Shane R. Yost

External quantum efficiency above 100% in a singlet-exciton-fission-based organic photovoltaic cell.

Splitting Singlets Solar cell efficiency is limited because light at wavelengths shorter than the cells absorption threshold does not channel any of its excess energy into the generated electricity. Congreve et al. (p. 334) have developed a method to harvest the excess energy in carbon-based absorbers through a process termed “singlet fission.” In this process, high-energy photons propel two current carriers, rather than just one, by populating a singlet state that spontaneously divides into a pair of triplet states. Although it works in a functioning organic solar cell, the efficiency needs improving. Single photons are shown to propel more than one carrier in a carbon-based solar cell. Singlet exciton fission transforms a molecular singlet excited state into two triplet states, each with half the energy of the original singlet. In solar cells, it could potentially double the photocurrent from high-energy photons. We demonstrate organic solar cells that exploit singlet exciton fission in pentacene to generate more than one electron per incident photon in a portion of the visible spectrum. Using a fullerene acceptor, a poly(3-hexylthiophene) exciton confinement layer, and a conventional optical trapping scheme, we show a peak external quantum efficiency of (109 ± 1)% at wavelength λ = 670 nanometers for a 15-nanometer-thick pentacene film. The corresponding internal quantum efficiency is (160 ± 10)%. Analysis of the magnetic field effect on photocurrent suggests that the triplet yield approaches 200% for pentacene films thicker than 5 nanometers.

Charge Transfer State Versus Hot Exciton Dissociation in Polymer−Fullerene Blended Solar Cells

We examine the significance of hot exciton dissociation in two archetypical polymer-fullerene blend solar cells. Rather than evolving through a bound charge transfer state, hot processes are proposed to convert excitons directly into free charges. But we find that the internal quantum yields of carrier photogeneration are similar for both excitons and direct excitation of charge transfer states. The internal quantum yield, together with the temperature dependence of the current-voltage characteristics, is consistent with negligible impact from hot exciton dissociation.

A transferable model for singlet-fission kinetics

Exciton fission is a process that occurs in certain organic materials whereby one singlet exciton splits into two independent triplets. In photovoltaic devices these two triplet excitons can each generate an electron, producing quantum yields per photon of >100% and potentially enabling single-junction power efficiencies above 40%. Here, we measure fission dynamics using ultrafast photoinduced absorption and present a first-principles expression that successfully reproduces the fission rate in materials with vastly different structures. Fission is non-adiabatic and Marcus-like in weakly interacting systems, becoming adiabatic and coupling-independent at larger interaction strengths. In neat films, we demonstrate fission yields near unity even when monomers are separated by >5 Å. For efficient solar cells, however, we show that fission must outcompete charge generation from the singlet exciton. This work lays the foundation for tailoring molecular properties like solubility and energy level alignment while maintaining the high fission yield required for photovoltaic applications.

Singlet Exciton Fission Photovoltaics

Singlet exciton fission, a process that generates two excitons from a single photon, is perhaps the most efficient of the various multiexciton-generation processes studied to date, offering the potential to increase the efficiency of solar devices. But its unique characteristic, splitting a photogenerated singlet exciton into two dark triplet states, means that the empty absorption region between the singlet and triplet excitons must be filled by adding another material that captures low-energy photons. This has required the development of specialized device architectures. In this Account, we review work to develop devices that harness the theoretical benefits of singlet exciton fission. First, we discuss singlet fission in the archetypal material, pentacene. Pentacene-based photovoltaic devices typically show high external and internal quantum efficiencies. They have enabled researchers to characterize fission, including yield and the impact of competing loss processes, within functional devices. We review in situ probes of singlet fission that modulate the photocurrent using a magnetic field. We also summarize studies of the dissociation of triplet excitons into charge at the pentacene-buckyball (C60) donor-acceptor interface. Multiple independent measurements confirm that pentacene triplet excitons can dissociate at the C60 interface despite their relatively low energy. Because triplet excitons produced by singlet fission each have no more than half the energy of the original photoexcitation, they limit the potential open circuit voltage within a solar cell. Thus, if singlet fission is to increase the overall efficiency of a solar cell and not just double the photocurrent at the cost of halving the voltage, it is necessary to also harvest photons in the absorption gap between the singlet and triplet energies of the singlet fission material. We review two device architectures that attempt this using long-wavelength materials: a three-layer structure that uses long- and short-wavelength donors and an acceptor and a simpler, two-layer combination of a singlet-fission donor and a long-wavelength acceptor. An example of the trilayer structure is singlet fission in tetracene with copper phthalocyanine inserted at the C60 interface. The bilayer approach includes pentacene photovoltaic cells with an acceptor of infrared-absorbing lead sulfide or lead selenide nanocrystals. Lead selenide nanocrystals appear to be the most promising acceptors, exhibiting efficient triplet exciton dissociation and high power conversion efficiency. Finally, we review architectures that use singlet fission materials to sensitize other absorbers, thereby effectively converting conventional donor materials to singlet fission dyes. In these devices, photoexcitation occurs in a particular molecule and then energy is transferred to a singlet fission dye where the fission occurs. For example, rubrene inserted between a donor and an acceptor decouples the ability to perform singlet fission from other major photovoltaic properties such as light absorption.

