Triplet Exciton Formation Research Articles

The role of charge recombination to triplet excitons in organic solar cells.

The use of non-fullerene acceptors (NFAs)in organic solar cells has led to power conversion efficiencies as high as 18%1. However, organic solar cells are still less efficient than inorganic solar cells, which typically have power conversion efficiencies of more than 20%2. A key reason for this difference is that organic solar cells have low open-circuit voltages relative to their optical bandgaps3, owing to non-radiative recombination4. For organic solar cells to compete with inorganic solar cells in terms of efficiency, non-radiative loss pathways must be identified and suppressed. Here we show that in most organic solar cells that use NFAs, the majority of charge recombination under open-circuit conditions proceeds via the formation of non-emissive NFA triplet excitons; in the benchmark PM6:Y6 blend5, this fraction reaches 90%, reducing the open-circuit voltage by 60 mV. We prevent recombination via this non-radiative channel by engineering substantial hybridization between the NFA triplet excitons and the spin-triplet charge-transfer excitons. Modelling suggests that the rate of back charge transfer from spin-triplet charge-transfer excitons to moleculartriplet excitons may be reduced by an order of magnitude, enabling re-dissociation of the spin-triplet charge-transfer exciton. We demonstrate NFA systems in which the formation of triplet excitons is suppressed. This work thus provides a design pathway for organic solar cells with power conversion efficiencies of 20% or more.

Selective Heavy Atom Effect Forming Photosensitizing Hot Spots in Double-Stranded DNA Matrix.

Triplet exciton formation is essential for photosensitization-based photochemistry and photobiology. The heavy atom effect (HAE), in the form of either external or internal mode, is a basic mechanism for increasing the triplet exciton yield of photosensitizers. Herein, we report a new HAE mode by noncovalent cohosting of heavy atoms and photosensitizers in a double-stranded DNA (dsDNA) matrix. With dsDNA bearing several thymine (T) or cytosine (C) mismatches, heavy atoms (e.g., Hg2+ or Ag+) and dsDNA-staining dyes (photosensitizers) were spatially adjoined in close proximity, thus resulting in enhanced phosphorescence and 1O2 generation from the photosensitizers. The dsDNA-hosted HAE provides highly selective recognition for the heavy atoms, which is not applicable in either the external or the internal mode. Considering the simpleness and efficiency of the spatially adjoined HAE, as well as the functionality of DNA, the proposed HAE mode is appealing for various singlet oxygen- and phosphorescence-related applications.

Pressure-Driven Reverse Intersystem Crossing: New Path toward Bright Deep-Blue Emission of Lead-Free Halide Double Perovskites.

Maximizing the regeneration of singlet excitons remains a considerable challenge in deep-blue emission systems to obtain low-cost, high-efficiency fluorescent materials. However, the formation of the long-lifetime triplet excitons generally dominates the radiative process, making it greatly difficult to harvest deep-blue emission with high color purity because of the depression of singlet excitons. Here, a very bright deep-blue emission in double perovskite Cs2Na0.4Ag0.6InCl6 alloyed with Bi doping (CNAICB) was successfully achieved by pressure-driven reverse intersystem crossing (RISC), an abnormal photophysical process of energy transfer from the excited triplet state back to the singlet. Therein, the inherently broad emission of CNAICB was associated with the self-trapped excitons (STEs) at excited triplet states, whereas the radiative recombination of STEs populated in excited singlet states was responsible for the observed deep-blue emission. Moreover, the deep-blue emission corresponds to Commission Internationale de L'Eclairage (CIE) coordinates (0.16, 0.06) at 5.01 GPa, which meets the requirement of Rec. 2020 display standards. Likewise, pressure was introduced as an efficient tool to rule out the possibility of the recombination of free excitons and clarify the long-standing conventional dispute over the origin of the low-wavelength emission of Cs2AgInCl6. Our study not only demonstrates that pressure can be a robust means to boost the deep-blue emission but also provides deep insights into the structure-property relationship of lead-free CNAICB double perovskites.

