Odd-Even Alkyl Chain Effects on the Structure and Charge Carrier Transport of Two-Dimensional Sn-Based Perovskite Semiconductors.

Oscillations in the chemical or physical properties of materials, composed of an odd or even number of connected repeating methylene units, are a well-known phenomenon in organic chemistry and materials science. So far, such behavior has not been reported for the important class of materials, perovskite semiconductors. This work reports a distinct odd-even oscillation of the molecular structure and charge carrier transport properties of phenylalkylammonium two-dimensional (2D) Sn-based perovskites in which the alkyl chains in the phenylalkylammonium cations contain varying odd and even carbon numbers. Density functional theory calculations and grazing-incidence wide-angle X-ray scattering characterization reveal that perovskites with organic ligands containing an alkyl chain with an odd number of carbon atoms display a disordered crystal lattice and tilted inorganic octahedra accompanied by reduced mobilities. In contrast, perovskites with cations of an even number of carbon atoms in the alkyl chain form more ordered crystal structures, resulting in improved charge carrier mobilities. Our findings disclose the importance of minor changes in the molecular conformation of organic cations have an effect on morphology, photophysical properties, and charge carrier transport of 2D layered perovskites, showcasing alkyl chain engineering of organic cations to control key properties, of layered perovskite semiconductors.

Elimination of charge-carrier trapping by molecular design.

A common obstacle of many organic semiconductors is that they show highly unipolar charge transport. This unipolarity is caused by trapping of either electrons or holes by extrinsic impurities, such as water or oxygen. For devices that benefit from balanced transport, such as organic light-emitting diodes, organic solar cells and organic ambipolar transistors, the energy levels of the organic semiconductors are ideally situated within an energetic window with a width of 2.5 eV where charge trapping is strongly suppressed. However, for semiconductors with a band gap larger than this window, as used in blue-emitting organic light-emitting diodes, the removal or disabling of charge traps poses a longstanding challenge. Here we demonstrate a molecular strategy where the highest occupied molecular orbital and lowest unoccupied molecular orbital are spatially separated on different parts of the molecules. By tuning their stacking by modification of the chemical structure, the lowest unoccupied molecular orbitals can be spatially protected from impurities that cause electron trapping, increasing the electron current by orders of magnitude. In this way, the trap-free window can be substantially broadened, opening a path towards large band gap organic semiconductors with balanced and trap-free transport.

An ab initio method on large sized molecular aggregate system: Predicting absorption spectra of crystalline organic semiconducting films.

Theoretical description of electronically excited states of molecular aggregates at an ab initio level is computationally demanding. To reduce the computational cost, we propose a model Hamiltonian approach that approximates the electronically excited state wavefunction of the molecular aggregate. We benchmark our approach on a thiophene hexamer, as well as calculate the absorption spectra of several crystalline non-fullerene acceptors, including Y6 and ITIC, which are known for their high power conversion efficiency in organic solar cells. The method qualitatively predicts the experimentally measured spectral shape, which can be further linked to the molecular arrangement in the unit cell.

Electronic coarse-graining of long conjugated molecules: Case study of non-fullerene acceptors.

By considering only one electronic state per molecule, charge transport models of molecular solids neglect intramolecular charge transfer. This approximation excludes materials with quasi-degenerate spatially separated frontier orbitals, such as non-fullerene acceptors (NFAs) and symmetric thermally activated delayed fluorescence emitters. By analyzing the electronic structure of room-temperature molecular conformers of a prototypical NFA, ITIC-4F, we conclude that the electron is localized on one of the two acceptor blocks with the mean intramolecular transfer integral of 120 meV, which is comparable with intermolecular couplings. Therefore, the minimal basis for acceptor-donor-acceptor (A-D-A) molecules consists of two molecular orbitals localized on the acceptor blocks. This basis is robust even with respect to geometry distortions in an amorphous solid, in contrast to the basis of two lowest unoccupied canonical molecular orbitals withstanding only thermal fluctuations in a crystal. The charge carrier mobility can be underestimated by a factor of two when using single site approximation for A-D-A molecules in their typical crystalline packings.

Intrinsic efficiency limits in low-bandgap non-fullerene acceptor organic solar cells.