Assessment of the ΔSCF density functional theory approach for electronic excitations in organic dyes.

This paper assesses the accuracy of the ΔSCF method for computing low-lying HOMO→LUMO transitions in organic dye molecules. For a test set of vertical excitation energies of 16 chromophores, surprisingly similar accuracy is observed for time-dependent density functional theory and for ΔSCF density functional theory. In light of this performance, we reconsider the ad hoc ΔSCF prescription and demonstrate that it formally obtains the exact stationary density within the adiabatic approximation, partially justifying its use. The relative merits and future prospects of ΔSCF for simulating individual excited states are discussed.

Triplet Exciton Dissociation in Singlet Exciton Fission Photovoltaics

Triplet exciton dissociation in singlet exciton fission devices with three classes of acceptors are characterized: fullerenes, perylene diimides, and PbS and PbSe colloidal nanocrystals. Using photocurrent spectroscopy and a magnetic field probe it is found that colloidal PbSe nanocrystals are the most promising acceptors, capable of efficient triplet exciton dissociation and long wavelength absorption.

Electronic properties of disordered organic semiconductors via QM/MM simulations.

Organic semiconductors (OSCs) have recently received significant attention for their potential use in photovoltaic, light emitting diode, and field effect transistor devices. Part of the appeal of OSCs is the disordered, amorphous nature of these materials, which makes them more flexible and easier to process than their inorganic counterparts. In addition to their technological applications, OSCs provide an attractive laboratory for examining the chemistry of heterogeneous systems. Because OSCs are both electrically and optically active, researchers have access to a wealth of electrical and spectroscopic probes that are sensitive to a variety of localized electronic states in these materials. In this Account, we review the basic concepts in first-principles modeling of the electronic properties of disordered OSCs. There are three theoretical ingredients in the computational recipe. First, Marcus theory of nonadiabatic electron transfer (ET) provides a direct link between energy and kinetics. Second, constrained density functional theory (CDFT) forms the basis for an ab initio model of the diabatic charge states required in ET. Finally, quantum mechanical/molecular mechanical (QM/MM) techniques allow us to incorporate the influence of the heterogeneous environment on the diabatic states. As an illustration, we apply these ideas to the small molecule OSC tris(8- hydroxyquinolinato)aluminum (Alq(3)). In films, Alq(3) can possess a large degree of short-range order, placing it in the middle of the order-disorder spectrum (in this spectrum, pure crystals represent one extreme and totally amorphous structures the opposite extreme). We show that the QM/MM recipe reproduces the transport gap, charge carrier hopping integrals, optical spectra, and reorganization energies of Alq(3) in quantitative agreement with available experiments. However, one cannot specify any of these quantities accurately with a single number. Instead, one must characterize each property by a distribution that reflects the influence of the heterogeneous environment on the electronic states involved. For example, the hopping integral between a given pair of Alq(3) molecules can vary by as much as a factor of 5 on the nanosecond timescale, but the integrals for two different pairs can easily differ by a factor of 100. To accurately predict mesoscopic properties such as carrier mobilities based on these calculations, researchers must account for the dynamic range of the microscopic inputs, rather than just their average values. Thus, we find that many of the computational tools required to characterize these materials are now available. As we continue to improve this computational toolbox, we envision a future scenario in which researchers can use basic information about OSC deposition to simulate device operation on the atomic scale. This type of simulation could allow researchers to obtain data that not only aids in the interpretation of experimental results but also guides the design of more efficient devices.