Singlet Fission in Terrylenediimide Single Crystals: Competition between Biexciton Annihilation and Free Triplet Exciton Formation

Understanding singlet fission (SF) is an important strategy for extending the power conversion efficiency of next-generation solar cells beyond the Shockley–Queisser limit. Thus far, most studies of SF have focused on polycrystalline films, whose heterogeneity often makes it difficult to probe the electronic states involved in the formation of the correlated triplet biexciton state, 1(T1T1), and its decorrelation into free triplet excitons. Polarization-resolved, femtosecond transient absorption microscopy of a 1,6,9,14-tetraphenylterrylene-3,4:11,13-bis(dicarboximide) (Ph4TDI) single crystal reveals the formation of transient spectra in <200 fs having features characteristic of 1(T1T1), 1(S1S0), and Ph4TDI•+-Ph4TDI•– charge-transfer (CT) states. This indicates that either an ultrafast equilibrium between these states occurs or that the initially formed biexciton state is a mixture of these states. This spectrum evolves in time to give the Tn ← T1 spectrum of the free triplet excitons. We show further that this initially formed state has its optical transition polarized nearly perpendicular to that of the Tn ← T1 transition in the free triplet excitons. This indicates that the observed free triplet excitons have migrated from the π-stacked Ph4TDI columns where the 1(T1T1) state is produced to neighboring, nearly orthogonal π-stacked Ph4TDI columns, resulting in a weaker electronic interaction between the free triplet excitons essential to extending their lifetimes. However, the mobility of the 1(T1T1) state in the Ph4TDI π-stacking direction results in significant annihilation of biexciton pairs limiting the yield of free triplet excitons to about 60%.

Up- and Down-Converting Photons in Molecular Carbon Materials

The Shockley-Queisser limit places an upper bound on solar conversion efficiency for a single p-n junction solar cell at slightly more than 30%. To surpass this limit, multi-exciton generation is being explored in inorganic semiconductors, while singlet fission (SF) is being investigated in arrays of conjugated organic molecules. In an optimal SF process, the lowest singlet excited state of one molecule (S1) that is positioned next to a second molecule in its ground state (S0) is down-converted into two triplet excited states (T1) each residing on one of the two adjacent molecules. The two triplet states initially form a correlated pair state 1(T1T1), which then evolves into two separated triplet states (T1 + T1). As such, the energetic requirement for SF is E(S1) ≥ 2 ´ E(T1).We have set our focus in recent years on intramolecular SF in molecular carbon materials and their studies in solution rather than on intermolecular SF investigations in crystalline films.Implicit in intramolecular SF is a resonant, direct excitation of the SF material. In dimers of molecular carbon materials linked by a myriad of molecular spacers, SF takes place with quantum yields of up to 200%. In addition, all key intermediates in the SF process, including the formation and decay of a quintet state that precedes formation of the pentacene triplet excitons, have been identified. This approach is, however, limited to the part of the solar spectrum, where, for example, the dimers of carbon materials feature a significant absorption cross-section. To employ the remaining part of the solar spectrum necessitates non-resonant, indirect excitation of the SF materials via either up- or down-conversion. For example, the up-conversion approach is realized with singlet excited states , which are accessed by two-photon absorptions (TPA). TPA is then followed in the second step of the sequence by an intramolecular SF – similar to what is seen upon resonant, direct excitation. Quite different is the down-conversion approach, which is based on an intramolecular Förster resonance energy transfer (FRET) and thereby the (photo)activation of the SF material. FRET requires the use of a complementary absorbing chromophore and enables funneling its excited state energy unidirectionally to the SF performing pentacene dimer. Again, SF completes the reaction sequence.

Triplet exciton formation for non-radiative voltage loss in high-efficiency nonfullerene organic solar cells

<h2>Summary</h2> Nonfullerene acceptor (NFA) organic solar cells (OSCs) with power conversion efficiency (PCE) reaching up to 18% has shown tremendous potential toward practical applications. However, the non-radiative recombination loss in high-efficiency NFA OSCs is evidently large, and the origin remains unclear. Herein, by combining transient absorption spectroscopy, photovoltaic characterization, and detailed energy loss analysis, we unambiguously show the formation of NFA triplet exciton from free carrier recombination as a main non-radiative recombination and energy loss channel. More importantly, in contrast to the previous energetics point of view, we show side-chain fluorination in high-efficiency NFA OSCs has little effect on charge transfer energy landscapes but efficiently inhibits charge recombination to NFA triplet excitons, leading to higher <mml:math><mml:mrow><mml:mi>V</mml:mi>OC</mml:mrow></mml:math> and PCE. Our findings provide a new view about energy loss in NFA OSCs and pave the way toward OSCs with lower <mml:math><mml:mrow><mml:mi>V</mml:mi>OC</mml:mrow></mml:math> loss and efficiency exceeding 20%.

