Helical conjugated polymers are of great interest for their potential as sources of circularly polarized luminescence for numerous electro-optical device applications including display technologies. Due to their relatively strong absorption cross sections and high emissivity in the visible wavelength range, these materials permit a detailed investigation of how the transition between helical and random coil forms are driven by polymer structural features such as chain length and chemical defects as well as environmental properties such as solvent and temperature. Bulk methods such as circular dichroism, absorption, and fluorescence as well as single-particle microscopy is used to probe the helix-to-coil phase transition in a model chiral polyfuran and to determine whether the conformations favored in solution are retained in the solid state. In addition, the transient dynamics and the effects of chemical doping on the electronic properties of the helix and coiled forms are explored.
Aggregation in conjugated polymers is a well-recognized driver of performance in organic opto-electronic devices. In particular, good device performance is correlated with processing methods that also minimize non-radiative traps that quench emission in thin films. Here we compare the efficacy of various solvent systems in producing weakly versus highly emissive aggregates in the well-studied polymer poly(3-hexylthiophene) or P3HT and show that many systems that appear highly quenched in bulk solution are strongly emissive in the solid state. Microscopy, transient dynamical measurements, and structural studies to probe the electronic and structural differences between weakly and highly emissive aggregates are described.
Helical conjugated polymers are of great interest for their potential as sources of circularly polarized luminescence for numerous electro-optical device applications including display technologies. Due to their relatively strong absorption cross sections and high emissivity in the visible wavelength range, these materials permit a detailed investigation of how the transition between helical and random coil forms are driven by polymer structural features such as chain length and chemical defects as well as environmental properties such as solvent and temperature. Bulk methods such as temperature dependent absorption, emission, and circular dichroism as well as single-particle microscopy are used to probe the helix-to-coil phase transition in a model chiral polyfuran and to determine whether the conformations favored in solution are retained in the solid state. In addition, the transient dynamics and the effects of chemical doping on the electronic properties of the helix and coiled forms are explored.
Helical conjugated polymers are of great interest for their potential as sources of circularly polarized luminescence and as magnetic field sensors. Due to their relatively strong absorption cross sections and high emissivity in the visible wavelength range, these materials permit a detailed investigation of how the transition between helical and random coil forms are driven by polymer structural features such as chain length and chemical defects as well as environmental properties such as solvent and temperature. Bulk methods such as circular dichroism, absorption, and fluorescence as well as single-particle microscopy is used to probe the helix-to-coil phase transition in a model chiral polyfuran and to determine whether the conformations favored in solution are retained in the solid state.
While fluorescent conjugated polymers are seeing increased use in optoelectronics, aggregation remains a roadblock due to emission quenching. It is therefore important to more fully understand the conditions that drive the emissive behavior. To properly interpret the spectral changes of P3HT from solvent poisoning, we employed a variety of single-molecule fluorescence techniques. In general, is impossible to assign spectral features in bulk emission spectra to the monomer versus aggregate or a mixture of different aggregate types without additional information. However, by measuring the difference in something like diffusion time as a function of emission wavelength, the spectral features that correspond to monomeric and aggregated chains can be assigned. Notably, these aggregates are highly emissive in the solid state though not in solution. The results suggest solvent poisoning provides a simple method of producing highly emissive aggregates from otherwise weakly emissive materials.
Organic semiconductors are commonly used for the development optoelectronic devices. However, these materials degrade rapidly in the presence of light and oxygen. we expand upon our previously methods of using thin metal films to enhance the stability of a polymer via metal enhanced fluorescence. When overlap of the plasmon peak and peak fluorescence of the polymer is achieved the radiative decay rate increases. The plasmon can be tuned via changing the deposition time and current settings of the sputter coater used for coating. By obtaining fluorescence images of the polymer deposited on the metal film compare to on glass in ambient air, a high degree of stabilization is found via plasmonic interactions. Lifetimes were also obtained of the polymer on glass, an electron transporting layer, and a gold film to compare the changes in lifetime from plasmonic interactions versus charge transfer. The usefulness of plasmonic for organic solar cell materials was probed in this way.
