Structural Order in Cellulose Thin Films Prepared from a Trimethylsilyl Precursor.

Biopolymer cellulose is investigated in terms of the crystallographic order within thin films. The films were prepared by spin-coating of a trimethylsilyl cellulose precursor followed by an exposure to HCl vapors; two different source materials were used. Careful precharacterization of the films was performed by infrared spectroscopy and atomic force microscopy. Subsequently, the films were investigated by grazing incidence X-ray diffraction using synchrotron radiation. The results showed broad diffraction peaks, indicating a rather short correlation length of the molecular packing in the range of a few nanometers. The analysis of the diffraction patterns was based on the known structures of crystalline cellulose, as the observed peak pattern was comparable to cellulose phase II and phase III. The dominant fraction of the film is formed by two different types of layers, which are oriented parallel to the substrate surface. The stacking of the layers results in a one-dimensional crystallographic order with a defined interlayer distance of either 7.3 or 4.2 Å. As a consequence, two different preferred orientations of the polymer chains are observed. In both cases, polymer chain axes are aligned parallel to the substrate surface, and the orientation of the cellulose molecules are concluded to be either edge-on or flat-on. A minor fraction of the cellulose molecules form nanocrystals that are randomly distributed within the films. In this case, the molecular packing density was found to be smaller in comparison to the known crystalline phases of cellulose.

GIDVis: a comprehensive software tool for geometry-independent grazing-incidence X-ray diffraction data analysis and pole-figure calculations.

GIDVis is a software package based on MATLAB specialized for, but not limited to, the visualization and analysis of grazing-incidence thin-film X-ray diffraction data obtained during sample rotation around the surface normal. GIDVis allows the user to perform detector calibration, data stitching, intensity corrections, standard data evaluation (e.g. cuts and integrations along specific reciprocal-space directions), crystal phase analysis etc. To take full advantage of the measured data in the case of sample rotation, pole figures can easily be calculated from the experimental data for any value of the scattering angle covered. As an example, GIDVis is applied to phase analysis and the evaluation of the epitaxial alignment of pentacene-quinone crystallites on a single-crystalline Au(111) surface.

Indexing of grazing-incidence X-ray diffraction patterns: the case of fibre-textured thin films.

Crystal structure solutions from thin films are often performed by grazing-incidence X-ray diffraction (GIXD) experiments. In particular, on isotropic substrates the thin film crystallites grow in a fibre texture showing a well defined crystallographic plane oriented parallel to the substrate surface with random in-plane order of the microcrystallites forming the film. In the present work, analytical mathematical expressions are derived for indexing experimental diffraction patterns, a highly challenging task which hitherto mainly relied on trial-and-error approaches. The six lattice constants a, b, c, α, ß and γ of the crystallographic unit cell are thereby determined, as well as the rotation parameters due to the unknown preferred orientation of the crystals with respect to the substrate surface. The mathematical analysis exploits a combination of GIXD data and information acquired by the specular X-ray diffraction. The presence of a sole specular diffraction peak series reveals fibre-textured growth with a crystallographic plane parallel to the substrate, which allows establishment of the Miller indices u, v and w as the rotation parameters. Mathematical expressions are derived which reduce the system of unknown parameters from the three- to the two-dimensional space. Thus, in the first part of the indexing routine, the integers u and v as well as the Laue indices h and k of the experimentally observed diffraction peaks are assigned by systematically varying the integer variables, and by calculating the three lattice parameters a, b and γ. Because of the symmetry of the derived equations, determining the missing parameters then becomes feasible: (i) w of the surface parallel plane, (ii) the Laue indices l of the diffraction peak and (iii) analogously the lattice constants c, α and ß. In a subsequent step, the reduced unit-cell geometry can be identified. Finally, the methodology is demonstrated by application to an example, indexing the diffraction pattern of a thin film of the organic semiconductor pentacenequinone grown on the (0001) surface of highly oriented pyrolytic graphite. The preferred orientation of the crystallites, the lattice constants of the triclinic unit cell and finally, by molecular modelling, the full crystal structure solution of the as-yet-unknown polymorph of pentacenequinone are determined.

Crystal alignment of caffeine deposited onto single crystal surfaces via hot-wall epitaxy.

