Polaron Pairs Research Articles

Enhanced Optical Gain Through Efficient Polaron Pairs Recombination in F8xBTy

AbstractOrganic semiconductors combine excellent optoelectronic properties with simple fabrication to obtain the desired features by tuning their chemical structures. Förster resonant energy transfer (FRET) is in designing blended gain media, but it does not enhance efficient optical gain in most cases. This is due to the competition between polaron pairs and stimulated emission (SE), leading to quenching of SE. Thus a challenge to design efficient optical gain systems via FRET. Here, a series of copolymers, F8xBTy, through uniformly inserting benzothiadiazole (BT) units into the 9,9‐dioctylfluorene (F8) chain, were synthesized. They consist of both charge transfer (CT) and FRET is synthesized. These copolymers can prevent the local F8 aggregation and lead to efficient polaron pair recombination into singlet excitons. The F8 excitons are thus spatially confined, increasing efficient SE. Efficient light amplification has low amplified spontaneous emission (ASE) thresholds (as low as 5.3 µJ cm−2) and significantly enhanced optical gain with gain coefficients up to 37 cm−1. The distributed feedback (DFB) lasers has low lasing thresholds down to 5.4 nJ per pulse. The results suggest that these copolymers provide a organic gain media design strategy with efficient optical gain, introducing a new approach to developing laser materials for electrically pumped lasers.

Modulating Polaron Behavior in PM6 Blends with Nonfullerene and Fullerene Acceptors: The Importance of Singlet Energy Transfer

AbstractNon‐fullerene acceptors are paving the way toward high‐efficiency organic photovoltaics. In the quest to both understand the origins of these high efficiencies and to push them ever higher, the interactions between the different excited states that contribute to device function ineeds to be understood. In this work, the presence and behavior of bimodal polarons are investigated in high‐performing conjugated polymer PM6 and its blends with non‐fullerene acceptor ITIC‐4F and fullerene acceptor PC60BM. Transient absorption spectroscopy is used to gain insight into the blends’ polarons as a function of blend ratio. Two types of polymer polaron are identified in the PM6:fullerene blends: bound polarons located in pure polymer domains and “interfacial” polarons located in mixed domains. In contrast, the PM6 polarons observed in PM6:ITIC‐4F blends show very different behavior, most notably an almost complete lack of the bound polarons. This loss is attributed to efficient singlet energy transfer from donor to acceptor prior to charge photogeneration taking place. This energy transfer suppresses the formation of bound polaron pairs that rapidly decay back to the ground state, thereby providing another pathway that enables high efficiencies in non‐fullerene acceptor‐based organic photovoltaics.

Analysis of polaron pair lifetime dynamics and secondary processes in exciplex driven TADF OLEDs using organic magnetic field effects

Magnetic field effects (MFEs) in thermally activated delayed fluorescence (TADF) materials have been shown to influence the reverse intersystem crossing (RISC) and to impact on electroluminescence (EL) and conductivity. Here, we present a novel model combining Cole–Cole and Lorentzian functions to describe low and high magnetic field effects originating from hyperfine coupling, the g mechanism, and triplet processes. We applied this approach to organic light-emitting devices of third generation based on tris(4-carbazoyl-9-ylphenyl)amine (TCTA) and 2,2′,2″-(1,3,5-benzinetriyl)-tris(1-phenyl-1-H-benzimidazole) (TPBi), exhibiting blue emission, to unravel their loss mechanisms. The quality of the regression function was evaluated using k-fold cross-validation. The scoring was compared to various alternative fitting functions, which were previously proposed in literature. Density functional theory calculations, photoluminescence, and electroluminescence studies validated the formation of a TADF exciplex system. Furthermore, we propose successful encapsulation using a semi-permeable polymer, showing promising results for magnetic field sensing applications on arbitrary geometry. This study provides insights into the origin of magnetic field effects in exciplex-TADF materials, with potential applications in optoelectronic devices and sensing technologies.

Polaron Pair-Mediated Radiative Recombination of Singlet Excitons in a Conjugated Polymer Aggregate by Plasmonic and Semiconductor Nanocrystals.

