Nicholas R. Monahan

The Quantum Coherent Mechanism for Singlet Fission: Experiment and Theory

The absorption of one photon by a semiconductor material usually creates one electron-hole pair. However, this general rule breaks down in a few organic semiconductors, such as pentacene and tetracene, where one photon absorption may result in two electron-hole pairs. This process, where a singlet exciton transforms to two triplet excitons, can have quantum yields as high as 200%. Singlet fission may be useful to solar cell technologies to increase the power conversion efficiency beyond the so-called Shockley-Queisser limit. Through time-resolved two-photon photoemission (TR-2PPE) spectroscopy in crystalline pentacene and tetracene, our lab has recently provided the first spectroscopic signatures in singlet fission of a critical intermediate known as the multiexciton state (also called a correlated triplet pair). More importantly, we found that population of the multiexciton state rises at the same time as the singlet state on the ultrafast time scale upon photoexcitation. This observation does not fit with the traditional view of singlet fission involving the incoherent conversion of a singlet to a triplet pair. However, it provides an experimental foundation for a quantum coherent mechanism in which the electronic coupling creates a quantum superposition of the singlet and the multiexciton state immediately after optical excitation. In this Account, we review key experimental findings from TR-2PPE experiments and present a theoretical analysis of the quantum coherent mechanism based on electronic structural and density matrix calculations for crystalline tetracene lattices. Using multistate density functional theory, we find that the direct electronic coupling between singlet and multiexciton states is too weak to explain the experimental observation. Instead, indirect coupling via charge transfer intermediate states is two orders of magnitude stronger, and dominates the dynamics for ultrafast multiexciton formation. Density matrix calculation for the crystalline tetracene lattice satisfactorily accounts for the experimental observations. It also reveals the critical roles of the charge transfer states and the high dephasing rates in ensuring the ultrafast formation of multiexciton states. In addition, we address the origins of microscopic relaxation and dephasing rates, and adopt these rates in a quantum master equation description. We show the need to take the theoretical effort one step further in the near future by combining high-level electronic structure calculations with accurate quantum relaxation dynamics for large systems.

Charge Transfer Excitons at van der Waals Interfaces.

The van der Waals interfaces of molecular donor/acceptor or graphene-like two-dimensional (2D) semiconductors are central to concepts and emerging technologies of light-electricity interconversion. Examples include, among others, solar cells, photodetectors, and light emitting diodes. A salient feature in both types of van der Waals interfaces is the poorly screened Coulomb potential that can give rise to bound electron-hole pairs across the interface, i.e., charge transfer (CT) or interlayer excitons. Here we address common features of CT excitons at both types of interfaces. We emphasize the competition between localization and delocalization in ensuring efficient charge separation. At the molecular donor/acceptor interface, electronic delocalization in real space can dictate charge carrier separation. In contrast, at the 2D semiconductor heterojunction, delocalization in momentum space due to strong exciton binding may assist in parallel momentum conservation in CT exciton formation.

Charge Transfer–Mediated Singlet Fission

Singlet fission, the splitting of a singlet exciton into two triplet excitons in molecular materials, is interesting not only as a model many-electron problem, but also as a process with potential applications in solar energy conversion. Here we discuss limitations of the conventional four-electron and molecular dimer model in describing singlet fission in crystalline organic semiconductors, such as pentacene and tetracene. We emphasize the need to consider electronic delocalization, which is responsible for the decisive role played by the Mott-Wannier exciton, also called the charge transfer (CT) exciton, in mediating singlet fission. At the strong electronic coupling limit, the initial excitation creates a quantum superposition of singlet, CT, and triplet-pair states, and we present experimental evidence for this interpretation. We also discuss the most recent attempts at translating this mechanistic understanding into design principles for CT state-mediated intramolecular singlet fission in oligomers and polymers.

Harvesting singlet fission for solar energy conversion via triplet energy transfer

The efficiency of a conventional solar cell may be enhanced if one incorporates a molecular material capable of singlet fission, that is, the production of two triplet excitons from the absorption of a single photon. To implement this, we need to successfully harvest the two triplets from the singlet fission material. Here we show in the tetracene (Tc)/copper phthalocyanine (CuPc) model system that triplets produced from singlet fission in the former can transfer to the later on the timescale of 45±5 ps. However, the efficiency of triplet energy transfer is limited by a loss channel due to faster formation (400±100 fs) and recombination (2.6±0.5 ps) of charge transfer excitons at the interface. These findings suggest a design principle for efficient energy harvesting from singlet fission: one must reduce interfacial area between the two organic chromophores to minimize charge transfer/recombination while optimizing light absorption, singlet fission and triplet rather than singlet transfer.