Investigation of selective triplet exciton formation by scanning tunneling luminescence

Investigation of selective triplet exciton formation by scanning tunneling luminescence

The Interplay of Stability between Donor and Acceptor Materials in a Fullerene‐Free Bulk Heterojunction Solar Cell Blend

AbstractWith rapid advances in material synthesis and device performance, the long‐term stability of organic solar cells has become the main remaining challenge toward commercialization. An investigation of photodegradation in blend films of the donor polymer poly(3‐hexylthiophene) (P3HT) and the rhodanine‐flanked small molecule acceptor 5,5′‐[(9,9‐dioctyl‐9H‐fluorene‐2,7‐diyl)bis(2,1,3‐benzothiadiazole‐7,4‐diylmethylidyne)]bis[3‐ethyl‐2‐thioxo‐4‐thiazolidinone] (FBR) is presented in an ambient atmosphere. The photobleaching kinetics of the pure materials and their blends is correlated with the generation of radicals and triplet excitons using optical and magnetic resonance techniques. In addition, spin‐trapping methods are employed to identify reactive oxygen species (ROS). In films of P3HT, FBR, and the P3HT:FBR blend, superoxide is generated by electron transfer to molecular oxygen. However, it is found that the generation of singlet oxygen by energy transfer from the FBR triplet state is responsible for the poor stability of FBR and for the accelerated photodegradation at later times of the P3HT:FBR blend. In the early stage of degradation of the neat blend, it is protected from singlet oxygen by the fast donor–acceptor charge transfer, which competes with triplet exciton formation. These results provide initial input for a rational design of donor and acceptor materials through tuning the molecular singlet and triplet energy levels to prevent ROS‐related photodegradation.

Tuning the charge transfer character of the multiexciton state in singlet fission.

Intramolecular singlet fission (SF) produces the multiexciton correlated triplet pair state, (T1T1), prior to the formation of free triplet excitons. The nature of the multiexciton state is complex, as generation of the (T1T1) state may involve a charge transfer (CT) intermediate and has been shown to have both mixed electronic and spin characters. According to transient absorption spectroscopy, a linear terrylene-3,4:11,12-bis(dicarboximide) dimer (TDI2) exhibits solvent-dependent excited-state dynamics. As solvent polarity increases from 1,2,4-trichlorobenzene (ε = 2.2) to chlorobenzene (ε = 5.6) to 1,2-dichlorobenzene (ε = 9.9), the SF rate in TDI2 increases and the multiexciton state, which can be thought of as a linear combination of the 1(S1S0), CT, and (T1T1) states, gains more CT character. Eventually, the CT state becomes a trap state as indicated by symmetry-breaking charge separation in TDI2 in pyridine (ε = 12.3). The dielectric environment influences not only the SF rate and the relative contributions of the 1(S1S0), CT, and (T1T1) states to the overall multiexciton state but also the rate at which the state mixing evolves, with faster dynamics in higher polarity solvents. More importantly, the tunability and presence of strong CT character in the multiexciton state have implications for SF applications since they often rely on electron transfer from the free triplet excitons. This enhanced CT character in the (T1T1) state may assist with two-electron transfer directly from the (T1T1) state, allowing for facile extraction of charges in intramolecular SF systems whose (T1T1) states do not always efficiently dissociate to two triplet excitons.

The Leap from Organic Light-Emitting Diodes to Organic Semiconductor Laser Diodes

In recent years, organic light-emitting device technology has expanded from organic light-emitting diodes (OLEDs) to organic semiconductor laser diodes (OSLDs) with the progress of sophisticated mo...

Understanding the luminescent nature of organic radicals for efficient doublet emitters and pure-red light-emitting diodes.

