Bimolecular Annihilation Research Articles

Unexpected Performance of a Bifunctional Sensitizer/Activator Component for Photon Energy Management via Upconversion.

We here report on the observation of upconverted photoluminescence (UC-PL) from the blue-light-emitting 9,10-diphenylanthracene (DPA) mixed with the yellow-light-absorbing bifunctional sensitizer/activator component of (3,3,7,8,12,13,17,18-octaethylporphyrin-22,24-diid-2-one) PtII (PtOEP-K). Yellow-to-blue UC-PL (0.680 eV spectral upshift) is achieved at room temperature under ultralow power continuous incoherent photoexcitation (220 μW/cm2) despite the absence of triplet energy transfer (TET) between PtOEP-K and DPA. Under selective CW-laser photoexcitation of PtOEP-K in DPA:PtOEP-K, a 2.5% UC-PL quantum yield is obtained; that is an improvement exceeding by more than 3 orders of magnitude the UC-PL quantum yield of TTA-UC material combinations wherein no TET is operative. The PL response of DPA:PtOEP-K to varying laser fluence suggests that bimolecular annihilation reactions between triplet-excited PtOEP-K facilitate the UC-PL activation in DPA. These findings pave the way toward low-complexity strategies for the reduction of transmission losses in solar energy technologies through an innovative wavelength upshifting protocol involving excitonic materials.

Impact of Photoluminescence Imaging Methodology on Transport Parameters in Semiconductors.

Triplet-triplet annihilation-induced delayed emission provides a pathway for investigating triplets via emission spectroscopy. This bimolecular annihilation depends directly on the transport properties of triplet excitons in disordered organic semiconductors. Photoluminescence (PL) imaging is a direct method for studying exciton and charge-carrier diffusivity. However, most of these studies neglect dispersive transport. Early time scale measurements using this technique can lead to an overestimation of the diffusion coefficient (DT) or diffusion length (Ld). In this study, we investigated the time-dependent triplet DT using PL imaging. We observed an overestimation of Ld in classical delayed PL imaging, often 1 order of magnitude higher than the actual Ld value. We compared various thicknesses of polymeric thin films to study the dispersive nature of triplet excitons. Transient analysis of delayed PL imaging and steady state imaging reveals the importance of considering the time-dependent nature of DT for the triplet excitons in disordered electronic materials.

Resolving Nonlinear Recombination Dynamics in Semiconductors via Ultrafast Excitation Correlation Spectroscopy: Photoluminescence versus Photocurrent Detection.

We explore the application of excitation correlation spectroscopy to detect nonlinear photophysical dynamics in two distinct semiconductor classes through time-integrated photoluminescence and photocurrent measurements. In this experiment, two variably delayed femtosecond pulses excite the semiconductor, and the time-integrated photoluminescence or photocurrent component arising from the nonlinear dynamics of the populations induced by each pulse is measured as a function of inter-pulse delay by phase-sensitive detection with a lock-in amplifier. We focus on two limiting materials systems with contrasting optical properties: a prototypical lead-halide perovskite (LHP) solar cell, in which primary photoexcitations are charge photocarriers, and a single-component organic-semiconductor diode, which features Frenkel excitons as primary photoexcitations. The photoexcitation dynamics perceived by the two detection schemes in these contrasting systems are distinct. Nonlinear-dynamic contributions in the photoluminescence detection scheme arise from contributions to radiative recombination in both materials systems, while photocurrent arises directly in the LHP but indirectly following exciton dissociation in the organic system. Consequently, the basic photophysics of the two systems are reflected differently when comparing measurements with the two detection schemes. Our results indicate that photoluminescence detection in the LHP system provides valuable information about trap-assisted and Auger recombination processes, but that these processes are convoluted in a nontrivial way in the photocurrent response and are therefore difficult to differentiate. In contrast, the organic-semiconductor system exhibits more directly correlated responses in the nonlinear photoluminescence and photocurrent measurements, as charge carriers are secondary excitations only generated through exciton dissociation processes. We propose that bimolecular annihilation pathways mainly contribute to the generation of charge carriers in single-component organic semiconductor devices. Overall, our work highlights the utility of excitation correlation spectroscopy in modern semiconductor materials research, particularly in the analysis of nonlinear photophysical processes, which are deterministic for their electronic and optical properties.

