Measuring Intermolecular Excited State Geometry for Favorable Singlet Fission in Tetracene.

Singlet fission (SF) is the process of converting an excited singlet to a pair of excited triplets. Harvesting two charges from a single photon has the potential to increase photovoltaic device efficiencies. Acenes, such as tetracene and pentacene, are model molecules for studying SF.

Compact, portable, automatic sample changer stick for cryostats and closed-cycle refrigerators.

Beamlines are facilities that produce and deliver highly focused and intense beams of radiation, typically x rays, synchrotron radiation, or neutrons, for scientific research purposes. Millions of dollars are spent annually to maintain and operate these scientific beamlines, oftentimes running continuously between cycles. To reduce human intervention and improve productivity, mechanical sample changers are often commissioned for use.

Photochemistry sample sticks for inelastic neutron scattering.

Every material experiences atomic and molecular motions that are generally termed vibrations in gases and liquids or phonons in solid state materials. Optical spectroscopy techniques, such as Raman, infrared absorption spectroscopy, or inelastic neutron scattering (INS), can be used to measure the vibrational/phonon spectrum of ground state materials properties. A variety of optical pump probe spectroscopies enable the measurement of excited states or elucidate photochemical reaction pathways and kinetics.

Elucidating correlated defects in metal organic frameworks using theory-guided inelastic neutron scattering spectroscopy.

Metal organic frameworks (MOFs) that incorporate metal oxide cluster nodes, exemplified by UiO-66, have been widely studied, especially in terms of their deviations from the ideal, defect-free crystalline structures. Although defects such as missing linkers, missing nodes, and the presence of adventitious synthesis-derived node ligands (such as acetates and formates) have been proposed, their exact structures remain unknown. Previously, it was demonstrated that defects are correlated and span multiple unit cells.

Quantitative Hole Mobility Simulation and Validation in Substituted Acenes.

Knowledge of the full phonon spectrum is essential to accurately calculate the dynamic disorder (σ) and hole mobility (μ) in organic semiconductors (OSCs). However, most vibrational spectroscopy techniques under-measure the phonons, thus limiting the phonon validation. Here, we measure and model the full phonon spectrum using multiple spectroscopic techniques and predict μ using σ from only the Γ-point and the full Brillouin zone (FBZ).

Comparing the Expense and Accuracy of Methods to Simulate Atomic Vibrations in Rubrene.

Atomic vibrations can inform about materials properties from hole transport in organic semiconductors to correlated disorder in metal-organic frameworks. Currently, there are several methods for predicting these vibrations using simulations, but the accuracy-efficiency tradeoffs have not been examined in depth. In this study, rubrene is used as a model system to predict atomic vibrational properties using six different simulation methods: density functional theory, density functional tight binding, density functional tight binding with a Chebyshev polynomial-based correction, a trained machine learning model, a pretrained machine learning model called ANI-1, and a classical forcefield model.

Davis Computational Spectroscopy Workflow-From Structure to Spectra.

We describe an automated workflow that connects a series of atomic simulation tools to investigate the relationship between atomic structure, lattice dynamics, materials properties, and inelastic neutron scattering (INS) spectra. Starting from the atomic simulation environment (ASE) as an interface, we demonstrate the use of a selection of calculators, including density functional theory (DFT) and density functional tight binding (DFTB), to optimize the structures and calculate interatomic force constants. We present the use of our workflow to compute the phonon frequencies and eigenvectors, which are required to accurately simulate the INS spectra in crystalline solids like diamond and graphite as well as molecular solids like rubrene.

Computing inelastic neutron scattering spectra from molecular dynamics trajectories.

Inelastic neutron scattering (INS) provides a weighted density of phonon modes. Currently, INS spectra can only be interpreted for perfectly crystalline materials because of high computational cost for electronic simulations. INS has the potential to provide detailed morphological information if sufficiently large volumes and appropriate structural variety are simulated.

Super-Resolution Photothermal Patterning in Conductive Polymers Enabled by Thermally Activated Solubility.

Doping-induced solubility control (DISC) patterning is a recently developed technique that uses the change in polymer solubility upon doping, along with an optical dedoping process, to achieve high-resolution optical patterning. DISC patterning can produce features smaller than predicted by the diffraction limit; however, no mechanism has been proposed to explain such high resolution. Here, we use diffraction to spatially modulate the light intensity and determine the dissolution rate, revealing a superlinear dependence on light intensity.

Anion Exchange Doping: Tuning Equilibrium to Increase Doping Efficiency in Semiconducting Polymers.

