OCELOT: An infrastructure for data-driven research to discover and design crystalline organic semiconductors.

Materials design and discovery are often hampered by the slow pace and materials and human costs associated with Edisonian trial-and-error screening approaches. Recent advances in computational power, theoretical methods, and data science techniques, however, are being manifest in a convergence of these tools to enable in silico materials discovery. Here, we present the development and deployment of computational materials data and data analytic approaches for crystalline organic semiconductors. The OCELOT (Organic Crystals in Electronic and Light-Oriented Technologies) infrastructure, consisting of a Python-based OCELOT application programming interface and OCELOT database, is designed to enable rapid materials exploration. The database contains a descriptor-based schema for high-throughput calculations that have been implemented on more than 56 000 experimental crystal structures derived from 47 000 distinct molecular structures. OCELOT is open-access and accessible via a web-user interface at https://oscar.as.uky.edu.

Modification of the LiFePO4 (010) Surface Due to Exposure to Atmospheric Gases.

First-principles thermodynamics enables the description of the surface chemistry of inorganic materials as a function of temperature and partial pressures of atmospheric gases, providing a framework to connect atomistic simulations with macroscopic materials properties. Here we re-examine the surface chemistry of LiFePO4 (LFP), a widely studied material for use as the cathode in Li-ion batteries. Our results reveal that at room temperature and under standard pressures the LFP (010) surface is covered with water. At elevated temperatures and reduced H2 partial pressure, one water molecule loses a hydrogen atom and the preferred binding moieties are OH and H2O; while further reducing the H2O partial pressure results in the desorption of water leaving only the OH behind. This work also shines new light on the configuration, and resulting electronic properties, of the LFP (010) surface when molecular oxygen (O2) is adsorbed. The molecular adsorbates are also shown to have an impact on the LFP surface potentials and magnetic properties. These simulations provide an enhanced picture of the LFP surface chemistry and the potential impact of these adsorbates on understanding the characteristics of LFP in different materials applications.

Presence of Short Intermolecular Contacts Screens for Kinetic Stability in Packing Polymorphs.

Polymorphism is pervasive in molecular solids. While computational predictions of the molecular polymorphic landscape have improved significantly, identifying which polymorphs are preferentially accessed and experimentally stable remains a challenge. We report a framework that correlates short intermolecular contacts with polymorphic stability. The presence of short contacts between neighboring molecules prevents structural rearrangement and stabilizes the packing arrangement, even when the stabilized polymorph is not enthalpically favored. In the absence of such intermolecular short contacts, the molecules have added degrees of freedom for structural rearrangement, and solid-solid polymorphic transformations occur readily. Starting with a series of core-halogenated naphthalene tetracarboxylic diimides, we establish this framework with the packing polymorphs of more than 20 compounds, ranging from molecular semiconductors to pharmaceutics and biological building blocks. This framework, widely applicable across molecular solids, can help refine computational predictions by identifying the polymorphs that are kinetically stable.

Unusual Electronic Structure of the Donor-Acceptor Cocrystal Formed by Dithieno[3,2-a:2',3'-c]phenazine and 7,7,8,8-Tetracyanoquinodimethane.

Mixed cocrystals derived from electron-rich donor (D) and electron-deficient acceptor (A) molecules showcase electronic, optical, and magnetic properties of interest for a wide range of applications. We explore the structural and electronic properties of a cocrystal synthesized from dithieno[3,2-a:2',3'-c]phenazine (DTPhz) and 7,7,8,8-tetracyanoquinodimethane (TCNQ), which has a mixed-stack packing arrangement of the (π-electronic) face-to-face stacks in a 2:1 D:A stoichiometry. Density functional theory investigations reveal that the primary electronic characteristics of the cocrystal are not determined by electronic interactions along the face-to-face stacks, but rather they are characterized by stronger electronic interactions orthogonal to these stacks that follow the edge-to-edge donor-donor or acceptor-acceptor contacts. These distinctive electronic characteristics portend semiconducting properties that are unusual for semiconducting mixed cocrystals and suggest further potential to design organic semiconductors with orthogonal transport characteristics for different charge carriers.