Molecules that undergo thermally activated delayed fluorescence (TADF) represent an important class of systems for the design of efficient organic lighting (OLEDS) because they utilize both singlet and triplet excitons for electrically-generated light emission. Most molecules of this type have considerable charge transfer (CT) character as this is known to result in nearly degenerate singlet and triplet energies. Another important consequence of this CT character is that the TADF efficiency as well as the emission wavelength and color purity are highly sensitive to the polarity of the local environment. Here we present data demonstrating the effect of local polarity on the fluorescence intermittency (blinking) of single TADF molecules isolated in a series of host matrices of varying dielectric constants. The on and off times of the fluorescence of single chromophores are shown to be highly sensitive to local polarity and are used to model the dynamics of singlet-triplet crossing.
Organic semi-conductors are widely used in the development and manufacturing of certain optoelectronics. However, these materials are susceptible to photodegradation in the presence of oxygen. This is due to a polymer’s populated triplet state creating singlet oxygen. In recent years, the use of plasmonic metal nanoparticles in the polymer systems or deposited on a substrate, have yielded polymer films that degrade much slower than films with the polymer alone, as long as there is good overlap with the plasmon of the metal and the emission of the polymer. Since this overlap is crucial, tunability of the plasmon is essential to “fit” various polymer systems. The research presented here provides methodology for the facile manufacturing and tuning of metal deposits for such purposes. Not only this, but through increasing the tunability of these plasmons we are able to better image various emissive pathways and species better in a polymer system deposited on film.
The integration of furan based repeat units into conjugated systems meant for optoelectronic applications has generally been limited by the photostability of the furan unit. This limitation is due to the susceptibility of furan towards reaction with singlet oxygen, which disrupts the conjugation of the system. Here, we present a family of helical, ester-functionalized polyfurans with dramatically enhanced photostability. Within this family, the emission intensity of P3HEF is essentially non-existent while a chiral branched variant, (S)-P3EHEF, is highly fluorescent. This discrepancy is due to the difference in the compactness of the helical structure of the two polymers. Interestingly, the emission wavelength of (S)-P3EHEF can be tuned through several different techniques such as deposition speed and solvation conditions. The mechanism behind the tunability was explored using fluorescence-based techniques.
Organic semiconductors are promising for the development of many applications including in solid state lighting, flexible displays and organic-based lasing. However, a critical factor limiting their utility is their inherently low stability relative to inorganic materials. This instability causes organic molecules to be susceptible to oxygen damage in an irreversible process known as photo-bleaching. This effect necessitates the development of highly impermeable encapsulation strategies and limits device lifetimes. Plasmonic engineering offers one avenue to alter the decay rates of fluorophores and modify the emission from single molecules and thin films. Here, we demonstrate that by carefully engineering the properties of ultra-thin gold films to match the plasmon with the emission of organic molecules a photostability enhancement of more than 60-fold can be achieved. As an example, we successfully demonstrated that OPPV-13, an oligomer of poly [2-methoxy-5(2'-ethylhexyloxy)-1,4-phenylene]vinylene, deposited on 2 nm thick Au substrates retains its fluorescence under constant illumination in ambient conditions for 45 minutes compared to less than 2 minutes when it is deposited on glass substrates. The underlying mechanism of this remarkable enhanced photostability is probed using a variety of microscopy-based tools and extensions to other opto-electronic materials are described.
In recent decades, fluorescent conjugated polymers have been widely studied due to their ability to produce low-cost and lightweight organic electronics. However, given that their solid state packing arrangements are difficult to control or predict, maintaining the desired emissive properties of the materials is challenging. As the emission wavelengths and quantum yields of these materials are highly sensitive to their solid state packing arrangements, pre-aggregation in solution can assist in maintaining properties through the transition between solution and solid state. Here we use poly(3- hexylthiophene) (P3HT), a well-studied organic semi-conductor, to explore the impact of aggregation on the photophysical properties of the material. We have employed various bulk and single molecule fluorescence-based methods to better understand the effect of aggregation on the emission properties of the polymer system. The addition of a highly-polar solvents to induce aggregation leads to strong emission quenching, but no change in the lifetime in solution. However, in the solid state the aggregates exhibit enhanced emission intensity combined with shorter lifetimes as demonstrated by fluorescence lifetime imaging microscopy (FLIM). To better understand the differences of the aggregate properties in the solution and solid state, fluorescence anti-bunching was used to probe the degree of electronic coupling of the polymer chains. Surprisingly, fluorescence anti-bunching measurements reveal the highly collective nature of the P3HT aggregate emission, which likely accounts for its strong fluorescence intensity in the solid state. Studying the aggregated system at both the bulk and single-molecule level will yield a better understanding of the aggregate properties which will lead to better control and higher performance of organic semiconductors in device applications.