Highly Crystalline Rubrene Light‐Emitting Diodes with Epitaxial Growth

AbstractConventional organic optoelectronic devices suffer from low carrier mobility limited by the static and dynamic disorder. Organic crystals with long‐range order can circumvent the effects of disorder and significantly improve the charge transport. While highly ordered organic crystals offer the desirable electronic coupling strength and charge transport, their integration into large‐area optoelectronic devices remains a challenge. Here, monolithic integrated triclinic crystal rubrene light‐emitting diodes (LEDs) are presented using epitaxial growth with functional additives being engineered into the films. Superior charge transport, excellent operational and long‐term stability in these light‐emitting devices are demonstrated. By comparing two rubrene‐based LEDs, one made from amorphous and one from crystalline rubrene layers, their exciton dynamics are estimated using comprehensive transient electroluminescence simulation. The crystalline LEDs show high triplet‐triplet annihilation (TTA) rate constant similar to TTA rate constant of triclinic single crystals determined by optical spectroscopy. At the same time, the crystalline phase enhances drastically the singlet‐fission and bimolecular annihilation rates, which reduces the overall performance of the LED compared to its amorphous counterpart. Finally, an outlook on the potential applications of rubrene and/or its derivatives crystalline films are provided for enhancing the performance of organic and hybrid optoelectronic devices.

Boosting the Efficiency of Organic Solid‐State Lasers by Solvato‐Tailored Assemblies

AbstractThe photophysical properties of pure organic materials in solid‐state are widely related to the crystal's arrangements. Herein, 4,6‐bis((E)‐4‐(dibenzothiophene)styryl)‐5(ethoxycarbonyl)‐2,2‐difluoro‐2H‐1,3,2‐dioxaborinin‐1‐ium‐2‐uide (BBSF) is employed as a mode molecule to explore the relationship between molecular arrangement and performance. Three elegant crystals (solvent‐free‐J‐aggregation of EA‐crystal, solvent‐J‐aggregations of CB‐crystal, and FB‐crystal) are obtained by solvato‐tailored strategy. Detailed single crystal structures and photophysical data reveal that all the three crystals adopt a J‐type aggregation model. EA‐crystal does not involve solvent molecular while the CB‐ and FB‐crystals involve chlorobenzene (CB) and fluorobenzene (FB) molecules, respectively. Solvent molecules can effectively separate the two columns of BBSF molecules, resulting in high brightness emission. Laser behaviors indicate that the solvent‐microcrystals display higher brightness, lower threshold, as well as higher quality factor than solvent‐free‐microcrystal due to the weakened bimolecular exciton annihilation process. This strategy not only paves an intriguing way to the construction and preparation of pure organic J‐aggregation laser materials but also offers a guideline for suppressing bmEA process through introducing solvent molecules.

Kinetics of the Photoexcited States in Thin Films of Metallo-Supramolecular Polymers With Ditopic Thiophene-Bridged Terpyridine Ligands.

Managing the excited-state decay by a supramolecular structure is a crucial issue for organic photovoltaics. We show that in thin films of metallo-supramolecular polymers made of bis(terpyridine-4′-yl)terthiophenes and coupling ions, the photoexcited states generated by ultrashort laser pulses at the wavelength of 440 nm decay by the bi-molecular annihilation predominantly controlled by the Förster transfer between singlet states. During this bi-molecular annihilation of singlet states, intermediate hot triplet pairs are formed, which subsequently dissociate into long-living diffusing triplet states. It explains a significant shortening of the triplet state rise time with increasing pump fluence. The diffusion coefficient of triplets showed power-law time dependence, with its exponent proportional to the pump fluence, decreasing thus the diffusivity of triplets.

Triplet Sensitization by Lead Halide Perovskite Thin Films for Efficient Solid-State Photon Upconversion at Subsolar Fluxes

Summary We investigate the rubrene triplet sensitization by perovskite thin films based on methylammonium formamidinium lead triiodide (MAFA) of varying thicknesses. The power-law dependence of both the MAFA photoluminescence (PL) intensity and upconverted emission is tracked as a function of the incident power density. Bimolecular triplet-triplet annihilation (TTA) exhibits a unique power-law dependence with a slope change from quadratic-to-linear at the threshold Ith. The underlying MAFA PL power-law dependence dictates the power law of the upconverted PL: (1) below Ith, the slope of the upconverted PL is twice the value of the MAFA PL; (2) above Ith, it follows the same power law as the underlying recombination of mobile electrons and holes in the MAFA films. We find that the Ith shifts to subsolar incident laser powers when increasing the MAFA thickness above 30 nm. For the thickest MAFA film of 380 nm we find an upconversion threshold of Ith = 7.1 mW/cm2.

