Inclusion of heavy metal atoms in a polymer backbone allows transitions between the singlet and triplet manifolds. Interfacial dissociation of triplet excitons constitutes a viable mechanism for enhancing photovoltaic (PV) efficiencies in polymer heterojunction-based solar cells. The PV efficiency from polymer solar cells utilizing a ladder-type poly (para-phenylene) polymer (PhLPPP) with trace quantity of Pd atoms and a fullerene derivative (PCBM) is much higher than its counterpart (MeLPPP) with no Pd atom. Evidence is presented for the formation of a weak ground-state charge-transfer complex (CTC) in the blended films of the polymer and PCBM, using photo-induced absorption (PIA) spectroscopy. The CTC state in MeLPPP:PCBM has a singlet character to it, resulting in a radiative recombination. In contrast, the CTC states in PhLPPP:PCBM are more localized with a triplet character. An absorption peak at 1.65 eV is observed in PhLPPP:PCBM blend in the PIA, which may be converted to weakly-bound polaron-pairs, contributing to the enhancement of PV efficiency.
We demonstrate that the interaction between excitons and a sea of incoherent electrons does not preclude excitons dressing by light. We investigate the role of exciton-electron scattering in the light dressing by measuring the dynamical absorption spectrum of a modulation-doped CdTe quantum well, which shows a clear evidence for significant electron scattering of the excitonic states. We show the occurrence of dressed and correlated excitons by detecting quantum coherent interferences through excitonic Autler-Townes doublet and ac Stark splitting, which evolves to Mollow triplet with gain. We …
Advances in opto-electronics require the development of materials with novel and engineered characteristics. A class of materials that has garnered tremendous interest is metal-halide perovskites, stimulated by meteoric increases in photovoltaic efficiencies of perovskite solar cells. In addition, recent advances have applied perovskite nanocrystals (NCs) in light-emitting devices. It was discovered recently that, for cesium lead-halide perovskite NCs, their unusually efficient light-emission may be due to a unique excitonic fine-structure composed of three bright triplet states that minimally…
Spin-polarized triplet excitonic insulators in Ta3X8 (X=I, Br) monolayers
Beijing National Laboratory for Condensed Matter Physics, and Institute of Physics, Chinese Academy of Sciences（中国科学院物理研究所）；University of Chinese Academy of Sciences（中国科学院大学）；Department of Physics, Hong Kong University of Science and Technology（香港科技大学物理系）
Exciton-polaritons are quasiparticles with mixed photon and exciton character that demonstrate rich quantum phenomena, novel optoelectronic devices and the potential to modify chemical properties of materials. Organic semiconductors are of current interest for their room-temperature polariton formation. However, within organic optoelectronic devices, it is often the 'dark' spin-1 triplet excitons that dominate operation. These triplets have been largely ignored in treatments of polariton physics. Here we demonstrate polariton population from the triplet manifold via triplet-triplet annihilatio…
We investigate the optical properties of spin-triplet interlayer excitons in heterobilayer transition metal dichalcogenides in comparison with the spin-singlet ones. Surprisingly, the optical transition dipole of the spin-triplet exciton is found to be in the same order of magnitude to that of the spin-singlet exciton, in sharp contrast to the monolayer excitons where the spin triplet species is considered as dark compared to the singlet. Unlike the monolayer excitons whose spin-conserved (spin-flip) transition dipole can only couple to light of in-plane (out-of-plane) polarization, such restr…
Organic bulk-heterojunctions (BHJ) and solar cells containing the trimetallic nitride endohedral fullerene 1-[3-(2-ethyl)hexoxy carbonyl]propyl-1-phenyl-Lu3N@C80 (Lu3N@C80-PCBEH) show an open circuit voltage (VOC) 0.3 V higher than similar devices with [6,6]-phenyl-C[61]-butyric acid methyl ester (PC61BM). To fully exploit the potential of this acceptor molecule with respect to the power conversion efficiency (PCE) of solar cells, the short circuit current (JSC) should be improved to become competitive with the state of the art solar cells. Here, we address factors influencing the JSC in blend…
