The Epitaxial Growth of Self-Assembled Ternaphthalene Fibers on Muscovite Mica

The morphology and structure of 2,2′:6′,2″-ternaphthalene (NNN) deposited on muscovite mica(001) substrates was investigated by scanning force microscopy (SFM) and specular X-ray diffraction measurements. Consistently, both methods reveal the coexistence of needle-like structures with a {111} contact plane and {001} orientated island-like crystallites, which are built up by almost upright standing NNN molecules. Both orientations are characterized by a well-defined azimuthal alignment relative to the substrate surface, which is analyzed by X-ray diffraction pole figure (XRD-PF) measurements. Based on XRD-PF and SFM analysis, the azimuthal alignment of {001} orientated crystallites is explained by ledge-directed epitaxy along the fibers’ sidewalls. These fibers are found to orient along two dominant directions, which is verified and explained by a doubling of the energetically preferred molecular adsorption site by mirror symmetry of the substrate surface. The experimental findings are confirmed by force-field simulations and are discussed based on a recently reported growth model

Interfacial Morphology and Effects on Device Performance of Organic Bilayer Heterojunction Solar Cells

The effects of interface roughness between donor and acceptor in a bilayer heterojunction solar cell were investigated on a polymer–polymer system based on poly­(3-hexylthiophene) (P3HT) and poly­(dioctylfluorene-<i>alt</i>-benzothiadiazole) (F8BT). Both polymers are known to reorganize into semicrystalline structures when heated above their glass-transition temperature. Here, the bilayers were thermally annealed below glass transition of the bulk polymers (≈140 °C) at temperatures of 90, 100, and 110 °C for time periods from 2 min up to 250 min. No change of crystallinity could be observed at those temperatures. However, X-ray reflectivity and device characteristics reveal a coherent trend upon heat treatment. In X-ray reflectivity investigations, an increasing interface roughness between the two polymers is observed as a function of temperature and annealing time, up to a value of 1 nm. Simultaneously, according bilayer devices show an up to 80% increase of power conversion efficiency (PCE) for short annealing periods at any of the mentioned temperatures. Together, this is in agreement with the expectations for enlargement of the interfacial area. However, for longer annealing times, a decrease of PCE is observed, despite the ongoing increase of interface roughness. The onset of decreasing PCE shifts to shorter durations the higher the annealing temperature. Both, X-ray reflectivity and device characteristics display a significant change at temperatures below the glass transition temperatures of P3HT and F8BT

Morphological and Structural Investigation of Sexithiophene Growth on KCl (100)

The morphology and structure of sexithiophene deposited on KCl (100) substrates was investigated by scanning force microscopy and specular X-ray diffraction measurements. Two different needle-like structures with {010} and {4̅11} contact planes have been observed as well as islands of almost upright standing sexithiophene molecules with a {100} contact plane. Furthermore an azimuthal alignment of all three crystal orientations was observed by X-ray diffraction pole figure measurements, and the growth directions reflect the 4-fold rotational symmetry of the substrate surface. In addition the analysis of crystals with {4̅11} and {100} contact planes unveiled that they share a common crystallographic direction which is explained by ledge directed epitaxy

Complex Behavior of Caffeine Crystallites on Muscovite Mica Surfaces

Defined fabrication of organic thin films is highly desired in technological, as well as pharmaceutical, applications since morphology and crystal structure are directly linked to physical, electrical, and optical properties. Within this work, the directed growth of caffeine deposited by hot wall epitaxy (HWE) on muscovite mica is studied. Optical and atomic force microscopy measurements reveal the presence of caffeine needles exhibiting a preferable alignment in the azimuthal directions with respect to the orientation of the defined mica surface. Specular X-ray diffraction and X-ray diffraction pole figure measurements give evidence that the β-polymorphic form of caffeine forms on the mica surface. All results consent that caffeine molecules have an edge-on conformation i.e. minimizing their interaction area with the surface. Furthermore, the azimuthal alignment of the long caffeine needle axis takes place along the [11̅0], [100], and [110] real space directions of mica; needles are observed every 60° azimuthally. While mica has a complex surface structure with mirror planes and lowered oxygen rows, the slightly disturbed 3-fold symmetry dictates the crystal alignment. This is different to previous findings for solution cast caffeine growth on mica. For HWE the needles align solely along the mica main directions whereby solution cast needles show an additional needle splitting due to a different alignment of caffeine with respect to the surface

Accessing Phase-Pure and Stable Acetaminophen Polymorphs by Thermal Gradient Crystallization

We employ a simple and reproducible methodology based on thermal gradient crystallization to access forms <b>I</b> and <b>II</b> of acetaminophen. This methodology provides insight into the role of heat flux in the control over polymorphism and phase transitions. We report the crystallization of different polymorphs of acetaminophen as a function of the thermal gradient parameters (magnitude of the gradient, sample velocity) in a thin film geometry. The thin-film samples were displaced at well-defined velocities (1 ≤ <i>v</i> ≤ 75 μm/s) to control both the direction and the rate of crystal growth. We carried out a detailed structural analysis combining polarized optical microscopy and X-ray diffraction (specular and grazing-incidence) to characterize the crystalline forms isolated by the thermal gradient technique. The resulting polymorphic forms have been found to exhibit high phase purity and remarkable stability over time