Crossover from band-like to thermally activated charge transport in organic transistors due to strain-induced traps.

The temperature dependence of the charge-carrier mobility provides essential insight into the charge transport mechanisms in organic semiconductors. Such knowledge imparts critical understanding of the electrical properties of these materials, leading to better design of high-performance materials for consumer applications. Here, we present experimental results that suggest that the inhomogeneous strain induced in organic semiconductor layers by the mismatch between the coefficients of thermal expansion (CTE) of the consecutive device layers of field-effect transistors generates trapping states that localize charge carriers. We observe a universal scaling between the activation energy of the transistors and the interfacial thermal expansion mismatch, in which band-like transport is observed for similar CTEs, and activated transport otherwise. Our results provide evidence that a high-quality semiconductor layer is necessary, but not sufficient, to obtain efficient charge-carrier transport in devices, and underline the importance of holistic device design to achieve the intrinsic performance limits of a given organic semiconductor. We go on to show that insertion of an ultrathin CTE buffer layer mitigates this problem and can help achieve band-like transport on a wide range of substrate platforms.

Electron tomography analysis of 3D interfacial nanostructures appearing in annealed Si rich SiC films.

The optical and electrical properties of Si rich SiC (SRSC) solar cell absorber layers will strongly depend on interfacial layers between the Si and the SiC matrix and in this work, we analyze hitherto undiscovered interfacial layers. The SRSC thin films were deposited using a plasma-enhanced chemical vapor deposition (PECVD) technique and annealed in a nitrogen environment at 1100 °C. The thermal treatment leads to metastable SRSC films spinodally decomposed into a Si-SiC nanocomposite. After the thermal treatment, the coexistence of crystalline Si and SiC nanostructures was analysed by high resolution transmission electron microscopy (HRTEM) and electron diffraction. From the quantitative extraction of the different plasmon signals from electron energy-loss spectra, an additional structure, amorphous SiC (a-SiC) was found. Quantitative spectroscopic electron tomography was developed to obtain three dimensional (3D) plasmonic maps. In these 3D spectroscopic maps, the Si regions appear as network structures inside the SiC matrix where the a-SiC appears as an interfacial layer separating the matrix and Si network. The presence of the a-SiC interface can be explained in the framework of the nucleation and growth model.

Indacenodibenzothiophenes: synthesis, optoelectronic properties and materials applications of molecules with strong antiaromatic character.

Indeno[1,2-b]fluorenes (IFs), while containing 4n π-electrons, are best described as two aromatic benzene rings fused to a weakly paratropic s-indacene core. In this study, we find that replacement of the outer benzene rings of an IF with benzothiophenes allows the antiaromaticity of the central s-indacene to strongly reassert itself. Herein we report a combined synthetic, computational, structural, and materials study of anti- and syn-indacenodibenzothiophenes (IDBTs). We have developed an efficient and scalable synthesis for preparation of a series of aryl- and ethynyl-substituted IDBTs. NICS-XY scans and ACID calculations reveal an increasingly antiaromatic core from [1,2-b]IF to anti-IDBT, with syn-IDBT being nearly as antiaromatic as the parent s-indacene. As an initial evaluation, the intermolecular electronic couplings and electronic band structure of a diethynyl anti-IDBT derivative reveal the potential for hole and / or electron transport. OFETs constructed using this molecule show the highest hole mobilities yet achieved for a fully conjugated IF derivative.

Nanocrystal size distribution analysis from transmission electron microscopy images.

We propose a method, with minimal bias caused by user input, to quickly detect and measure the nanocrystal size distribution from transmission electron microscopy (TEM) images using a combination of Laplacian of Gaussian filters and non-maximum suppression. We demonstrate the proposed method on bright-field TEM images of an a-SiC:H sample containing embedded silicon nanocrystals with varying magnifications and we compare the accuracy and speed with size distributions obtained by manual measurements, a thresholding method and PEBBLES. Finally, we analytically consider the error induced by slicing nanocrystals during TEM sample preparation on the measured nanocrystal size distribution and formulate an equation to correct this effect.