While various excitonic insulators have been studied in the literature, due to the perceived too-small spin splitting, spin-triplet excitonic insulator is rare. In two-dimensional systems such as a graphone, however, it is possible, as revealed by first-principles calculations coupled with Bethe-Salpeter equation. The critical temperature, given by an effective Hamiltonian, is 11.5 K. While detecting excitonic insulators is still a daunting challenge, the condensation of triplet excitons will result in spin superfluidity, which can be directly measured by a transport experiment. Nonlocal diele…
Exciton Coherence in CsPbBr3 Nanocrystals is Bounded by Phonon-Mediated Bright-Triplet Relaxation
Massachusetts Institute of Technology（麻省理工学院）；Center for Hybrid Organic Inorganic Semiconductors for Energy（有机无机半导体混合能源中心）；National Laboratory of the Rockies（落基山国家实验室）；U.S. Naval Research Laboratory（美国海军研究实验室）；Lund University（隆德大学）
The ground state of negatively charged excitons (trions) in high magnetic fields is shown to be a dark triplet state, confirming long-standing theoretical predictions. Photoluminescence (PL), reflection, and PL excitation spectroscopy of CdTe quantum wells reveal that the dark triplet trion has lower energy than the singlet trion above 24 Tesla. The singlet-triplet crossover is "hidden" (i.e., the spectral lines themselves do not cross due to different Zeeman energies), but is confirmed by temperature-dependent PL above and below 24 T. The data also show two bright triplet states.
The excitonic insulator (EI) state is a strongly correlated many-body ground state, arising from an instability in the band structure towards exciton formation. We show that the flat valence and conduction bands of a semiconducting diatomic Kagome lattice, as exemplified in a superatomic graphene lattice, can possibly conspire to enable an interesting triplet EI state, based on density functional theory (DFT) calculations combined with many-body GW and Bethe-Salpeter Equation(BSE). Our results indicate that massive carriers in flat bands with highly localized electron and hole wavefunctions si…
Quantifying the spin-spin interactions which influence electronic transitions in organic semiconductors is crucial for understanding their magneto-optoelectronic properties. By combining a theoretical model for three spin interactions in the coherent regime with pulsed electrically detected magnetic resonance experiments on MEH-PPV diodes, we quantify the spin-coupling within complexes comprising three spin-half particles. We determine that these particles form triplet-exciton:polaron pairs, where the polaron:exciton exchange is over 5 orders of magnitude weaker (less than 170 MHz) than that w…
Singlet fission (SF), an exciton multiplication process occurring in organic semiconductors, offers a way to break the Shockley-Queisser limit in single-bandgap photovoltaics (PV). If the triplet excitons generated by SF can be transferred to inorganic quantum dots (QDs), where they radiatively recombine, SF based photon multiplication is achieved, converting a single high-energy photon into two low-energy photons. Such a SF photon multiplication film (SF-PMF) could raise the efficiency of the best Si-PV from 26.7% to 32.5%. But a precise nanoscale morphology is required within such a film con…
BaCuSi$_2$O$_6$, a $S=1/2$ quantum antiferromagnet with a double-layer structure of Cu$^{2+}$ ions in a distorted planar-rectangular coordination and with a dimerized spin singlet ground state, is studied by means of the electron paramagnetic resonance technique. It is argued that multiple absorptions observed at low temperatures are intimately related to a thermally-activated spin-triplet exciton superstructure. Analysis of the angular dependence of exciton modes in BaCuSi$_2$O$_6$ allows us to accurately estimate anisotropy parameters. In addition, the temperature dependence of EPR intensity…
Triplet Excitons Reconcile Charge Generation and Recombination in Low-Offset Organic Solar Cells: Efficiency Limits from a 5-State Model
Paul-Drude-Institut für Festkörperelektronik (PDI), Leibniz-Institut im Forschungsverbund Berlin e.V.（柏林莱布尼茨研究所保罗·德鲁德固态电子学研究所）；University of Potsdam（波茨坦大学）
We present a comparative study of ultrafast photo-conversion dynamics in tetracene (Tc) and pentacene (Pc) single crystals and Pc films using optical pump-probe spectroscopy. Photo-induced absorption in Tc and Pc crystals is activated and temperature-independent respectively, demonstrating dominant singlet-triplet exciton fission. In Pc films (as well as C$_{60}$-doped films) this decay channel is suppressed by electron trapping. These results demonstrate the central role of crystallinity and purity in photogeneration processes and will constrain the design of future photovoltaic devices.