Metal‐Free OLED Triplet Emitters by Side‐Stepping Kasha’s Rule

With organic light-emitting diodes (OLEDs) emerging in ever more applications, such as smart phones, televisions, and lighting, it is easy to forget that the present technology is based on a brilliantly simple patch to an inherent problem of fluorescent hydrocarbons: three quarters of the electrically generated energy is dissipated as heat by triplet excitons. Radiative decay from the triplet state via phosphorescence is generally very weak, and has only been resolved in transient spectroscopy at low temperatures in select organic semiconductors. The solution to this problem has been to incorporate metal–organic emitters in OLEDs, which mix spin by enhancing intersystem crossing through spin-orbit coupling: the heavy-atom effect. As this approach relies on the longevity of triplet excitons and the associated diffusion lengths, it is highly effective: in a suitably homogeneous environment even ppm concentrations of covalently bound metal atoms are sufficient to activate electrophosphorescence. The second conceivable approach to harvesting energy from triplets is based on endothermic conversion to a fluorescent singlet by reverse intersystem crossing. This method necessitates control not only over spin–orbit coupling, requiring a heavy atom or a carefully engineered charge-transfer state, but also over the singlet–triplet exchange gap, which can be tuned by excitonic confinement. Although progress has been made recently, conceptually it parallels the former approach: all excitations are converted to either triplets or singlets, thereby losing information on the underlying spin correlations of charge carriers. Evidence is emerging, however, that spin correlations in excitonic electron–hole precursor pairs can be used for exquisitely sensitive measurements of magnetic fields and possibly even for quantum coherence phenomenology, with analogies to avian radical-pair photomagnetosensory processes. To quantify such spin correlations, it is desirable to develop materials without heavy-atom spin mixing that show both intrinsic fluorescence and phosphorescence. The third approach to triplet harvesting has not been explored previously: tuning spin–orbit coupling without heavy atoms such that non-radiative internal conversion from the triplet excited state to the singlet ground state is suppressed and phosphorescence is the only remaining relaxation mechanism. Even in low-atomic-order-number compounds such as hydrocarbons, the orbital component of the wavefunction can give rise to substantial magnetic moments, leading to non-negligible spin–orbit energy terms. The effect is well-studied in carbon nanotubes and graphene, where zero-field splitting correlates with nanoscale curvature. For molecular materials, orbital symmetry can induce unusual spin–orbital coupling effects, such as in pyrazine, which shows direct singlet–triplet absorption. Polycyclic aromatic hydrocarbons, such as triphenylenes or annulated compounds like phenazine, are classic metal-free materials that are known to exhibit substantial phosphorescence yields. Although triphenylenes have previously been explored both as emitters and as charge-transporting materials in OLEDs, there are no reports of direct electrophosphorescence, despite renewed interest in room-temperature organic phosphors. Herein, we demonstrate the feasibility of creating a triplet relaxation bottleneck to internal conversion that is so effective that radiative emission can even arise from higher-lying triplets in electroluminescence (EL), bypassing Kasha s rule of internal conversion. Figure 1a shows the two materials developed, a thiophene-decorated phenazine 1; and 1 linked to a triphenylene block in 2. Details of synthesis and characterization of the materials, and fabrication and performance of the OLEDs, are given in the Supporting Information. To construct OLEDs, we have to prevent concentration quenching, which is particularly strong for long-lived triplets. Therefore a dense film of the compounds cannot be used. The emitters are dispersed in a conducting matrix, poly(9-vinylcarbazole) (PVK). This material has a large optical gap, so that suitable electronand hole-transporting moieties have to be included: 2-(4-tert-butylphenyl)-5-(4-biphenyl)-1,3,4-oxadiazole (PBD) and N,N’-bis(3-methylphenyl)-N,N’-diphenylbenzi[*] P. Klemm, S. Lautenschlager, A. Schmid, Dr. S. Bange, Prof. Dr. J. M. Lupton Institut f r Angewandte und Experimentelle Physik Universit t Regensburg Universit tsstrasse 31, 93053 Regensburg (Germany) E-mail: john.lupton@ur.de

Charge Transfer or J‑Coupling? Assignment of an Unexpected Red- Shifted Absorption Band in a Naphthalenediimide-Based Metal− Organic Framework

We investigate and assign a previously reported unexpected transition in the metal-organic framework Zn2(NDC)2(DPNI) (1; NDC = 2,6-naphthalenedicarboxylate, DPNI = dipyridyl-naphthalenediimide) that displays linear arrangements of naphthalenediimide ligands. Given the longitudinal transition dipole moment of the DPNI ligands, J-coupling seemed possible. Photophysical measurements revealed a broad, new transition in 1 between 400 and 500 nm. Comparison of the MOF absorption spectra with that of a charge transfer (CT) complex formed by manual grinding of DPNI and H2NDC led to the assignment of the new band in 1 as arising from an interligand CT. Constrained density functional theory utilizing a custom long-range-corrected hybrid functional was employed to determine which ligands were involved in the CT transition. On the basis of relative oscillator strengths, the interligand CT was assigned as principally arising from π-stacked DPNI/NDC dimers rather than the alternative orthogonal pairs within the MOF.

Highly efficient, dual state emission from an organic semiconductor

We report highly efficient, simultaneous fluorescence and phosphorescence (74% yield) at room temperature from a single molecule ensemble of (BzP)PB [N,N′-bis(4-benzoyl-phenyl)-N,N′-diphenyl-benzidine] dispersed into a polymer host. The slow phosphorescence (208 ms lifetime) is very efficient (50%) at room temperature and only possible because the non-radiative rate for the triplet state is extremely low (2.4 × 100 s−1). The ability of an organic molecule to function as an efficient dual state emitter at room temperature is unusual and enables a wide range of applications including the use as broadband down-conversion emitters, optical sensors and attenuators, exciton probes, and spin-independent intermediates for Forster resonant energy transfer.