High electron affinity (EA) molecules p-type dope low ionization energy (IE) polymers, resulting in an equilibrium doping level based on the energetic driving force (IE-EA), reorganization energy, and dopant concentration. Anion exchange doping (AED) is a process whereby the dopant anion is exchanged with a stable ion from an electrolyte. We show that the AED level can be predicted using an isotherm equilibrium model.

Toward Fast Screening of Organic Solar Cell Blends.

The ever increasing library of materials systems developed for organic solar-cells, including highly promising non-fullerene acceptors and new, high-efficiency donor polymers, demands the development of methodologies that i) allow fast screening of a large number of donor:acceptor combinations prior to device fabrication and ii) permit rapid elucidation of how processing affects the final morphology/microstructure of the device active layers. Efficient, fast screening will ensure that important materials combinations are not missed; it will accelerate the technological development of this alternative solar-cell platform toward larger-area production; and it will permit understanding of the structural changes that may occur in the active layer over time. Using the relatively high-efficiency poly[(5,6-difluoro-2,1,3-benzothiadiazol-4,7-diyl)-alt-(3,3'''-di(2-octyldodecyl)-2,2';5',2'';5'',2'''-quaterthiophen-5,5'''-diyl)] (PCE11):phenyl-C61-butyric acid-methyl-ester acceptor (PCBM) blend systems, it is demonstrated that by means of straight-forward thermal analysis, vapor-phase-infiltration imaging, and transient-absorption spectroscopy, various blend compositions and processing methodologies can be rapidly screened, information on promising combinations can be obtained, reliability issues with respect to reproducibility of thin-film formation can be identified, and insights into how processing aids, such as nucleating agents, affect structure formation, can be gained.

Predictive Model of Charge Mobilities in Organic Semiconductor Small Molecules with Force-Matched Potentials.

Charge mobility of crystalline organic semiconductors (OSC) is limited by local dynamic disorder. Recently, the charge mobility for several high mobility OSCs, including TIPS-pentacene, were accurately predicted from a density functional theory (DFT) simulation constrained by the crystal structure and the inelastic neutron scattering spectrum, which provide direct measures of the structure and the dynamic disorder in the length scale and energy range of interest. However, the computational expense required for calculating all of the atomic and molecular forces is prohibitive.

High-Speed Photothermal Patterning of Doped Polymer Films.

Organic semiconductors (OSCs) offer a new avenue to the next-generation electronics, but the lack of a scalable and inexpensive nanoscale patterning/deposition technique still limits their use in electronic applications. Recently, a new lithographic etching technique has been introduced that uses molecular dopants to reduce semiconducting polymer solubility in solvents and a direct-write laser to remove dopants locally, enabling rapid OSC etching with diffraction limited resolution. Previous publications postulated that the reaction that enables patterning is a photochemical reaction between photoexcited dopants with neutral solvent molecules.

Double doping of conjugated polymers with monomer molecular dopants.

Molecular doping is a crucial tool for controlling the charge-carrier concentration in organic semiconductors. Each dopant molecule is commonly thought to give rise to only one polaron, leading to a maximum of one donor:acceptor charge-transfer complex and hence an ionization efficiency of 100%. However, this theoretical limit is rarely achieved because of incomplete charge transfer and the presence of unreacted dopant.

Controlling Molecular Doping in Organic Semiconductors.

The field of organic electronics thrives on the hope of enabling low-cost, solution-processed electronic devices with mechanical, optoelectronic, and chemical properties not available from inorganic semiconductors. A key to the success of these aspirations is the ability to controllably dope organic semiconductors with high spatial resolution. Here, recent progress in molecular doping of organic semiconductors is summarized, with an emphasis on solution-processed p-type doped polymeric semiconductors.

Optical Dedoping Mechanism for P3HT:F4TCNQ Mixtures.

Doping-induced solubility control (DISC) is a recently introduced photolithographic technique for semiconducting polymers, which utilizes reversible changes in polymer solubility upon doping to allow the polymer to function as its own photoresist. Central to this process is a wavelength sensitive optical dedoping reaction, which is poorly understood but generates subdiffraction-limited topographic features and provides optical control of the polymer doping level. Here, we examine the mechanism of optical dedoping in the semiconducting polymer poly-3-hexylthiophene (P3HT) doped by 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), via a combination of ultrafast and steady-state spectroscopy, ab initio calculations, and multidimensional NMR.

Direct-Write Optical Patterning of P3HT Films Beyond the Diffraction Limit.

Doping-induced solubility control is a patterning technique for semiconducting polymers, which utilizes the reduction in polymer solubility upon p-type doping to provide direct, optical control of film topography and doping level. In situ direct-write patterning and imaging are demonstrated, revealing sub-diffraction-limited topographic features. Photoinduced force microscopy shows that doping level can be optically modulated with similar resolution.