The great progress in organic photovoltaics (OPV) over the past few years has been largely achieved by the development of non-fullerene acceptors (NFAs), with power conversion efficiencies now approaching 20%. To further improve device performance, loss mechanisms must be identified and minimized. Triplet states are known to adversely affect device performance, since they can form energetically trapped excitons on low-lying states that are responsible for non-radiative losses or even device degradation. Halogenation of OPV materials has long been employed to tailor energy levels and to enhance…
Photochemical upconversion is a promising way to boost the efficiency of solar cells using triplet exciton annihilation. Currently, predicting the performance of photochemical upconversion devices is challenging. We present an open source software package which takes experimental parameters as inputs and gives the figure of merit of an upconversion system, enabling theory-driven design of better solar energy devices. We incorporate the statistical distribution of triplet excitons between the sensitizer and the emitter. Using the dynamic quenching effect of the sensitizer on emitter triplet exc…
In a recent Letter Lee et al. studied the spin 1/2 photoluminescence-detected magnetic resonance (PLDMR) of a soluble derivative of poly-phenylene vinylene [MEH-PPV] and argued that it originates from the interaction of triplet excitons with polarons. We show that in MEH-PPV as well as in other conjugated polymers the spin 1/2 PLDMR does not depend on the triplet exciton density and thus cannot be associated with triplet excitons.
Measurements of the diffusion length L for triplet excitons in small molecular-weight organic semiconductors are commonly carried out using a technique in which a phosphorescent-doped probe layer is set in the vicinity of a supposed exciton generation zone. However, analyses commonly used to retrieve $L$ ignore microcavity effects that may induce a strong modulation of the emitted light as the position of the exciton probe is shifted. The present paper investigates in detail how this technique may be improved to obtain more accurate results for L. The example of 4,4'-bis(carbazol-9-yl)1,1'-bip…
Singlet fission, the molecular process through which photons are effectively converted into pairs of lower energy triplet excitons, holds promise as a means of boosting photovoltaic device efficiencies. In the preceding article of this series, we formulated a vibronic theory of singlet fission, inspired by previous experimental and theoretical studies suggesting that vibronic coupling plays an important role in fission dynamics. Here, we extend our model in order to simulate two-dimensional electronic spectra, through which the theory is further validated based on a comparison to recent measur…
Understanding and controlling exciton transport is a strategic way to enhance the optoelectronic properties of high-performance organic devices. In this article we study triplet exciton migration in crystalline poly($p$-phenylene vinylene) polymer (PPV) using comprehensive electronic structure and quantum dynamical methods. We solve the coupled electron-nuclear dynamics for the triplet energy migrating between two neighboring Frenkel sites in J- and H-aggregate arrangements. From the two-site model we extract key parameters for use with a master-equation approach that allows us to treat nanosi…
Organic solar cells (OSCs) have recently shown a rapid improvement in their performance, bringing power conversion efficiencies (PCEs) closer to the point where commercial applications of the technology become viable. However, the low open-circuit voltage (Voc) of OSCs relative to their optical gap still limits PCEs to below 20%. A key factor contributing to the large Voc deficit in OSCs is non-radiative recombination to spin-triplet excitons, which is widely, but not universally, observed in blends using both fullerene and non-fullerene electron acceptors. Here, we present an experimental fra…
The rise of organic electronics calls for versatile modeling tools. In this context, we develop a semiclassical Boltzmann theory that describes transport and excitonic processes in crystalline organic semiconductors on equal footing. The generation of singlet and triplet excitons out of the ground state, their formation from free electrons and holes, the reverse processes, as well as the fusion and fission of excitons are included. The corresponding scattering integrals respect spin conservation, which requires matrix-valued distribution functions. They also include fermionic and bosonic many-…
