SS) ∼ 1). The lower intrachain order in H-type NFs, similar to P3HT thin-film aggregates, localizes excitons and polarons, leading to efficient geminate recombination that suppresses triplet formation at longer time scales. Our results demonstrate the promise of self-assembly strategies to control intrachain ordering within multichromophoric polymeric aggregate assemblies to tune exciton coupling and interconversion processes between different spin states.

A time-temperature integrator based on fluorescent and polymorphic compounds

Despite the variety of functional properties of molecular materials, which make them of interest for a number of technologies, their tendency to form inhomogeneous aggregates in thin films and to self-organize in polymorphs are considered drawbacks for practical applications. Here, we report on the use of polymorphic molecular fluorescent thin films as time temperature integrators, a class of devices that monitor the thermal history of a product. The device is fabricated by patterning the fluorescent model compound thieno(bis)imide-oligothiophene. The fluorescence colour of the pattern changes as a consequence of an irreversible phase variation driven by temperature, and reveals the temperature at which the pattern was exposed. The experimental results are quantitatively analysed in the range 20–200°C and interpreted considering a polymorph recrystallization in the thin film. Noteworthy, the reported method is of general validity and can be extended to every compound featuring irreversible temperature-dependent change of fluorescence.

Designed Suppression of Aggregation in Polypyrene: Toward High‐Performance Blue‐Light‐Emitting Diodes

A novel non-aggregating polypyrene, which can be synthesized via a simple three-step chemical route from pyrene in good yields, is presented. Poly-7-tert-butyl-1,3-pyrenylene shows a high solid-state fluorescence quantum yield with blue emission, excellent solubility and stability, no aggregation in thin films, and good electro-optical performance in single-layer organic light-emitting diodes (see figure).

Aggregation quenching in thin films of MEH-PPV studied by near-field scanning optical microscopy and spectroscopy

Aggregates in thin films of conjugated polymers form excimer states and significantly reduce the photo- and electroluminescence efficiency in devices produced from these materials. We have studied the aggregate formation in thin films of poly(2-methoxy,5-(2′-ethyl-hexyloxy)- p-phenylene-vinylene) (MEH-PPV) by near-field scanning optical microscopy and spectroscopy. Local photoluminescence spectroscopy and photo-bleaching experiments have been used to show that thin films of MEH-PPV are homogeneously aggregated and do not form aggregated domains.

COMPUTER SIMULATION OF AGGREGATION-FRACTALS IN THIN FILMS

The formation of aggregation fractals in thin polycrystalline bilayer films has been simulated by using the ripening mechanism of nonuniform grains.Based on the analysis of the aggregation of thin films,three parameters are introduced:the velocity factor of grain boundary b,the relaxation range L and the curvature factor U.By using certain values of such parameters,the simulation results are consistent with the patterns formed in experiments.

Aggregation and growth processes in thin films of magnetic fluid

The appearance and growth process of needle-like aggregates in thin films of magnetic fluid within a magnetic field are investigated. The results show that the average length of aggregates in a given magnetic field depends on the method of application of the magnetic field. However, the full needle length per unit area as a first approximation to a condensed phase volume is approximately the same.

Multifractal characteristics of magnetic-microsphere aggregates in thin films.

Multifractal characteristics of magnetic-microsphere aggregates in thin films.