The doublet-spin nature of radical emitters is advantageous for applications in organic light-emitting diodes, as it avoids the formation of triplet excitons that limit the electroluminescence efficiency of non-radical emitters. However, radicals generally show low optical absorption and photoluminescence yields. Here we explain the poor optical properties of radicals based on alternant hydrocarbons, and establish design rules to increase the absorption and luminescence yields for donor-acceptor-type radicals. We show that non-alternant systems are necessary to lift the degeneracy of the lowest energy orbital excitations; moreover, intensity borrowing from an intense high-lying transition by the low-energy charge-transfer excitation enhances the oscillator strength of the emitter. We apply these rules to design tris(2,4,6-trichlorophenyl)methyl-pyridoindolyl derivatives with a high photoluminescence quantum yield (>90%). Organic light-emitting diodes based on these molecules showed a pure-red emission with an over 12% external quantum efficiency. These insights may be beneficial for the rational design and discovery of highly luminescent doublet emitters.

Up- and Down-Converting Photons in Molecular Carbon Materials

The Shockley-Queisser limit places an upper bound on solar conversion efficiency for a single p-n junction solar cell at slightly more than 30%. To surpass this limit, multi-exciton generation is being explored in inorganic semiconductors, while singlet fission (SF) is being investigated in arrays of conjugated organic molecules. In an optimal SF process, the lowest singlet excited state of one molecule (S1) that is positioned next to a second molecule in its ground state (S0) is down-converted into two triplet excited states (T1) each residing on one of the two adjacent molecules. The two triplet states initially form a correlated pair state 1(T1T1), which then evolves into two separated triplet states (T1 + T1). As such, the energetic requirement for SF is E(S1) ≥ 2 ´ E(T1).We have set our focus in recent years on intramolecular SF in molecular carbon materials and their studies in solution rather than on intermolecular SF investigations in crystalline films.Implicit in intramolecular SF is a resonant, direct excitation of the SF material. In dimers of molecular carbon materials linked by a myriad of molecular spacers, SF takes place with quantum yields of up to 200%. In addition, all key intermediates in the SF process, including the formation and decay of a quintet state that precedes formation of the pentacene triplet excitons, have been identified. This approach is, however, limited to the part of the solar spectrum, where, for example, the dimers of carbon materials feature a significant absorption cross-section. To employ the remaining part of the solar spectrum necessitates non-resonant, indirect excitation of the SF materials via either up- or down-conversion. For example, the up-conversion approach is realized with singlet excited states , which are accessed by two-photon absorptions (TPA). TPA is then followed in the second step of the sequence by an intramolecular SF – similar to what is seen upon resonant, direct excitation. Quite different is the down-conversion approach, which is based on an intramolecular Förster resonance energy transfer (FRET) and thereby the (photo)activation of the SF material. FRET requires the use of a complementary absorbing chromophore and enables funneling its excited state energy unidirectionally to the SF performing pentacene dimer. Again, SF completes the reaction sequence.

Singlet exciton fission via an intermolecular charge transfer state in coevaporated pentacene-perfluoropentacene thin films.

Singlet exciton fission is a spin-allowed process in organic semiconductors by which one absorbed photon generates two triplet excitons. Theory predicts that singlet fission is mediated by intermolecular charge-transfer states in solid-state materials with appropriate singlet-triplet energy spacing, but direct evidence for the involvement of such states in the process has not been provided yet. Here, we report on the observation of subpicosecond singlet fission in mixed films of pentacene and perfluoropentacene. By combining transient spectroscopy measurements to nonadiabatic quantum-dynamics simulations, we show that direct excitation in the charge-transfer absorption band of the mixed films leads to the formation of triplet excitons, unambiguously proving that they act as intermediate states in the fission process.

Discovery of blue singlet exciton fission molecules via a high-throughput virtual screening and experimental approach.