We investigated the excited-state dynamics of a conjugated polymer (CP:P3HT)-based ternary hybrid system containing P3HT-coated gold nanoparticles and quantum dots. Transient absorption spectroscopy results revealed that polaron pairs (PPs) originating from nonrelaxed singlet (S1) excitons of the CP aggregate in the ternary system have shorter electron-hole separation distances than those of PPs in the neat CP aggregate because of the photophysical effects of plasmonic and semiconductor nanocrystals. In particular, the shorter electron-hole distances of PPs led to more back-recombination to S1 excitons than dissociation into positive polarons in the ternary system, resulting in increased S1 radiative recombination compared with that in the neat CP system. Thus, the photoluminescence intensity of the CP aggregate in the ternary system increased. Our findings provide new insights into the excited-state dynamics of CPs and pave the way for the development of next-generation high-efficiency optoelectronic devices.

RadicalPy: A Tool for Spin Dynamics Simulations.

Radical pairs (electron-hole pairs, polaron pairs) are transient reaction intermediates that are found and exploited in all areas of science, from the hard realm of physics in the form of organic semiconductors, spintronics, quantum computing, and solar cells to the soft domain of chemistry and biology under the guise of chemical reactions in solution, biomimetic systems, and quantum biology. Quantitative analysis of radical pair phenomena has historically been successful by a few select groups. With this in mind, we present an intuitive open-source framework in the Python programming language that provides classical, semiclassical, and quantum simulation methodologies. A radical pair kinetic rate equation solver, Monte Carlo-based spin dephasing rate estimations, and molecule database functionalities are implemented. We introduce the kine-quantum method, a new approach that amalgamates classical rate equations, semiclassical, and quantum techniques. This method resolves the prohibitively large memory requirement issues of quantum approaches while achieving higher accuracy, and it also offers wavelength-resolved simulations, producing time- and wavelength-resolved magnetic field effect simulations. Model examples illustrate the versatility and ease of use of the software, including the new approach applied to the magnetosensitive absorption and fluorescence of flavin adenine dinucleotide photochemistry, spin-spin interaction estimation from molecular dynamics simulations on radical pairs inside reverse micelles, radical pair anisotropy inside proteins, and triplet exciton pairs in anthracene crystals. The intuitive interface also allows this software to be used as a teaching or learning aid for those interested in the field of spin chemistry. Furthermore, the software aims to be modular and extensible, with the aim to standardize how spin dynamics simulations are performed.

Unlocking amplified magneto-photocurrent using multi-field manipulation in nonfullerene organic bulk heterojunction systems.

An effective manipulation of polaron pairs (PPs) for realizing amplified magneto-photocurrent (AMPC) is of critical importance toward the development of low power consumption and high-performance organic spin-optoelectronic devices, for instance magneto-photo-volatile memories. By far, it is challenging and there is a lack of method to reach AMPC. The typical magneto-photocurrent due to the light-matter interanion is primarily for unveiling the spin-dependent electron-hole dissociation in organic solar cells. Herein, we achieved an AMPC of ∼140% in nonfullerene organic bulk heterojunction systems at room temperature. We found that the amplification can be effectively triggered by a multi-field to a large number of photogenerated PPs at intermediate charge transfer states. We further postulate that, at steady state, they may experience a cyclic photophysical process due to the triplet-exciton polaron interaction. This study paves the way for the realization of AMPC in the organic spin-optoelectronic system.

(Invited) Influence of Vibronic Interaction of Charge Transfer Excitons in PTB7/BTA-Based Nonfullerene Organic Solar Cells

For the design of rational D/A interfaces, it is important to elucidate the dynamic processes of excitons generated at the D/A stacking structure interface and the photoelectric conversion mechanism. We predict that the charge-transfer excitons initially formed are weakly bound electron-hole polaron pairs, which dissociate without relaxing to the charge-transfer state and diffuse as free electron polarons and hole polarons. We consider this to be a nonadiabatic process due to oscillatory interactions in the initial charge-transfer excitonic state. In this study, we use time-dependent DFT to investigate the electronic structure, electron-hole distance, electron coupling in charge transfer state generated by photoexcitaion and the Huang- Rhys factors of the D/A complex BTAx, PCTBT/BTAx and PDCBT/BTAx (x = 1, 3)) in the excited state and the exciton-phonon coupling and nonadiabatic process. Based on the above, we aim to elucidate the role of vibronic interactions in CT excitonic states and the control of JSC and electron-hole recombination.