Nanoscale Morphology of PTB7 Based Organic Photovoltaics as a Function of Fullerene Size.

High efficiency polymer:fullerene photovoltaic device layers self-assemble with hierarchical features from ångströms to 100's of nanometers. The feature size, shape, composition, orientation, and order all contribute to device efficiency and are simultaneously difficult to study due to poor contrast between carbon based materials. This study seeks to increase device efficiency and simplify morphology measurements by replacing the typical fullerene acceptor with endohedral fullerene Lu3N@PC80BEH.

Measurement of Small Molecular Dopant F4TCNQ and C60F36 Diffusion in Organic Bilayer Architectures.

The diffusion of molecules through and between organic layers is a serious stability concern in organic electronic devices. In this work, the temperature-dependent diffusion of molecular dopants through small molecule hole transport layers is observed. Specifically we investigate bilayer stacks of small molecules used for hole transport (MeO-TPD) and p-type dopants (F4TCNQ and C60F36) used in hole injection layers for organic light emitting diodes and hole collection electrodes for organic photovoltaics.

Reversible optical control of conjugated polymer solubility with sub-micrometer resolution.

Organic electronics promise to provide flexible, large-area circuitry such as photovoltaics, displays, and light emitting diodes that can be fabricated inexpensively from solutions. A major obstacle to this vision is that most conjugated organic materials are miscible, making solution-based fabrication of multilayer or micro- to nanoscale patterned films problematic. Here we demonstrate that the solubility of prototypical conductive polymer poly(3-hexylthiophene) (P3HT) can be reversibly "switched off" using high electron affinity molecular dopants, then later recovered with light or a suitable dedoping solution.

Packing dependent electronic coupling in single poly(3-hexylthiophene) H- and J-aggregate nanofibers.

Nanofibers (NFs) of the prototype conjugated polymer, poly(3-hexylthiophene) (P3HT), displaying H- and J-aggregate character are studied using temperature- and pressure-dependent photoluminescence (PL) spectroscopy. Single J-aggregate NF spectra show a decrease of the 0-0/0-1 vibronic intensity ratio from ~2.0 at 300 K to ~1.

A comparative MD study of the local structure of polymer semiconductors P3HT and PBTTT.

Atomistic molecular dynamics simulations of P3HT and PBTTT-C12 at finite temperatures are carried out to investigate the nanoscale structural properties that lead to higher measured hole mobility in PBTTT versus P3HT field-effect transistors. Simulations of the polymer melts show that the structural properties in PBTTT facilitate both intra- and inter-chain charge transport compared with P3HT due to a greater degree of planarity, closer and more parallel stacking of the thiophene and thienothiophene rings, and possible interdigitation of the dodecyl side chains. The crucial role played by the bulky dodecyl side chain and thienothiophene ring, respectively, in determining intra-chain and inter-chain structural order is clarified.

Coarse-Grained Computer Simulations of Polymer/Fullerene Bulk Heterojunctions for Organic Photovoltaic Applications.

We develop coarse-grained (CG) computer simulation models of poly(3-hexylthiophene) (P3HT) and P3HT/fullerene-C60 mixtures, in which collections of atoms from a physically accurate atomistic model are mapped onto a smaller number of "superatoms". These CG models allow much larger systems to be simulated for longer durations than is achievable atomistically, making it possible to study in molecular detail the morphology of polymer/fullerene bulk heterojunctions at length and time scales relevant to organic photovoltaic devices. We demonstrate that our CG models, parametrized at two state points, accurately capture the structure of atomistic systems at other points in the mixture phase diagram.

Efficiency enhancements in solid-state hybrid solar cells via reduced charge recombination and increased light capture.

We compare a series of molecular sensitizers in dye-sensitized solar cells containing the organic hole transporter 2,2',7,7'-tetrakis(N,N-di-p-methoxypheny-amine)-9,9'-spirobifluorene (spiro-MeOTAD). Charge recombination is reduced by the presence of "ion-coordinating" moieties on the dye, with the longest electron lifetime and highest solar cell efficiency achieved using a novel sensitizer with diblock alkoxy-alkane pendent groups. By further increasing the optical path length in the active layer, we achieve a power conversion efficiency of over 5% under simulated sun light.

High-resolution NMR of static samples by rotation of the magnetic field.

Mechanical rotation of a sample at 54.7 degrees with respect to the static magnetic field, so-called magic-angle spinning (MAS), is currently a routine procedure in nuclear magnetic resonance (NMR). The technique enhances the spectral resolution by averaging away anisotropic spin interactions thereby producing isotropic-like spectra with resolved chemical shifts and scalar couplings.