All-Solution-Based Aggregation Control in Solid-State Photon Upconverting Organic Model Composites.

Hitherto, great strides have been made in the development of organic systems that exhibit triplet-triplet annihilation-induced photon-energy upconversion (TTA-UC). Yet, the exact role of intermolecular states in solid-state TTA-UC composites remains elusive. Here we perform a comprehensive spectroscopic study in a series of solution-processable solid-state TTA-UC organic composites with increasing segregated phase content for elucidating the impact of aggregate formation in their TTA-UC properties. Six different states of aggregation are reached in composites of the 9,10-diphenylanthracene (DPA) blue emitter mixed with the (2,3,7,8,12,13,17,18-octaethylporphyrinato)platinum(II) sensitizer (PtOEP) in a fixed nominal ratio (2 wt % PtOEP). Fine-tuning of the PtOEP and DPA phase segregation in these composites is achieved with a low-temperature solution-processing protocol when three different solvents of increasing boiling point are alternatively used and when the binary DPA:PtOEP system is dispersed in the optically inert polystyrene (PS) matrix (PS:DPA:PtOEP). Time-gated (in the nanosecond and microsecond time scales) photoluminescence measurements identify the upper level of PtOEP segregation at which the PtOEP aggregate-based networks favor PtOEP triplet exciton migration toward the PtOEP:DPA interfaces and triplet energy transfer to the DPA triplet manifold. The maximum DPA TTA-UC luminescence intensity is ensured when the bimolecular annihilation constant of PtOEP remains close to γTTA-PtOEP = 1.1 × 10-13 cm3 s-1. Beyond this PtOEP segregation level, the DPA TTA-UC luminescence intensity decreases because of losses caused by the generation of PtOEP delayed fluorescence and DPA phosphorescence in the nanosecond and microsecond time scales, respectively.

Determining the Origin of Half-bandgap-voltage Electroluminescence in Bifunctional Rubrene/C60 Devices

Lowering the driving voltage of organic light-emitting diodes (OLEDs) is an important approach to reduce their energy consumption. We have fabricated a series of bifunctional devices (OLEDs and photovoltaics) using rubrene and fullerene (C60) as the active layer, in which the electroluminescence threshold voltage(~1.1 V) was half the value of the bandgap of rubrene. Magneto-electroluminescence (MEL) response of planner heterojunction diodes exhibited a small increase in response to a low magnetic field strength (<20 mT); however, a very large decay was observed at a high magnetic field strength (>20 mT). When a hole-transport layer with a low mobility was included in these devices, the MEL response reversed in shape, and simultaneously, the EL threshold voltage became larger than the bandgap voltage. When bulk heterojunction device was examined, the amplitude of MEL curves presented an anomalous voltage-dependence. Following an analysis of the MEL responses of these devices, we proposed that the EL of half-bandgap-voltage device originated from bimolecular triplet-triplet annihilation in the rubrene film, rather than from singlet excitons that formed via an interface auger recombination. This work provides critical insight into the mechanisms of OLED emission and will help advance the applications of bifunctional devices.

Effect of reverse intersystem crossing rate to suppress efficiency roll-off in organic light-emitting diodes with thermally activated delayed fluorescence emitters

Electroluminescence efficiency roll-off in organic light-emitting diodes with thermally activated delayed fluorescence emitters 1,2-bis(carbazol-9-yl)-4,5-dicyanobenzene (2CzPN) and 3-(9,9-dimethylacridin-10(9H)-yl)-9H-xanthen-9-one (ACRXTN) is investigated by considering intramolecular exciton relaxation processes. Electroluminescence efficiency roll-off at high current density is dramatically suppressed using ACRXTN as an emitter instead of 2CzPN because of suppressed bimolecular exciton annihilation processes such as singlet⿿triplet and triplet⿿triplet annihilation. The rate constant of reverse intersystem crossing from triplet to singlet excited states of ACRXTN is about 300 times higher than that of 2CzPN, decreasing triplet exciton density and suppressing exciton annihilation processes under optical and electrical excitation.

Self-Assembled Microdisk Lasers of Perylenediimides.