Slow vibrational relaxation drives ultrafast formation of photoexcited polaron pair states in glycolated conjugated polymers

Glycol sidechains are often used to enhance the performance of organic photoconversion and electrochemical devices. Herein, we study their effects on electronic states and electronic properties. We find that polymer glycolation not only induces more disordered packing, but also results in a higher reorganisation energy due to more localised π-electron density. Transient absorption spectroscopy and femtosecond stimulated Raman spectroscopy are utilised to monitor the structural relaxation dynamics coupled to the excited state formation upon photoexcitation. Singlet excitons are initially formed, followed by polaron pair formation. The associated structural relaxation slows down in glycolated polymers (5 ps vs. 1.25 ps for alkylated), consistent with larger reorganisation energy. This slower vibrational relaxation is found to drive ultrafast formation of the polaron pair state (5 ps vs. 10 ps for alkylated). These results provide key experimental evidence demonstrating the impact of molecular structure on electronic state formation driven by strong vibrational coupling.

P‐253: Late‐News Poster: The Evaluation on the Stability of Electroluminescent Materials Using Polaron Pair Formation Kinetics

We developed the method for evaluation of the stability of electroluminescent materials by using QEMS (quantum efficiency measurement system). Relative PL (photoluminescence) intensity decay of BDs (blue dopants) with BHs (blue hosts) in solution under UV light irradiation were measured and the rate constants for polaron pair formation by electron transfer were determined through first‐order kinetics analyses. The rate constants of polaron pair formation (6.487E‐04 –1.805E‐03 min‐1 ) were inversely proportional to the lifetime of OLED (organic light‐emitting diode) devices. We expect that this evaluation method can be applied to the development of new OLED materials and longer lifetime OLED devices.

An Electronic Structure Investigation of PEDOT with AlCl4- Anions-A Promising Redox Combination for Energy Storage Applications.

In this work, we use density functional theory to investigate the electronic structure of poly(3,4-ethylenedioxythiophene) (PEDOT) oligomers with co-located AlCl4- anions, a promising combination for energy storage. The 1980s bipolaron model remains the dominant interpretation of the electronic structure of PEDOT despite recent theoretical progress that has provided new definitions of bipolarons and polarons. By considering the influence of oligomer length, oxidation or anion concentration and spin state, we find no evidence for many of the assertions of the 1980s bipolaron model and so further contribute to a new understanding. No self-localisation of positive charges in PEDOT is found, as predicted by the bipolaron model at the hybrid functional level. Instead, our results show distortions that exhibit a single or a double peak in bond length alternations and charge density. Either can occur at different oxidation or anion concentrations. Rather than representing bipolarons or polaron pairs in the original model, these are electron distributions driven by a range of factors. Distortions can span an arbitrary number of nearby anions. We also contribute a novel conductivity hypothesis. Conductivity in conducting polymers has been observed to reduce at anion concentrations above 0.5. We show that at high anion concentrations, the energy of the localised, non-bonding anionic orbitals approaches that of the system HOMO due to Coulombic repulsion between anions. We hypothesize that with nucleic motion in the macropolymer, these orbitals will interfere with the hopping of charge carriers between sites of similar energy, lowering conductivity.