Though bulk silicon (Si) is an indirect bandgap material and therefore non-emissive, nm-sized Si quantum dots (Si QDs) exhibit direct band-gap characteristics due to quantum confinement. As a result, Si QDs are emissive though their fluorescence is relatively weak and limited to red or near-infrared. Recently, visible and color-tunable emission with up to 90% quantum yield has been achieved through surface-modification of Si QDs with nitrogen-capped ligands. However, the emission mechanism operating in these surface-modified Si QDs is unclear and the factors that determine their emission maxima are still unknown. Here we report that the emission maximum wavelength of these species can be predicted quantitatively from the calculated ground-state dipole moment of the ligand. This is consistent with the origin of the emission being a charge-transfer (CT) transition between the Si surface and the ligand. A detailed study of the photon statistics behavior of isolated Si QDs reveals two types of emission, the dominant one being characteristic of single quantum states and the weaker one being characteristics of a bulk material. Understanding the emission mechanism of these unique systems and how their properties can be tuned synthetically will enable the design of Si QDs with a broader wavelength range and higher quantum yields for applications in light-emitting diodes, bio-imaging and sensing.
Fluorescent conjugated polymers are attractive materials to produce low-cost and lightweight displays, lighting, and organic electronics. However, when transitioning from solution to solid state, maintaining the desired emissive properties of these materials remains a challenge; the emission wavelength and quantum yield of fluorescent polymers are highly sensitive to their solid state packing arrangements which are difficult to control or predict. Additionally, their susceptibility to photo-degradation limits their widespread use. Aggregation of the polymer can protect the material from most oxidative damage by reducing the diffusivity of the oxygen through the aggregate structure. Here we employ various bulk and single molecule fluorescence-based methods to explore this aspect of a well-studied organic semi-conductor, poly(3-hexylthiophene) (P3HT). Pre-aggregating P3HT with highly-polar solvents prior to spin casting leads to aggregate structures and thin films with significantly enhanced emissive intensity and photo-stability relative to films cast without pre-aggregation. Additionally, enhanced photo-oxidative stability was seen in films formed from the pre-aggregated samples. A better understanding of aggregate properties should lead to better control and higher performance of organic semiconductors in device applications.
Applications of conjugated polymers in photovoltaics and displays drive the need to understand how morphology and aggregation affect emission yields, spectra, and the facility with which charges are generated and migrate through the sample. It is known that solvent-polymer interactions in solution critically affect the properties of thin films formed when these solutions are evaporated onto substrates. Our work demonstrates that the propensity of conjugated oligomers and polymers to form emissive versus non-emissive aggregates in solution and in thin films is likewise governed by the solvent properties. Fluorescence correlation spectroscopy is used as a tool to identify both emissive and non-emissive species in dilute solutions while dynamic light scattering (DLS) is used to measure diffusion properties. In some solvents, such as toluene, conjugated materials form non-emissive aggregates even at picomolar concentrations. Under similar conditions, the same materials exhibit single-emitter properties in more polar solvents such as tetrahydrofuran (THF). These distinctions persist when the molecules are forcibly aggregated by addition of poor solvent and are correlated to variations in chain packing within the aggregate due to differences in their preferred conformation. Transient absorption spectroscopy is used to understand the impact of altering chain packing on the propensity for energy transfer and charge separation in the aggregated state and in films.