In bulk heterojunction (BHJ) organic solar cells (OSCs) both the electron affinity (EA) and ionization energy (IE) offsets at the donor-acceptor interface should equally control exciton dissociation. Here, we demonstrate that in low-bandgap non-fullerene acceptor (NFA) BHJs ultrafast donor-to-acceptor energy transfer precedes hole transfer from the acceptor to the donor and thus renders the EA offset virtually unimportant. Moreover, sizeable bulk IE offsets of about 0.5 eV are needed for efficient charge transfer and high internal quantum efficiencies, since energy level bending at the donor-NFA interface caused by the acceptors' quadrupole moments prevents efficient exciton-to-charge-transfer state conversion at low IE offsets. The same bending, however, is the origin of the barrier-less charge transfer state to free charge conversion. Our results provide a comprehensive picture of the photophysics of NFA-based blends, and show that sizeable bulk IE offsets are essential to design efficient BHJ OSCs based on low-bandgap NFAs.

Tuning interfacial charge transfer in atomically precise nanographene-graphene heterostructures by engineering van der Waals interactions.

Combining strong light absorption and outstanding electrical conductivity, hybrid nanographene-graphene (NG-Gr) van der Waals heterostructures (vdWHs) represent an emerging material platform for versatile optoelectronic devices. Interfacial charge transfer (CT), a fundamental process whose full control remains limited, plays a paramount role in determining the final device performance. Here, we demonstrate that the interlayer vdW interactions can be engineered by tuning the sizes of bottom-up synthesized NGs to control the interfacial electronic coupling strength and, thus, the CT process in NG-Gr vdWHs. By increasing the dimensions of NGs from 42 to 96 sp2 carbon atoms in the polyaromatic core to enhance the interfacial coupling strength, we find that the CT efficiency and rate in NG-Gr vdWHs display a drastic increase of one order of magnitude, despite the fact that the interfacial energy driving the CT process is unfavorably reduced. Our results shed light on the CT mechanism and provide an effective knob to tune the electronic coupling at NG-Gr interfaces by controlling the size-dependent vdW interactions.

A window to trap-free charge transport in organic semiconducting thin films.

Organic semiconductors, which serve as the active component in devices, such as solar cells, light-emitting diodes and field-effect transistors1, often exhibit highly unipolar charge transport, meaning that they predominantly conduct either electrons or holes. Here, we identify an energy window inside which organic semiconductors do not experience charge trapping for device-relevant thicknesses in the range of 100 to 300 nm, leading to trap-free charge transport of both carriers. When the ionization energy of a material surpasses 6 eV, hole trapping will limit the hole transport, whereas an electron affinity lower than 3.6 eV will give rise to trap-limited electron transport. When both energy levels are within this window, trap-free bipolar charge transport occurs. Based on simulations, water clusters are proposed to be the source of hole trapping. Organic semiconductors with energy levels situated within this energy window may lead to optoelectronic devices with enhanced performance. However, for blue-emitting light-emitting diodes, which require an energy gap of 3 eV, removing or disabling charge traps will remain a challenge.

Publisher Correction: Universal strategy for Ohmic hole injection into organic semiconductors with high ionization energies.

In the html version of this Article originally published, Paul W. M. Blom and Gert-Jan A. H. Wetzelaer were incorrectly listed as Paul M. W. Blom and Gert-Jan H. A. Wetzelaer, respectively, due to a technical error. This has now been amended in all online versions of the Article.

Universal strategy for Ohmic hole injection into organic semiconductors with high ionization energies.

Barrier-free (Ohmic) contacts are a key requirement for efficient organic optoelectronic devices, such as organic light-emitting diodes, solar cells, and field-effect transistors. Here, we propose a simple and robust way of forming an Ohmic hole contact on organic semiconductors with a high ionization energy (IE). The injected hole current from high-work-function metal-oxide electrodes is improved by more than an order of magnitude by using an interlayer for which the sole requirement is that it has a higher IE than the organic semiconductor. Insertion of the interlayer results in electrostatic decoupling of the electrode from the semiconductor and realignment of the Fermi level with the IE of the organic semiconductor. The Ohmic-contact formation is illustrated for a number of material combinations and solves the problem of hole injection into organic semiconductors with a high IE of up to 6 eV.

Self-Organization and Charge Transport Properties of Selenium and Tellurium Analogues of Polythiophene.

A series of conjugated polymers comprising polythiophene, polyselenophene, and polytellurophene with branched 3,7-dimethyloctyl side chains, well-matched molecular weight, dispersity, and regioregularity is synthesized. The ionization potential is found to vary from 5.14 to 5.32 eV, with polytellurophene having the lowest potential. Field-effect transistors based on these materials exhibit distinct hole transport mobility that varies by nearly three orders of magnitude, with polytellurophene having the highest mobility (2.5 × 10-2 cm² V-1 s-1 ). The large difference in mobility demonstrates the significant impact of heteroatom substitution. Although the series of polymers are very similar in structure, their solid-state properties are different. While the thin film microstructure of polythiophene and polyselenophene is identical, polytellurophene reveals globular features in the film topography. Polytellurophenes also appear to be the least crystalline, even though their charge transport properties are superior to other samples. The torsional barrier and degree of planarity between repeat units increase as one moves down group-16 elements. These studies show how a single atom in a polymer chain can have a substantial influence on the bulk properties of a material, and that heavy group-16 atoms have a positive influence on charge transport properties when all other variables are kept unchanged.