Singlet exciton fission is a mechanism that could potentially enable solar cells to surpass the Shockley-Queisser efficiency limit by converting single high-energy photons into two lower-energy triplet excitons with minimal thermalization loss. The ability to make use of singlet exciton fission to enhance solar cell efficiencies has been limited, however, by the sparsity of singlet fission materials with triplet energies above the bandgaps of common semiconductors such as Si and GaAs. Here, we employ a high-throughput virtual screening procedure to discover new organic singlet exciton fission candidate materials with high-energy (>1.4 eV) triplet excitons. After exploring a search space of 4482 molecules and screening them using time-dependent density functional theory, we identify 88 novel singlet exciton fission candidate materials based on anthracene derivatives. Subsequent purification and characterization of several of these candidates yield two new singlet exciton fission materials: 9,10-dicyanoanthracene (DCA) and 9,10-dichlorooctafluoroanthracene (DCOFA), with triplet energies of 1.54 eV and 1.51 eV, respectively. These materials are readily available and low-cost, making them interesting candidates for exothermic singlet exciton fission sensitization of solar cells. However, formation of triplet excitons in DCA and DCOFA is found to occur via hot singlet exciton fission with excitation energies above ∼3.64 eV, and prominent excimer formation in the solid state will need to be overcome in order to make DCA and DCOFA viable candidates for use in a practical device.

Effect of the Interfacial Energy Landscape on Photoinduced Charge Generation at the ZnPc/MoS2 Interface.

Monolayer transition-metal dichalcogenide crystals (TMDC) can be combined with other functional materials, such as organic molecules, to form a wide range of heterostructures with tailorable properties. Although a number of works have shown that ultrafast charge transfer (CT) can occur at organic/TMDC interfaces, conditions that would facilitate the separation of interfacial CT excitons into free carriers remain unclear. Here, time-resolved and steady-state photoemission spectroscopy are used to study the potential energy landscape, charge transfer, and exciton dynamics at the zinc phthalocyanine (ZnPc)/monolayer (ML) MoS2 and ZnPc/bulk MoS2 interfaces. Surprisingly, although both interfaces have a type-II band alignment and exhibit sub-100 fs CT, the CT excitons formed at the two interfaces show drastically different evolution dynamics. The ZnPc/ML-MoS2 behaves like typical donor-acceptor interfaces in which CT excitons dissociate into electron-hole pairs. On the contrary, back electron transfer occur at ZnPc/bulk-MoS2, which results in the formation of triplet excitons in ZnPc. The difference can be explained by the different amount of band bending found in the ZnPc film deposited on ML-MoS2 and bulk-MoS2. Our work illustrates that the potential energy landscape near the interface plays an important role in the charge separation behavior. Therefore, considering the energy level alignment at the interface alone is not enough for predicting whether free charges can be generated effectively from an interface.

Selective triplet exciton formation in a single molecule

The formation of excitons in organic molecules by charge injection is an essential process in organic light-emitting diodes (OLEDs)1-7. According to a simple model based on spin statistics, the injected charges form spin-singlet (S1) excitons and spin-triplet (T1) excitons in a 1:3 ratio2-4. After the first report of a highly efficient OLED2 based on phosphorescence, which is produced by the decay of T1 excitons, more effective use of these excitons has been the primary strategy for increasing the energy efficiency of OLEDs. Another route to improving OLED energy efficiency is reduction of the operating voltage2-6. Because T1 excitons have lower energy than S1 excitons (owing to the exchange interaction), use of the energy difference could-in principle-enable exclusive production of T1 excitons at low OLED operating voltages. However, a way to achieve such selective and direct formation of these excitons has not yetbeen established. Here we report a single-molecule investigation of electroluminescence using a scanning tunnelling microscope8-20 and demonstrate a simple method of selective formation of T1 excitons that utilizes a charged molecule. A 3,4,9,10-perylenetetracarboxylicdianhydride (PTCDA) molecule21-25 adsorbed on a three-monolayer NaCl film atop Ag(111) shows both phosphorescence and fluorescence signals at high applied voltage. In contrast, only phosphorescence occurs at low applied voltage, indicating selective formation of T1 excitons without creating their S1 counterparts. The bias voltage dependence of the phosphorescence, combined with differential conductance measurements, reveals that spin-selective electron removal from a negatively charged PTCDA molecule is the dominant formation mechanism of T1 excitons in this system, which can be explained by considering the exchange interaction in the charged molecule. Our findings show that the electron transport process accompanying exciton formation can be controlled by manipulating an electron spin inside a molecule. We anticipate that designing a device taking into account the exchange interaction could realize an OLED with a lower operating voltage.