Dynamics of the triplet-pair state reveals the likely coexistence of coherent and incoherent singlet fission in crystalline hexacene

The absorption of a photon usually creates a singlet exciton (S1) in molecular systems, but in some cases S1 may split into two triplets (2×T1) in a process called singlet fission. Singlet fission is believed to proceed through the correlated triplet-pair 1(TT) state. Here, we probe the 1(TT) state in crystalline hexacene using time-resolved photoemission and transient absorption spectroscopies. We find a distinctive 1(TT) state, which decays to 2×T1 with a time constant of 270 fs. However, the decay of S1 and the formation of 1(TT) occur on different timescales of 180 fs and <50 fs, respectively. Theoretical analysis suggests that, in addition to an incoherent S1→1(TT) rate process responsible for the 180 fs timescale, S1 may couple coherently to a vibronically excited 1(TT) on ultrafast timescales (<50 fs). The coexistence of coherent and incoherent singlet fission may also reconcile different experimental observations in other acenes.

Exceeding the Shockley-Queisser Limit in Solar Energy Conversion

We summarize our recent explorations of photophysical mechanisms that may be utilized in solar cells with power conversion efficiency theoretically exceeding the Shockley–Queisser limit. The dominant losses responsible for the Shockley–Queisser limit are below band-gap and thermalization (hot carrier) losses; together, they account for >55% of the total absorbed solar energy. This perspective focuses on two photophysical mechanisms, hot carrier equilibration and carrier multiplication, which may be used to reduce these losses through their utilization in novel solar cell designs. For the implementation of a hot carrier solar cell, we discuss the necessity of hot carrier scattering as well as the photon flux challenge. Although recent experiments have demonstrated the feasibility of hot-electron extraction from photo-excited semiconductor nano-crystals, the photon flux challenge cannot be met in these materials. We propose graphene and related materials as potentially ideal chromophores for hot carrier solar cells. For the multi-exciton solar cell, we focus on the molecular analog called singlet fission. Recent experiments in our lab revealed a quantum coherent mechanism in which photo-excitation of the organic semiconductor pentacene or tetracene creates a quantum superposition of singlet exciton and multi-exciton states. This quantum superposition and the corresponding decoherence time (i.e., singlet fission time) are critical to the competing dynamics of charge or energy harvesting. We discuss design principles for solar cells based on singlet fission materials.

Atomic-Scale Spectroscopy of Gated Monolayer MoS2

The electronic properties of semiconducting monolayer transition-metal dichalcogenides can be tuned by electrostatic gate potentials. Here we report gate-tunable imaging and spectroscopy of monolayer MoS2 by atomic-resolution scanning tunneling microscopy/spectroscopy (STM/STS). Our measurements are performed on large-area samples grown by metal-organic chemical vapor deposition (MOCVD) techniques on a silicon oxide substrate. Topographic measurements of defect density indicate a sample quality comparable to single-crystal MoS2. From gate voltage dependent spectroscopic measurements, we determine that in-gap states exist in or near the MoS2 film at a density of 1.3 × 10(12) eV(-1) cm(-2). By combining the single-particle band gap measured by STS with optical measurements, we estimate an exciton binding energy of 230 meV on this substrate, in qualitative agreement with numerical simulation. Grain boundaries are observed in these polycrystalline samples, which are seen to not have strong electronic signatures in STM imaging.

Ultrafast and band-selective Auger recombination in InGaN quantum wells

In InGaN quantum well based light-emitting diodes, Auger recombination is believed to limit the quantum efficiency at high injection currents. Here, we report the direct observation of carrier loss from Auger recombination on a sub-picosecond timescale in a single InGaN quantum well using time-resolved photoemission. Selective excitations of different valence sub-bands reveal that the Auger rate constant decreases by two orders of magnitude as the effective hole mass decreases, confirming the critical role of momentum conservation.

Correction to “Charge Transfer Excitons at van der Waals Interfaces”

J. Am. Chem. Soc. 2015, 137, 8313−8320. DOI:10.1021/jacs.5b03141 Page 8316. In the text following eq (2), the value “3.1 nm−1 ” for the parallel momentum vector at the zone boundary is wrong, which also affects the subsequent comments about the momentum uncertainty. The correct number should be 22.7 nm−1. The corrected text should read as follows: “...the parallel momentum vector at the zone boundary is 22.7 nm−1. Thus, the momentum uncertainty resulting from excitonic localization can cover 4−7% of the Brillouin zone and satisfy part of the requirement for momentum conservation in interfacial charge transfer.” Addition/Correction