Dynamics of electron-hole pairs in interface exciplex OLEDs investigated by magnetic field effects

Interface exciplex organic light-emitting diodes (OLEDs) have attracted intense attention due to the advantages including well-confined recombination regions, barrier-free charge transport and thermally activated delayed fluorescence (TADF) characteristics. To investigate the spin evolutions and dynamics of electron-hole (e-h) pairs, such as polaron pairs (PPs) and charge transfer (CT) excitons, in interface exciplex OLEDs is crucial for a better understanding on their energy gain and loss mechanisms. In this work, microscopic dynamics of e-h pairs in interface exciplex OLEDs were investigated by magneto-electroluminescence (MEL) and magneto-conductivity (MC) responses. The interface exciplex OLEDs were fabricated using 4,4,4-tris(N-3-methylphenyl-N-phenylamino) triphenylamine (m-MTDATA) as the donor and 2,4,6-tris(biphenyl-3-yl)-1,3,5-triazine (T2T) as the acceptor. Hyperfine interaction (HFI)- and different g-factors between electrons and holes (Δg mechanism)-dominated spin flip processes, and recombination and dissociation processes such as triplet-triplet annihilation (TTA) and triplet-charge annihilation (TQA) were identified, and their changes with temperature and current were explored. Our results may provide valuable insights into the evolution of carriers and facilitate the development of interface exciplex-based OLEDs.

Exploring charge generation and separation in tandem organic light-emitting diodes based on magneto-electroluminescence

5,6,11,12-tetraphenylnaphthacene (rubrene) exhibits resonant energy properties (E S1,rub ≈ 2E T1,rub), resulting in rubrene-based organic light-emitting diode (OLED) devices that undergo the singlet fission (STT) process at room temperature. This unique process gives rise to a distinct magneto-electroluminescence (MEL) profile, differing significantly from the typical intersystem crossing (ISC) process. Therefore, in this paper, we investigate charge generation and separation in the interconnector, and the mechanism of charge transport in tandem OLEDs at room temperature using MEL tools. We fabricate tandem OLEDs comprising green (Alq3) and yellow (Alq3:rubrene) electroluminescence (EL) units using different interconnectors. The results demonstrate that all devices exhibited significant rubrene emission. However, the MEL did not exhibit an STT process with an increasing magnetic field, but rather a triplet–triplet annihilation (TTA) process. This occurrence is attributed to direct carrier trapping within doped EL units, which hinders the transport of rubrene trapped charges, consequently prolonging the lifetime of triplet excitons (T1,rub). Thus, the increased T1,rub concentration causes TTA to occur at room temperature, causing the rapid decrease of MEL in all devices under high magnetic fields. In devices where only the TTA process occurs, the TTA increases with the increasing current. Consequently, the high magnetic field of devices A–C is only related to TTA. Notably, there exists a high magnetic field TTA of device D in the Alq3/1,4,5,8,9,11-Hexaazatriphenylene-hexacarbonitrile interconnector regardless of the current. This occurs because both EL units in the device emit simultaneously, resulting in the triplet-charge annihilation process of Alq3 in the high magnetic field of the MEL. Moreover, the rapid increase in MEL at low magnetic field across all devices is attributed to the ISC between Alq3 polaron pairs. This entire process involves Förster and Dexter energy transfer. This article not only provides novel insights into charge generation and separation in the interconnector but also enhances our understanding of the microscopic mechanisms in tandem OLED devices.

Tunable Charge Transport and Spin Dynamics in Two-Dimensional Conjugated Metal-Organic Frameworks.

Two-dimensional conjugated metal-organic frameworks (2D c-MOFs) have attracted increasing interest in electronics due to their (semi)conducting properties. Charge-neutral 2D c-MOFs also possess persistent organic radicals that can be viewed as spin-concentrated arrays, affording new opportunities for spintronics. However, the strong π-interaction between neighboring layers of layer-stacked 2D c-MOFs annihilates active spin centers and significantly accelerates spin relaxation, severely limiting their potential as spin qubits. Herein, we report the precise tuning of the charge transport and spin dynamics in 2D c-MOFs via the control of interlayer stacking. The introduction of bulky side groups on the conjugated ligands enables a significant dislocation of the 2D c-MOFs layers from serrated stacking to staggered stacking, thereby spatially weakening the interlayer interactions. As a consequence, the electrical conductivity of 2D c-MOFs decreases by 6 orders of magnitude, while the spin density achieves more than a 30-fold increase and the spin-lattice relaxation time (T1) is increased up to ∼60 μs, hence being superior to the reference 2D c-MOFs with compact stackings whose spin relaxation is too fast to be detected. Spin dynamics results also reveal that spinless polaron pairs or bipolarons play critical roles in the charge transport of these 2D c-MOFs. Our strategy provides a bottom-up approach for enlarging spin dynamics in 2D c-MOFs, opening up pathways for developing MOF-based spintronics.