Understanding three-body contributions to coarse-grained force fields.

Coarse-graining is a systematic reduction of the number of degrees of freedom used to describe a system of interest. Coarse-graining can be thought of as a projection on the coarse-grained degrees of freedom and is therefore dependent on the number and type of basis functions used to represent the coarse-grained force field. We show that many-body extensions of the coarse-grained force field can result in substantial changes of the two-body interactions, making them much more attractive at short distances. This interplay can be alleviated by first parametrizing the two-body potential and then fitting the additional three-body contribution to the residual forces. The approach is illustrated on liquid water where three-body interactions are essential to reproduce the structural properties, and liquid methanol where two-body interactions are sufficient to reproduce the main structural features of the atomistic system. Furthermore, we demonstrate that the structural and thermodynamic accuracy of the coarse-grained models can be controlled by varying the magnitude of the three-body interactions. Our findings motivate basis set extensions which separate the many-body contributions of different order.

Efficiency-limiting processes in cyclopentadithiophene-bridged donor-acceptor-type dyes for solid-state dye-sensitized solar cells.

The charge generation and recombination processes in three novel push-pull photosensitizers for dye-sensitized solar cells (DSSCs) are studied by ps-µs transient absorption (TA) and quasi-steady-state photoinduced absorption (PIA) spectroscopy. The three cyclopentadithiophene-based photosensitizer dye molecules exhibit comparably low power conversion efficiencies ranging from 0.8% to 1.7% in solid-state DSSCs. We find that the photocurrents increase in the presence of Li-salt additives. Both TA and PIA measurements observe long-lived dye cations created by electron injection from the dyes' excited state for two dyes from the series. However, the third dye shows significantly lower performance as a consequence of the less efficient electron injection even after the addition of Li-salts and faster electron-hole recombination on the ns-µs time scale. In essence, the prerequisites for this class of donor-π bridge-acceptor photosensitizers to reach higher charge generation efficiencies are a combination of strong dipole moments and fine tuning of the electronic landscape at the titania-dye interface by Li-salt addition.

Influence of orientation mismatch on charge transport across grain boundaries in tri-isopropylsilylethynyl (TIPS) pentacene thin films.

We present a multi-scale model for charge transport across grain boundaries in molecular electronic materials that incorporates packing disorder, electrostatic and polarisation effects. We choose quasi two-dimensional films of tri-isopropylsilylethynyl pentacene (TIPS-P) as a model system representative of technologically relevant crystalline organic semiconductors. We use atomistic molecular dynamics, with a force-field specific for TIPS-P, to generate and equilibrate polycrystalline two-dimensional thin films. The energy landscape is obtained by calculating contributions from electrostatic interactions and polarization. The variation in these contributions leads to energetic barriers between grains. Subsequently, charge transport is simulated using a kinetic Monte-Carlo algorithm. Two-grain systems with varied mutual orientation are studied. We find relatively little effect of long grain boundaries due to the presence of low impedance pathways. However, effects could be more pronounced for systems with limited inter-grain contact areas. Furthermore, we present a lattice model to generalize the model for small molecular systems. In the general case, depending on molecular architecture and packing, grain boundaries can result in interfacial energy barriers, traps or a combination of both with qualitatively different effects on charge transport.

Electrochemical TERS Elucidates Potential-Induced Molecular Reorientation of Adenine/Au(111).

Electrochemical surface activity arises from the interaction and geometric arrangement of molecules at electrified interfaces. We present a novel electrochemical tip-enhanced Raman spectroscope that can access the vibrational fingerprint of less than 100 small, non-resonant molecules adsorbed at atomically flat Au electrodes to study their adsorption geometry and chemical reactivity as a function of the applied potential. Combining experimental and simulation data for adenine/Au(111), we conclude that protonated physisorbed adenine adopts a tilted orientation at low potentials, whereas it is vertically adsorbed around the potential of zero charge. Further potential increase induces adenine deprotonation and reorientation to a planar configuration. The extension of EC-TERS to the study of adsorbate reorientation significantly broadens the applicability of this advanced spectroelectrochemical tool for the nanoscale characterization of a full range of electrochemical interfaces.