Electroluminescence in organic light emitting diode (OLED) materials occurs via the recombination of excitonic electrons-hole pairs Only the singlet excitons of commonly used OLED materials, e.g., Aluminum trihydroxyquinoline (AlQ$_3$), decay radiatively, limiting the external quantum efficiency to a maximum 25%. Thus 75% of the energy is lost due to the triplet bottleneck for radiative recombination. We consider molecules derived from AlQ$_3$ which bypass the triplet bottleneck by designing structures which contain strong spin-orbit coupling. As a first stage of this work, groundstate energie…
Triplet excitonic state in the organic molecule may arise from a singlet excitation and the following inter-system crossing. Especially for a spin-bearing molecule, an exchange interaction between the triplet exciton and the original spin on the molecule can be expected. In this paper, such exchange interaction in copper-phthalocyanine (CuPc, spin-$\frac{1}{2}$) was investigated from first-principles by using density-functional theory within a variety of approximations to the exchange correlation, ranging from local-density approximation to long-range corrected hybrid-exchange functional. The …
We extend the vibronic exciton theory introduced in our previous work to study singlet fission dynamics, in particular addressing recent indications of the importance of vibronic coupling in this process. A microscopic and non-perturbative treatment of electronic and selected vibrational degrees of freedom in combination with Redfield theory allows us to dynamically consider clusters of molecules under conditions close to those in molecular crystals that exhibit fission. Using bulk pentacene as a concrete example, our results identify a number of factors that render fission rapid and effective…
Organic light-emitting diodes (OLEDs) must be engineered to circumvent the efficiency limit imposed by the 3:1 ratio of triplet to singlet exciton formation following electron-hole capture. Here we show the spin nature of luminescent radicals such as TTM-3PCz allows direct energy harvesting from both singlet and triplet excitons through energy transfer, with subsequent rapid and efficient light emission from the doublet excitons. This is demonstrated with a model Thermally-Activated Delayed Fluorescence (TADF) organic semiconductor, 4CzIPN, where reverse intersystem crossing from triplets is c…
Singlet fission in tetracene generates two triplet excitons per absorbed photon. If these triplet excitons can be effectively transferred into silicon (Si) then additional photocurrent can be generated from photons above the bandgap of Si. This could alleviate the thermalization loss and increase the efficiency of conventional Si solar cells. Here we show that a change in the polymorphism of tetracene deposited on Si due to air exposure, facilitates triplet transfer from tetracene into Si. Magnetic field-dependent photocurrent measurements confirm that triplet excitons contribute to the photoc…
We develop a general theory of electron--hole recombination in organic light emitting diodes that leads to formation of emissive singlet excitons and nonemissive triplet excitons. We briefly review other existing theories and show how our approach is substantively different from these theories. Using an exact time-dependent approach to the interchain/intermolecular charge-transfer within a long-range interacting model we find that, (i) the relative yield of the singlet exciton in polymers is considerably larger than the 25% predicted from statistical considerations, (ii) the singlet exciton yi…
The surprising recent observation of highly emissive triplet-states in lead halide perovskites accounts for their orders-of-magnitude brighter optical signals and high quantum efficiencies compared to other semiconductors. This makes them attractive for future optoelectronic applications, especially in bright low-threshold nano-lasers. Whilst non-resonantly pumped lasing from all-inorganic lead-halide perovskites is now well-established as an attractive pathway to scalable low-power laser sources for nano-optoelectronics, here we showcase a resonant optical pumping scheme on a fast triplet-sta…