Observation of super-Nernstian proton-coupled electron transfer and elucidation of nature of charge carriers in a multiredox conjugated polymer.

Nernstian proton-coupled electron transfer (PCET) is a fundamental process central to many physical and biological systems, such as electrocatalysis, enzyme operation, DNA biosynthesis, pH-/bio-sensors, and electrochemical energy storage devices. We report herein the discovery of super-Nernstian PCET behavior with two protons per electron transferred in the electrochemical doping of a redox conjugated polymer, phenazine-substituted ladder poly(benzimidazobenzophenanthroline) (BBL-P), in aqueous electrolyte. We show that the super-Nernstian response originates from existence of multiredox centers that have a gradient of pKa on the conjugated polymer. Our use of various pH-dependent in operando techniques to probe the nature of charge carriers in n-doped BBL-P found that polarons are the charge carriers at low to intermediate levels of doping (0.1-1.0 electron per repeat unit (eru)) whereas at higher doing levels (1.3 eru), polarons, polaron pairs, and bipolarons co-exist, which evolve into strongly coupled polaron pairs at the highest doping levels (>1.5 eru). We show that PCET-assisted n-doping of BBL-P results in very high redox capacity (>1200 F cm-3) in acidic electrolyte. Our results provide important new insights into PCET in organic materials and the nature of charge carriers in n-doped conjugated polymers while having implications for various electrochemical devices.

Surface hopping simulations on charge photogeneration in conjugated polymers.

The mechanism of charge photogeneration in neat conjugated polymers has long been controversial and a unified explanation has not been achieved so far. In this paper, we use a surface hopping method to simulate the excited-state dynamics of a system composed of five π-stacked polymer chains. In this system, polaron pairs (PPs) with large electron-hole distance can be seen as free charges. The surface hopping method is based on the Pariser-Parr-Pople (PPP) Hamiltonian and the excited states of the system are calculated with configuration interaction singles (CIS) formalism. During the simulations, the yields of PPs and free charges are calculated using a statistical method. By comparison, it is found that impurity and excess energy have significant effects on the yields of PPs and free charges. Free charges are difficult to be generated in neat systems with small excess energy. Free charges come from direct dissociation of high-energy excitons.

Effect of electron-electron interaction on polarization process of exciton and biexciton in conjugated polymers

Abstract By using the one-dimensional tight-binding model modified to include electron-electric field interaction and electron-electron interaction, we theoretically explore the polarization process of exciton and biexciton in cis-polyacetylene. The dynamical simulation is performed by adopting the non-adiabatic evolution approach. The results show that under the effect of moderate electric field, when the strength of electron-electron interaction is weak, the singlet exciton is stable but its polarization presents obvious oscillation. With the enhancement of interaction, it is dissociated into polaron pair, the spin-flip of which could be observed through modulating the interaction strength. For the triplet exciton, the strong electron-electron interaction restrains its normal polarization, but it is still stable. In case of biexciton, the strong electron-electron interaction not only dissociate it, but also flip its charge distribution. We also calculate the yield of the possible states formed after the dissociation of exciton and biexciton.

Effect of the resonant ac-drive on the spin-dependent recombination of polaron pairs: Relation to organic magnetoresistance

The origin of magnetoresistance in bipolar organic materials is the influence of magnetic field on the dynamics of recombination within localized electron–hole pairs. Recombination from the S spin-state of the pair is preceded by the beatings between the states S and T0. Period of the beating is set by the random hyperfine field. For the case when recombination time from S is shorter than the period, we demonstrate that a weak resonant ac drive, which couples T0 to T+ and T− affects dramatically the recombination dynamics and, thus, the current. A distinctive characteristics of the effect is that the current versus the drive amplitude exhibits a maximum.