There is a growing demand to improve the operational lifetime of electroluminescent devices utilizing conjugated
polymers which are often deposited over metal electrodes. Photo-degradation of the emissive organic layer is one
factor that decreases the overall efficiency and longevity of these devices. Therefore, it is important to investigate the
underlying photochemistry at metal-polymer interface. Here, the effects of metal films on the emission properties of
organic polymers are studied using Total Internal Reflection Fluorescence (TIRF) microscopy and Fluorescence
Lifetime Imaging (FLIM). Poly(phenylene vinylene) (MEHPPV) is spun cast over gold films of varying thickness (2
nm to 8 nm). Whereas 8 nm gold films completely quench the MEHPPV fluorescence, thinner gold films (~ 2 nm)
cause minimal quenching. However, deposition on the thinner gold films leads to a dramatic increase in photo-stability
of MEH-PPV relative to that on glass, even in the presence of molecular oxygen and under continuous laser
illumination. Good overlap between the surface plasmon absorbance of gold films and the emission of MEHPPV is
required for this effect as it is not observed on metals without a plasmon band in this spectral region.
Silicon (Si) is known to have an indirect bandgap transition, which means it has poor fluorescence properties. However,
when engineered into sub-nm sized particles, Si nanoparticles become emissive due to quantum confinement. However,
in unmodified Si particles, this effect is limited to generating red or near-infrared emission with low quantum yield. To
resolve these limitations, surface-modification methods have successfully generated Si particles that emit in the blue,
cyan, and green with quantum yields up to ~90%.1,2 These modifications have also made the Si nanoparticles watersoluble,
making them promising in biological applications. To date, the mechanism of emission in these species is still
unclear although it has been speculated that charge transfer of Si-O-N could be responsible. To investigate whether
emission by these Si nanoparticles proceeds via a charge transfer mechanism, Stark spectroscopy is used. In this method,
an external electric field is applied to the Si nanoparticles. Changes in the absorption and/or emission spectra due to the
applied field can be taken as strong evidence for a charge transfer mechanism. From the results of Stark spectroscopy, Si
nanoparticles are revealed to have ligand to metal charge transfer mechanism along with electric-field quenching, which
is useful information for utilization into applications. Addition to the information found, a method of how to tune the
emission maxima based on selection of ligands is prosed.
There is a growing demand to improve the operational lifetime of electroluminescent (EL) devices utilizing conjugated polymers which are often deposited over metal electrodes. Photo-degradation of the emissive organic layer is one factor that decreases the overall efficiency and longevity of these devices. Therefore, it is important to investigate the underlying photochemistry at metal-polymer interface. Here, effects of metal films on the emission properties of organic polymers are studied using total internal reflection fluorescence (TIRF) microscopy. It is observed that poly(phenylene vinylene) (MEHPPV) exhibits a remarkable increase in photo-stability when deposited on gold films relative to that on glass even in the presence of molecular oxygen and under continuous laser illumination. It is proposed that this interesting property is due to the surface plasmon of Au films.
With the rising popularity of organic light-emitting diodes (OLEDs) in display applications, demand for more efficient blue emitters has increased. We have recently synthesized a novel blue-emitting, donor-acceptor system employing carbazole as the donor and a benzothiazole derivative as the acceptor, BTZ-CBZ. We find that the solution-phase emission of BTZ-CBZ is highly dependent on solvent polarity, both in lineshape and emission maximum, showing a Stokes shift of 50 nm in methylcyclohexane and 150 nm in acetonitrile. This is expected behavior for donor-acceptor compounds due to the presence of a charge-transfer excited state. However, the solid state properties are more important for OLED devices. Using time-dependent density functional theory calculations employing the linear-response (LR) and state-specific (SS) polarizable continuum model (PCM), we explore the effects of solvent reorganization on the emission properties of BTZ-CBZ. SS-PCM reproduces the solvatochromism behavior of BTZ-CBZ in solution, but LR-PCM shows effectively no shift with solvent polarity. We surmise that this is because solvent reorganization is necessary for the solvatochromic effect to occur. The effect of rigid matrices on the emission of BTZ-CBZ has direct implications on its viability as a blue emitter in solid-state OLEDs and which molecular environments will be ideal for devices.
Realization of energy efficient and cost effective electroluminescence applications of conjugated polymers, like organic light emitting diodes (OLEDs), requires a complete understanding of photo-chemical processes at metal-polymer interfaces. Therefore it is useful to study the effects of metal films on the photoluminescence of emissive organic layer fabricated on it. While investigating these processes we observed an interesting and unexpected phenomenon that, when conjugated polymer is deposited on thin gold film substrates, it exhibits remarkable photo-stability relative to that deposited on glass, even in the presence of molecular oxygen. This paper addresses the photo-stability enhancement by thin Au films and explores the photochemical mechanism behind it.