Organic solid-state lasers (OSSLs) have been a topic of intensive investigations. Perylenediimide (PDI) derivatives are widely used in organic thin-film transistors and solar cells. However, OSSLs based on neat PDIs have not been achieved yet, owing to the formation of H-aggregates and excimer trap-states. Here, we demonstrated the first PDI-based OSSL from whispering-gallery mode (WGM) hexagonal microdisk (hMD) microcavity of N,N'-bis(1-ethylpropyl)-2,5,8,11-tetrakis(p-methyl-phenyl)-perylenediimide (mp-PDI) self-assembled from solution. Single-crystal data reveal that mp-PDI molecules stack into a loosely packed twisted brickstone arrangement, resulting in J-type aggregates that exhibit a solid-state photoluminescence (PL) efficiency φ > 15%. Moreover, we found that exciton-vibration coupling in J-aggregates leads to an exceptional ultrafast radiative decay, which reduces the exciton diffusion length, in turn, suppresses bimolecular exciton annihilation (bmEA) process. These spectral features, plus the optical feedback provided by WGM-hMD microcavity, enable the observation of multimode lasing as evidenced by nonlinear output, spectral narrowing, and temporal coherence of laser emission. With consideration of high carrier-mobility associated with PDIs, hMDs of mp-PDI are attractive candidates on the way to achieve electrically driven OSSL.

Stress evolution in Si during low-energy ion bombardment

Abstract

Geminate and nongeminate recombination of triplet excitons formed by singlet fission.

We report the simultaneous observation of geminate and nongeminate triplet-triplet annihilation in a solution-processable small molecule TIPS-tetracene undergoing singlet exciton fission. Using optically detected magnetic resonance, we identify recombination of triplet pairs directly following singlet fission, as well as recombination of triplet excitons undergoing bimolecular triplet-triplet annihilation. We show that the two processes give rise to distinct magnetic resonance spectra, and estimate the interaction between geminate triplet excitons to be 60 neV.

Low-temperature solution-processed wavelength-tunable perovskites for lasing

Low-temperature solution-processed materials that show optical gain and can be embedded into a wide range of cavity resonators are attractive for the realization of on-chip coherent light sources. Organic semiconductors and colloidal quantum dots are considered the main candidates for this application. However, stumbling blocks in organic lasing include intrinsic losses from bimolecular annihilation and the conflicting requirements of high charge carrier mobility and large stimulated emission; whereas challenges pertaining to Auger losses and charge transport in quantum dots still remain. Herein, we reveal that solution-processed organic-inorganic halide perovskites (CH3NH3PbX3 where X = Cl, Br, I), which demonstrated huge potential in photovoltaics, also have promising optical gain. Their ultra-stable amplified spontaneous emission at strikingly low thresholds stems from their large absorption coefficients, ultralow bulk defect densities and slow Auger recombination. Straightforward visible spectral tunability (390-790 nm) is demonstrated. Importantly, in view of their balanced ambipolar charge transport characteristics, these materials may show electrically driven lasing.

Triplet Dynamics in Pentacene Crystals: Applications to Fission‐Sensitized Photovoltaics

The decay and transport of triplet excitons photogenerated via singlet exciton fission in polycrystalline and single-crystalline pentacene is reported. Using transient absorption spectroscopy, we find evidence for diffusion-mediated triplet-triplet annihilation. We estimate monomolecular lifetimes, bimolecular annihilation rate constants, and triplet exciton diffusion lengths. We discuss these results in the context of current solar cell device architectures.

Triplet dynamics in fluorescent polymer light-emitting diodes

We report a study of the triplet exciton dynamics and their effect on the performance of fluorescent organic light-emitting diodes. These polymer light-emitting diodes comprise metal oxide, injection electrodes, and poly(9,9${}^{\ensuremath{'}}$-dioctylfluorene-co-benzothiadiazole) as the emissive material and exhibit external quantum efficiencies up to 6.5$%$. Transient optical absorption measurements following a short (0.5 to 50 $\ensuremath{\mu}$s) electrical drive pulse were used to monitor triplet dynamics during device operation. Triplet generation and decay processes were modeled, and we find that triplet-triplet annihilation is the dominant triplet decay mechanism. Singlet states, generated from triplet-triplet annihilation were monitored as delayed electroluminescence after the end of the drive pulse. From the delayed electroluminescence dynamics, we determine monomolecular as well as bimolecular triplet decay rates and estimate the triplet-charge annihilation rate. Singlet states generated from bimolecular triplet-triplet annihilation contribute up to 33$%$ of the total amount of singlets generated in these fluorescent devices. To model these results, we require that triplet states can undergo bimolecular annihilation several times. With this model, we show that singlets can reach a maximum fraction of 40$%$ of all excitons generated by charge recombination, without violating spin statistics. Singlet states generated from triplet-triplet annihilation are one important explanation for high external quantum efficiencies found in these fluorescent devices.