Degradation Analysis of Organic Light-Emitting Diodes through Dispersive Magneto-Electroluminescence Response.

Understanding the stability and degradation of organic light-emitting diodes (OLEDs) under working conditions is a significant area of research for developing more effective OLEDs and further improving their performance. However, studies of degradation processes by in situ noninvasive methods have not been adequately developed. In this work, tris-(8-hydroxyquinolino) aluminum (Alq3)-based OLED degradation processes have been analyzed through the investigation of the device dispersive magneto-electroluminescence (MEL(B)) response measured at room temperature. By studying the change in the MEL(B) response during the device degradation under different external stimuli, such as exposing the device to the atmosphere and prolonged illumination by a strong visible light source, we have gained insight into the microscopic spin-dependent phenomena that control the recombination of e-h polaron pairs in the device. We found that the device degradation leads to a shorter e-h polaron lifetime, smaller dispersive parameter, and broader lifetime distribution function that shows increased disorder in the active layer. This study could offer a potential tool that may be beneficial for assessing the degradation of OLED devices based on various active layers.

Molecular Weight-Dependent Oxidation and Optoelectronic Properties of Defect-Free Macrocyclic Poly(3-hexylthiophene).

The redox behaviors of macrocyclic molecules with an entirely π-conjugated system are of interest due to their unique optical, electronic, and magnetic properties. In this study, defect-free cyclic P3HT with a degree of polymerization (DPn) from 14 to 43 was synthesized based on our previously established method, and its unique redox behaviors arising from the cyclic topology were investigated. Cyclic voltammetry (CV) showed that the HOMO level of cyclic P3HT decreases from -4.86 eV (14 mer) to -4.89 eV (43 mer), in contrast to the linear counterparts increasing from -4.94 eV (14 mer) to -4.91 eV (43 mer). During the CV measurement, linear P3HT suffered from electro-oxidation at the chain ends, while cyclic P3HT was stable. ESR and UV-Vis-NIR spectroscopy suggested that cyclic P3HT has stronger dicationic properties due to the interactions between the polarons. On the other hand, linear P3HT showed characteristics of polaron pairs with multiple isolated polarons. Moreover, the dicationic properties of cyclic P3HT were more pronounced for the smaller macrocycles.

Investigations on exciton recombination and annihilation in TmPyPB-ETL OLEDs using magnetic field effects.

Although the effect of the electron transport layer (ETL) material TmPyPb on the electroluminescence performance of organic light-emitting diodes (OLEDs) has been extensively studied, the process of TmPyPb regulating exciton recombination and annihilation within the device is still unclear. Here, we fabricated devices of various TmPyPb thicknesses with and without ETL. Subsequently, we measured the magneto-electroluminescence (MEL) of these devices. Specifically, at the same luminance, the triplet-charge annihilation (TQA) process is more likely to occur as the thickness of TmPyPb increases, resulting in a decrease in the maximum luminance of devices. Due to electron leakage and exciton recombination region moving towards the cathode, leading to a decrease in luminance efficiency at first and then an enhancement with an increase in the thickness of TmPyPb. Furthermore, at room temperature, the application of a large bias voltage suppresses singlet fission (SF) processes by modulating the dissociation of singlet polaron pairs (PPS) and the concentration of triplet exciton (T1). This leads to the conversion of SF to the TQA process. At low temperatures, the bias voltage and temperature can regulate the concentration and lifetime of PPS and T1. Therefore, as the temperature decreases, the transition of SF → TQA → triplet-triplet annihilation (TTA) and TQA coexistence → TTA process occurs. Moreover, MEL responses of the TmPyPb-ETL device show a W-linear pattern owing to the combined effect of the hyperfine interaction (HFI) and Zeeman splitting at 145 K. Accordingly, we explored the electroluminescence (EL) performance of TmPyPB-ETL OLEDs and investigated the evolution of SF, TQA, and TTA processes using MEL. Our study revealed the effect of exciton recombination and annihilation in OLEDs with varying thicknesses of TmPyPb.