Gold nanoclusters hold many potential applications such as biosensing and optics due to their emission characteristics, small size, and non-toxicity. However, their low quantum yields remain problematic for further applications, and their fluorescence mechanism is still unclear. To increase the low quantum yields, various methods have been performed: doping, tuning structures, and changing number of gold atoms. In the past, most characterizations have been performed on spherical shaped nanoclusters; in this paper, several characterizations of various rod-shaped Au nanoclusters specifically on Au25 are shown. It has been determined that the central gold atom in Au25 nano-rod is crucial in fluorescence. Furthermore, single molecule analysis of silver doped Au25 nano-rod revealed that it has more photo-stability than conjugated polymers and quantum dots.
The phenomenon of electric field-induced emission quenching is important in organic light-emitting diodes because operating conditions involve large electric fields. Past experimental work on light-emitting polymers and oligomers showed that field-induced quenching (FIQ) efficiencies are higher in non-rigid molecules such as poly(pphenylene vinylene) or PPV, than in similar, more planar molecules. Based on this relationship, we previously proposed that the applied field enhances internal conversion decay channels. Our further studies built on this idea by examining FIQ in PPV oligomers of varying length using computational methods. Calculations performed at the INDO/S-CI level showed the presence of free electron-hole pair (FEHP) states which are stabilized by the uniform external electric field. These FEHP states undergo an avoided crossing with the fluorescent 1Bu bound exciton state at sufficiently high field magnitudes. The magnitude of the electronic coupling between the FEHP and 1Bu state, determined from these avoided crossings, is found to be a function of the field at which these states cross. This function is universal in that it applies to all FEHP states in PPV. This includes FEHP states on different length oligomers and the multiple FEHP states on a given length oligomer. Combining this universal function with simple models for the surrounding dielectric medium and effects of disorder allowed Marcus theory to be used to develop a model of FIQ. The resulting model yields reasonable quantitative agreement with FIQ magnitudes, dependence on oligomer length, and threshold field strengths at which quenching is observed. Here, the universal curve, relating electronic coupling to the field at which the FEHP and 1Bu states cross, is examined for planar, ordered oligomers of polyfluorene and ladder-type poly(p-phenylene). The dependence is similar to PPV, suggesting that this curve is universal not just across states, but also across this family of conjugated polymers. Given that the electronic couplings are similar, the observed differences in FIQ may be attributed to other factors, including especially the reduced degree of structural disorder present for these more rigid systems.
Organic light-emitting diodes (OLEDs) have received a significant attention over the past decade due to their energy-saving potential. We have recently synthesized two novel carbazole-based donor-acceptor compounds and analyzed their optical properties to determine their suitability for use as blue emitters in OLEDs. These compounds show remarkable photo-stability and high quantum yields in the blue region of the spectrum. In addition, they have highly solvatochromic emission. In non-polar solvents, bright, blue-shifted (λmax ≈ 398 nm), and highly structured emission is seen. With increasing solvent dielectric constant, the emission becomes weaker, red-shifted (λmax ≈ 507 nm), and broad. We aim to determine the underlying cause of these changes. Electronic structure calculations indicate the presence of multiple excited states with comparable oscillator strength. These states are of interest because there are several with charge-transfer (CT) character, and others centered on the donor moiety. We theorize that CT states play a role in the observed changes in emission lineshape and may promote charge mobility for electrofluorescence in OLEDs. In the future, we plan to use Stark spectroscopy to analyze the polarity of excited states and transient absorption spectroscopy to observe the dynamics in the excited state.
Applications of conjugated polymers in photovoltaics and displays drive the need to understand how morphology affects
emission and charge migration. Due to the inherent complexity of polymers, parallel studies of oligomer aggregates are
required to ‘build-up' an understanding of the polymer features. Fluorescence lifetime imaging microscopy (FLIM) is
used to probe variations in vibronic patterns and emission lifetime between individual aggregates and trends in these
properties as a function of aggregate size. This technique yields insight into the structure and packing properties of these
materials in the aggregated state.
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