We conduct polarization-dependent ultrafast spectroscopy to study the dynamics of singlet fission in tetracene single crystals. The spectrotemporal species for singlet and triplet excitons in transient absorption spectra are found to be strongly dependent on probe polarization. By carefully analyzing the polarization dependence, the signals contributed by different transitions related to singlet excitons have been disentangled, which is further applied to construct the correlation between dynamics of singlet and triplet excitons. The anisotropy of exciton dynamics provides an alternative appro…
Singlet fission (SF), the spontaneous down-conversion of a singlet exciton into two triplet excitons residing on neighboring molecules, is a promising route to improving organic photovoltaic (OPV) device efficiencies by harvesting two charge carriers from one photon. However, only a few materials have been discovered that exhibit intermolecular SF in the solid state, most of which are acene derivatives. Recently, there has been a growing interest in rylenes as potential SF materials. We use many-body perturbation theory in the GW approximation and the Bethe-Salpeter equation (BSE) to investiga…
Recent time-resolved spectroscopic experiments have indicated that vibronic coupling plays a vital role in facilitating the process of singlet fission. In this work, which forms the first article of a series, we set out to unravel the mechanisms underlying singlet fission through a vibronic exciton theory. We formulate a model in which both electronic and vibrational degrees of freedom are treated microscopically and non-perturbatively. Using pentacene as a prototypical material for singlet fission, we subject our theory to comparison with measurements on polarization-resolved absorption of si…
It is well known that the ambient environment can dramatically renormalize the quasiparticle gap and exciton binding energies in low-dimensional materials, but the effect of the environment on the energy splitting of the spin-singlet and spin-triplet exciton states is less understood. A prominent effect is the renormalization of the exciton binding energy and optical strength (and hence the optical spectrum) through additional screening of the direct Coulomb term describing the attractive electron-hole interaction in the kernel of the Bethe-Salpeter equation (BSE). The repulsive exchange inter…
In photovoltaics (PVs) and artificial photosynthetic systems based on excitons, the question of how energy must be lost in overcoming the Coulomb barrier, converting excitons to free charges, is fundamental, as it determines the achievable open-circuit voltage or over-potential1-3. Here, using transient and steady-state optical spectroscopy we study a model system, pentacene/C60, where pentacene triplet excitons are dissociated to form charge transfer states, which we show to be degenerate in energy with the triplet excitons. We directly track these charge transfer states undergoing efficient …
We develop a new first-principles approach to predict and understand rates of singlet fission with an ab initio Green's-function formalism based on many-body perturbation theory. Starting with singlet and triplet excitons computed from a GW plus Bethe-Salpeter equation approach, we calculate the exciton--bi-exciton coupling to lowest order in the Coulomb interaction, assuming a final state consisting of two non-interacting spin-correlated triplets with finite center-of-mass momentum. For crystalline pentacene, symmetries dictate that the only purely Coulombic fission decay from a bright single…
To elucidate the high external quantum efficiency observed for organic light-emitting diodes using a bisanthracene derivative, BD1, as the emitting molecule, off-diagonal vibronic coupling constants (VCCs) between the excited states of BD1, which govern non-radiative transition rates, were calculated employing time-dependent density functional theory. The VCCs were analysed based on the concept of vibronic coupling density. The VCC calculations suggest a fluorescence via higher triplets (FvHT) mechanism, which entails the conversion of a T$_4$ exciton generated during electrical excitation int…
We report first-principles GW-Bethe Salpeter Equation and Quantum Monte Carlo calculations of the optical and electronic properties of molecular and crystalline rubrene (C$_{42}$H$_{28}$). Many-body effects dominate the optical spectrum and quasi-particle gap of molecular crystals. We interpret the observed yellow-green photoluminescence in rubrene microcrystals as a result of the formation of intermolecular, charge-transfer spin-singlet excitons. In contrast, spin-triplet excitons are localized and intramolecular with a predicted phosphorescence at the red end of the optical spectrum. We find…