The Binding Energy of Charge-Transfer Excitons Localized at Polymeric Semiconductor Heterojunctions

We address the binding energy of charge-transfer excitons at organic semiconductor heterojunctions by investigating a polymer blend where the energy of the intramolecular singlet exciton is just sufficient to create separated charge pairs, placing the system at the threshold for photovoltaic operation. At 10 K, we report long-lived photoluminescence arising from charge recombination and triplet-exciton bimolecular annihilation. Both mechanisms regenerate singlet excitons in the electron acceptor, but we demonstrate that charge recombination dominates singlet regeneration dynamics on ≤300 ns time scales. This occurs by tunnelling of separated electron and holes across heterojunctions. The separated charge pairs are therefore degenerate with repopulated singlet states. From the difference of the charge-transfer and intrachain exciton emission energies, we determine that the binding energy of charge-transfer excitons with respect to bulk charge separation is ≥250 meV. Directed charge flow away from the heterojunction would avoid formation of strongly bound charge-transfer excitons, that act as traps and limit current generation in organic solar cells.

Charge Recombination and Exciton Annihilation Reactions in Conjugated Polymer Blends

Bimolecular interactions between excitations in conjugated polymer thin films are important because they influence the efficiency of many optoelectronic devices that require high excitation densities. Using time-resolved optical spectroscopy, we measure the bimolecular interactions of charges, singlet excitons, and triplet excitons in intimately mixed polyfluorene blends with band-edge offsets optimized for photoinduced electron transfer. Bimolecular charge recombination and triplet-triplet annihilation are negligible, but exciton-charge interactions are efficient. The annihilation of singlet excitons by charges occurs on picosecond time-scales and reaches a rate equivalent to that of charge transfer. Triplet exciton annihilation by charges occurs on nanosecond time-scales. The surprising absence of nongeminate charge recombination is shown to be due to the limited mobility of charge carriers at the heterojunction. Therefore, extremely high densities of charge pairs can be maintained in the blend. The absence of triplet-triplet annihilation is a consequence of restricted triplet diffusion in the blend morphology. We suggest that the rate and nature of bimolecular interactions are determined by the stochastic excitation distribution in the polymer blend and the limited connectivity between the polymer domains. A model based on these assumptions quantitatively explains the effects. Our findings provide a comprehensive framework for understanding bimolecular recombination and annihilation processes in nanostructured materials.

Excitation Energy Transfer in Organic Materials: From Fundamentals to Optoelectronic Devices

In this review, we discuss investigations of electronic excitation energy transfer in conjugated organic materials at the bulk and single molecule level and applications of energy transfer in fluorescent and phosphorescent organic light emitting devices. A brief overview of common descriptions of energy transfer mechanisms is given followed by a discussion of some basic photophysics of conjugated materials including the generation of excited states and their subsequent decay through various channels. In particular, various examples of bimolecular excited state annihilation processes are presented. Energy transfer studies at the single molecule level provide a new tool to study electronic couplings in simple donor/acceptor dyads and conjugated polymers. Finally, energy transfer in organic electronic devices is discussed with particular emphasis on triplet emitter doped OLEDs and blends for white light emission.

Effect of F?rster-type bimolecular annihilation on fluorescence decay of porphyrin side-chain polymer

Transient fluorescence dynamics of a new kind of porphyrin side-chain polymer film ［poly［porphyrin acrylate-styrene］ (P［(por)A-S］) at high excitation density has been measured by using time-resolved fluorescence spectroscopy. The fluorescence decay becomes more rapid with the increase of the interchain polymer concentration. The origin of the concentration quenching has been analysed according to the Frster-type bimolecular annihilation theory. The theoretical analyses are in good agreement with the experimental results. Rosults show that, in the case of high excitation density, the Frster-type bimolecular annihilation is the main reason of the fast initial luminescence decay and the low luminescence efficiency of the porphyrin side-chain polymers.