Spin Filter Based on EuO Monoxide

The basis of spin filter operation is the possibility to obtain different population of states with spins up and down for free electrons. However, in a magnetic macroscopic field, scattering by heavy atoms reduces their population density by 106 times. To obtain the maximum possible degree of spin polarization it is proposed to use ferromagnetic EuO in semiconductor superlattices, e. g. EuO–SrO. The article substantiates the creation of a spin filter based on a superlattice composed of SrO and EuO nanolayers. The scheme of ferromagnetic semiconductor EuO energy levels is demonstrated as well as splitting of 5d EuO levels by crystal field. The position of 4f 7-multiplet and the energy of formation of triplet exciton are determined.

Evidence for Charge-Transfer Mediation in the Primary Events of Singlet Fission in a Weakly Coupled Pentacene Dimer

Summary Singlet fission (SF) is a process that converts one singlet excited state into two triplet states. The mechanism of SF is still not well understood. Here, we report on the use of a combination of transient absorption and electron paramagnetic resonance spectroscopies in conjunction with theoretical calculations to probe SF in a pentacene dimer linked by a non-conjugated, 1,4-diethynylbicyclo[2.2.2]octane spacer. Next to observing the key intermediates in solution-based SF, including the formation and decay of a quintet state that precedes formation of the pentacene triplet excitons, we demonstrate that the coupling is sufficiently weak that SF is essentially inoperative in non-polar media. Transitioning to a polar medium, however, amplifies the coupling strength such that SF becomes operative and supports long triplet lifetimes. Our results offer strong evidence for a charge-transfer mediation and, in turn, provide a solid framework for decoding the complete mechanism of SF in systems beyond pentacene.

Charge Separation and Triplet Exciton Formation Pathways in Small Molecule Solar Cells as Studied by Time-resolved EPR Spectroscopy.

Organic solar cells are a promising renewable energy technology, offering the advantages of mechanical flexibility and solution processability. An understanding of the electronic excited states and charge separation pathways in these systems is crucial if efficiencies are to be further improved. Here we use light induced electron paramagnetic resonance (LEPR) spectroscopy and density functional theory calculations (DFT) to study the electronic excited states, charge transfer (CT) dynamics and triplet exciton formation pathways in blends of the small molecule donors (DTS(FBTTh2)2, DTS(F2BTTh2)2, DTS(PTTh2)2, DTG(FBTTh2)2 and DTG(F2BTTh2)2) with the fullerene derivative PC61BM. Using high frequency EPR the g-tensor of the positive polaron on the donor molecules was determined. The experimental results are compared with DFT calculations which reveal that the spin density of the polaron is distributed over a dimer or trimer. Time-resolved EPR (TR-EPR) spectra attributed to singlet CT states were identified and the polarization patterns revealed similar charge separation dynamics in the four fluorobenzothiadiazole donors, while charge separation in the DTS(PTTh2)2 blend is slower. Using TR-EPR we also investigated the triplet exciton formation pathways in the blend. The polarization patterns reveal that the excitons originate from both intersystem crossing (ISC) and back electron transfer (BET) processes. The DTS(PTTh2)2 blend was found to contain substantially more triplet excitons formed by BET than the fluorobenzothiadiazole blends. The higher BET triplet exciton population in the DTS(PTTh2)2 blend is in accordance with the slower charge separation dynamics observed in this blend.

Tuning Singlet Fission in π-Bridge-π Chromophores

We have designed a series of pentacene dimers separated by homoconjugated or nonconjugated bridges that exhibit fast and efficient intramolecular singlet exciton fission (iSF). These materials are distinctive among reported iSF compounds because they exist in the unexplored regime of close spatial proximity but weak electronic coupling between the singlet exciton and triplet pair states. Using transient absorption spectroscopy to investigate photophysics in these molecules, we find that homoconjugated dimers display desirable excited-state dynamics, with significantly reduced recombination rates as compared to conjugated dimers with similar singlet fission rates. In addition, unlike conjugated dimers, the time constants for singlet fission are relatively insensitive to the interplanar angle between chromophores, since rotation about σ bonds negligibly affects the orbital overlap within the π-bonding network. In the nonconjugated dimer, where the iSF occurs with a time constant >10 ns, comparable to the fluorescence lifetime, we used electron spin resonance spectroscopy to unequivocally establish the formation of triplet-triplet multiexcitons and uncoupled triplet excitons through singlet fission. Together, these studies enable us to articulate the role of the conjugation motif in iSF.