Optical devices fabricated using conjugated polymer systems give rise to singlet exciton yields which are high compared to the statistically predicted estimate of 25% obtained using simple recombination schemes. In this study we evaluate the singlet exciton yield in conjugated polymers systems by fitting to a model that incorporates the Pauli exclusion principle. The rate equations which describe the exciton dynamics include quantum dynamical components (both density and spin-dependent) which arise during the spin-allowed conversion of composite intra-molecular excitons into loosely bound char…
The recombination of electron-hole pairs injected in extended conjugated systems is modeled as a multi-pathway vibron-driven relaxation in monoexcited state-space. The computed triplet-to-singlet ratio of exciton formation times $r = τ_T/τ_S$ increases from 0.9 for a model dimer to 2.5 for a 32-unit chain, in excellent agreement with experiments. Therewith we rationalize recombination efficiency in terms of spin-dependent interstate vibronic coupling and spin- and conjugation-length-dependent exciton binding energies.Our model calculations for various length polymers indicate that the ratio of…
The power conversion efficiencies (PCEs) of organic solar cells (OSCs) using non-fullerene acceptors (NFAs) have now reached 18%. However, this is still lower than inorganic solar cells, for which PCEs >20% are commonplace. A key reason is that OSCs still show low open-circuit voltages (Voc) relative to their optical band gaps, attributed to non-radiative recombination. For OSCs to compete with inorganics in efficiency, all non-radiative loss pathways must be identified and where possible, removed. Here, we show that in most NFA OSCs, the majority of charge recombination at open-circuit procee…
We investigate the lowest many-body excited states in carbon nanotubes by means of ab initio calculations. On the basis of these calculations and an additional theoretical analysis of the excitons, we demonstrate that the splitting between the dark and bright spin-singlet states is due to the direct Coulomb electron-hole interaction, that the dark exciton always has gerade symmetry, and that it is always lower in energy relative to the bright exciton. Applying these studies to 0.4-0.8-nm-diameter tubes, we find a gerade-ungerade splitting of several tens of an meV, and a singlet-triplet splitt…
Organic light emitting devices and solar cells are machines that create, manipulate and destroy excited states in organic semiconductors. It is crucial to characterize these excited states, or excitons, to optimize device performance in applications like displays and solar energy harvesting. This is complicated if the excited state is a triplet because the electronic transition is dark with a vanishing oscillator strength. As a consequence, triplet state spectroscopy must usually be performed at cryogenic temperatures to reduce competition from non-radiative rates. Here, we control non-radiati…
Singlet exciton fission (SEF) is a key process in the development of efficient opto-electronic devices. An aspect that is rarely probed directly, and yet has a tremendous impact on SEF properties, is the nuclear structure and dynamics involved in this process. Here we directly observe the nuclear dynamics accompanying the SEF process in single crystal pentacene using femtosecond electron diffraction. The data reveal coherent atomic motions at 1 THz, incoherent motions, and an anisotropic lattice distortion representing the polaronic character of the triplet excitons. Combining molecular dynami…
Carrier multiplication by singlet exciton fission enhances photovoltaic conversion efficiencies in organic solids. This decay of one singlet exciton into two triplet states promises to overcome the Shockley-Queisser limit as up to two electrons may be harvested per absorbed photon. Intermolecular coupling is deemed mandatory for both, singlet exciton fission and a band-like transport. Such a coupling is manifested, $e.g.$, by the Davydov-splitting of the lowest-energy exciton transition in crystalline organic solids. For the model system perfluoropentacene, the corresponding transitions in the…