Impact of mesoscale order on open-circuit voltage in organic solar cells.

Structural order in organic solar cells is paramount: it reduces energetic disorder, boosts charge and exciton mobilities, and assists exciton splitting. Owing to spatial localization of electronic states, microscopic descriptions of photovoltaic processes tend to overlook the influence of structural features at the mesoscale. Long-range electrostatic interactions nevertheless probe this ordering, making local properties depend on the mesoscopic order. Using a technique developed to address spatially aperiodic excitations in thin films and in bulk, we show how inclusion of mesoscale order resolves the controversy between experimental and theoretical results for the energy-level profile and alignment in a variety of photovoltaic systems, with direct experimental validation. Optimal use of long-range ordering also rationalizes the acceptor-donor-acceptor paradigm for molecular design of donor dyes. We predict open-circuit voltages of planar heterojunction solar cells in excellent agreement with experimental data, based only on crystal structures and interfacial orientation.

Design rules for organic donor-acceptor heterojunctions: pathway for charge splitting and detrapping.

Organic solar cells rely on the conversion of a Frenkel exciton into free charges via a charge-transfer state formed on a molecular donor-acceptor pair. These charge-transfer states are strongly bound by Coulomb interactions and yet efficiently converted into charge-separated states. A microscopic understanding of this process, though crucial to the functionality of any solar cell, has not yet been achieved. Here we show how long-range molecular order and interfacial mixing generate homogeneous electrostatic forces that can drive charge separation and prevent minority carrier trapping across a donor-acceptor interphase. Comparing a variety of small-molecule donor-fullerene combinations, we illustrate how tuning of molecular orientation and interfacial mixing leads to a trade-off between photovoltaic gap and charge-splitting and detrapping forces, with consequences for the design of efficient photovoltaic devices.

Charge carrier transport and photogeneration in P3HT:PCBM photovoltaic blends.

This article reviews the charge transport and photogeneration in bulk-heterojunction solar cells made from blend films of regioregular poly(3-hexylthiophene) (RR-P3HT) and methano-fullerene (PCBM). The charge transport, specifically the hole mobility in the RR-P3HT phase of the polymer:fullerene photovoltaic blend, is dramatically affected by thermal annealing. The hole mobility increases more than three orders of magnitude and reaches a value of up to 2 × 10(-4) cm(2) V(-1) s(-1) after the thermal annealing process as a result of an improved semi-crystallinity of the film. This significant increase of the hole mobility balances the electron and hole mobilities in a photovoltaic blend in turn reducing space-charge formation, and this is the most important factor for the strong enhancement of the photovoltaic efficiency compared to an as cast, that is, non-annealed device. In fact, the balanced charge carrier mobility in RR-P3HT:PCBM blends in combination with a field- and temperature-independent charge carrier generation and greatly reduced non-geminate recombination explains the large quantum efficiencies mea-sured in P3HT:PCBM photovoltaic devices.

Effect of mesoscale ordering on the density of States of polymeric semiconductors.

A multiscale simulation scheme, which incorporates both long-range conformational disorder and local molecular ordering, is proposed for predicting large-scale morphologies and charge transport properties of polymeric semiconductors. Using poly(3-hexylthiophene) as an example, it is illustrated how the energy landscape and its spatial correlations evolve with increasing degree of structural order in mesophases with amorphous, uniaxial, and biaxial nematic ordering. It is shown that the formation of low-lying energy states in more ordered systems is mostly due to larger (on average) conjugation lengths and not due to electrostatic interactions. The proposed scheme is general and can be applied to a wide range of polymeric organic materials.

Parameter-free continuous drift-diffusion models of amorphous organic semiconductors.

Continuous drift-diffusion models are routinely used to optimize organic semiconducting devices. Material properties are incorporated into these models via dependencies of diffusion constants, mobilities, and injection barriers on temperature, charge density, and external field. The respective expressions are often provided by the generic Gaussian disorder models, parametrized on experimental data. We show that this approach is limited by the fixed range of applicability of analytic expressions as well as approximations inherent to lattice models. To overcome these limitations we propose a scheme which first tabulates simulation results performed on small-scale off-lattice models, corrects for finite size effects, and then uses the tabulated mobility values to solve the drift-diffusion equations. The scheme is tested on DPBIC, a state of the art hole conductor for organic light emitting diodes. We find a good agreement between simulated and experimentally measured current-voltage characteristics for different film thicknesses and temperatures.