Icephobic Gradient Polymer Coatings Deposited via iCVD: A Novel Approach for Icing Control and Mitigation

Materials against ice formation and accretion are highly desirable for different industrial applications and daily activities affected by icing. Although several concepts have been proposed, no material has so far shown wide-ranging icephobic features, enabling durability and manufacturing on large scales. Herein, we present gradient polymers made of 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane (V4D4) and 1H,1H,2H,2H-perfluorodecyl acrylate (PFDA) deposited in one step via initiated chemical vapor deposition (iCVD) as an effective coating to mitigate ice accretion and reduce ice adhesion. The gradient structures easily overcome adhesion, stability, and durability issues of traditional fluorinated coatings. The coatings show promising icephobic performance by reducing ice adhesion, depressing the freezing point, delaying drop freezing, and inhibiting ice nucleation and frost propagation. Icephobicity correlates with surface energy discontinuities at the surface plane resulting from the random orientation of the fluorinated groups of PFDA, as confirmed by grazing-incidence X-ray diffraction measurements. The icephobicity could be further improved by tuning the surface crystallinity rather than surface wetting, as samples with random crystal orientation show the lowest ice adhesion despite high contact angle hysteresis. The iCVD-manufactured coatings show promising results, indicating the potential for ice control on larger scales and various applications

Initial Steps of Rubicene Film Growth on Silicon Dioxide

The film growth of the conjugated organic molecule rubicene on silicon dioxide was studied in detail. Since no structural data of the condensed material were available, we first produced high quality single crystals from solution and determined the crystal structure. This high purity material was used to prepare ultrathin films under ultrahigh vacuum conditions, by physical vapor deposition. Thermal desorption spectroscopy (TDS) was applied to delineate the adsorption and desorption kinetics. It could be shown that the initial sticking coefficient is only 0.2 ± 0.05, but the sticking coefficient increases with increasing coverage. TDS further revealed that first a closed, weakly bound bilayer develops (wetting layer), which dewets after further deposition of rubicene, leading to an island-like layer. These islands are crystalline and exhibit the same structure as the solution grown crystals. The orientation of the crystallites is with the (001) plane parallel to the substrate. A dewetting of the closed bilayer was also observed when the film was exposed to air. Furthermore, Ostwald ripening of the island-like film takes place under ambient conditions, leading to films composed of few, large crystallites. From TDS, we determined the heat of evaporation from the multilayer islands to be 1.47 eV, whereas the desorption energy from the first layer is only 1.25 eV

One Polymorph and Various Morphologies of Phenytoin at a Silica Surface Due to Preparation Kinetics

The preparation of solid crystalline films at surfaces is of great interest in a variety of fields. Within this work the preparation of pharmaceutically relevant thin films containing the active pharmaceutical ingredient phenytoin is demonstrated. The preparation techniques applied include drop casting, spin coating, and vacuum deposition. For the solution processed samples a decisive impact of the solution concentration and the applied film fabrication technique is observed; particular films form for all samples but with their extensions along different crystallographic directions strongly altered. Vacuum deposition of phenytoin reveals amorphous films, which over time crystallize into needle-like or particular-type structures whereby a nominal thickness of 50 nm is required to achieve a fully closed layer. Independent of all preparation techniques, the resulting polymorph is the same for each sample as confirmed by specular X-ray diffraction scans. Thus, morphologies observed via optical and atomic force microscope techniques are therefore a result of the preparation technique. This shows that the different time scales for which crystallization is obtained is the driving force for the various morphologies in phenytoin thin films rather than the presence of another polymorph forming

Stimulated Emission Properties of Sterically Modified Distyrylbenzene-Based H‑Aggregate Single Crystals

J-aggregation has been shown to be beneficial for light amplification in single crystals of π-conjugated organic molecules. In the case of H-aggregation, the criteria for such processes are still under debate. It has also been shown that H-aggregate arrangements with considerable π–π overlap are detrimental for light amplification. We show here that a proper alignment of the molecules in the crystal lattice, which minimizes π–π overlap between adjacent molecules, gives rise to (random) stimulated emission from cofacial arrangements similar to that of the herringbone aggregates

Substrate-Induced Phase of a [1]Benzothieno[3,2‑<i>b</i>]benzothiophene Derivative and Phase Evolution by Aging and Solvent Vapor Annealing

Substrate-induced phases (SIPs) are polymorphic phases that are found in thin films of a material and are different from the single crystal or “bulk” structure of a material. In this work, we investigate the presence of a SIP in the family of [1]­benzothieno­[3,2-<i>b</i>]­benzothiophene (BTBT) organic semiconductors and the effect of aging and solvent vapor annealing on the film structure. Through extensive X-ray structural investigations of spin coated films, we find a SIP with a significantly different structure to that found in single crystals of the same material forms; the SIP has a herringbone motif while single crystals display layered π–π stacking. Over time, the structure of the film is found to slowly convert to the single crystal structure. Solvent vapor annealing initiates the same structural evolution process but at a greatly increased rate, and near complete conversion can be achieved in a short period of time. As properties such as charge transport capability are determined by the molecular structure, this work highlights the importance of understanding and controlling the structure of organic semiconductor films and presents a simple method to control the film structure by solvent vapor annealing