Defined crystal growth is highly demanded for technological applications but also fundamental research. Within this work, the crystal growth of the asymmetric molecule caffeine was studied on single crystalline surfaces of muscovite mica, sodium chloride and potassium chloride. While elongated needle-like crystals grow on muscovite mica and sodium chloride, smaller individual "bird-like" structures were observed on potassium chloride. Depending on the surface type and temperature, the disk-shaped caffeine molecules prefer either an edge-on or flat-on orientation with respect to the surface, but in each case, a defined crystallographic relation between the surface and caffeine crystallites was determined by using the X-ray pole figure technique. On muscovite mica and sodium chloride, needle-like crystallites with edge-on oriented molecules aligned mainly with the unit cell c-axis (which coincides with the long needle axis) along the [1-10]mica, [100]mica, [110]mica and [110]NaCl, [1-10]NaCl directions, respectively. Crystals consisting of flat-on oriented molecules on KCl showed also defined alignments with respect to the substrate, but due to the altered molecule-substrate contact, the b-axis aligned along [110]KCl and [1-10]KCl. Growth at elevated temperatures enabled changes in the crystal growth whereby more defined structures formed on NaCl. On KCl, the bird-like structures remained very similar, while caffeine on the mica surface at elevated temperatures resulted in even additional texture forming with the caffeine molecules now also favoring a flat-on orientation with respect to the surface. The systematic variation of various system parameters demonstrates how sensitive the growth behavior of caffeine on this variety of substrates is.

Solution of an elusive pigment crystal structure from a thin film: a combined X-ray diffraction and computational study.

Epindolidione, a hydrogen-bonded derivative of the organic semiconductor tetracene, is an organic pigment which has previously been used to produce stable OFETs with relatively high hole mobilities. Despite its use as an inkjet pigment and organic semiconductor, the crystal structure of epindolidione has proved elusive and is currently unknown. In this work, we report a crystal structure solution of epindolidione determined from vapor deposited thin films using a combined experimental and theoretical approach. The structure is found to be similar to one of the previously reported epindolidione derivatives and is most likely a surface-mediated polymorph, with a slightly different crystal packing compared to the bulk powder. The effect of substrate temperature on film morphology and structure is also investigated, where it is found that the crystallite orientation can be tuned by deposition at different substrate temperatures. The results also illustrate the possibilities for crystal structures to be solved from thin films.

Self-Limited Growth in Pentacene Thin Films.

Pentacene is one of the most studied organic semiconducting materials. While many aspects of the film formation have already been identified in very thin films, this study provides new insight into the transition from the metastable thin-film phase to bulk phase polymorphs. This study focuses on the growth behavior of pentacene within thin films as a function of film thickness ranging from 20 to 300 nm. By employing various X-ray diffraction methods, combined with supporting atomic force microscopy investigations, one crystalline orientation for the thin-film phase is observed, while three differently tilted bulk phase orientations are found. First, bulk phase crystallites grow with their 00L planes parallel to the substrate surface; second, however, crystallites tilted by 0.75° with respect to the substrate are found, which clearly dominate the former in ratio; third, a different bulk phase polymorph with crystallites tilted by 21° is found. The transition from the thin-film phase to the bulk phase is rationalized by the nucleation of the latter at crystal facets of the thin-film-phase crystallites. This leads to a self-limiting growth of the thin-film phase and explains the thickness-dependent phase behavior observed in pentacene thin films, showing that a large amount of material is present in the bulk phase much earlier during the film growth than previously thought.

Surface-Induced Phase of Tyrian Purple (6,6'-Dibromoindigo): Thin Film Formation and Stability.

The appearance of surface-induced phases of molecular crystals is a frequently observed phenomenon in organic electronics. However, despite their fundamental importance, the origin of such phases is not yet fully resolved. The organic molecule 6,6'-dibromoindigo (Tyrian purple) forms two polymorphs within thin films. At growth temperatures of 150 °C, the well-known bulk structure forms, while at a substrate temperature of 50 °C, a surface-induced phase is observed instead. In the present work, the crystal structure of the surface-induced polymorph is solved by a combined experimental and theoretical approach using grazing incidence X-ray diffraction and molecular dynamics simulations. A comparison of both phases reveals that π-π stacking and hydrogen bonds are common motifs for the intermolecular packing. In-situ temperature studies reveal a phase transition from the surface-induced phase to the bulk phase at a temperature of 210 °C; the irreversibility of the transition indicates that the surface-induced phase is metastable. The crystallization behavior is investigated ex-situ starting from the sub-monolayer regime up to a nominal thickness of 9 nm using two different silicon oxide surfaces; island formation is observed together with a slight variation of the crystal structure. This work shows that surface-induced phases not only appear for compounds with weak, isotropic van der Waals bonds, but also for molecules exhibiting strong and highly directional hydrogen bonds.

Crystallization of Carbamazepine in Proximity to Its Precursor Iminostilbene and a Silica Surface.

Amorphous films of the anticonvulsant drug carbamazepine are easily accessible by various methods, while the crystallization into specific polymorphs represents a challenging and time-consuming task. In this work, the crystallization of drop cast carbamazepine at silica surfaces is investigated by atomic force microscopy and both in situ and ex situ grazing incidence X-ray diffraction. The pristine films grow with low crystallization rates into a triclinic polymorph, exhibiting poor orientational order within films. However, if iminostilbene, a chemical precursor of carbamazepine, is added to the solution, enhanced crystallization rates result. The individual components crystallize phase-separated upon solvent evaporation without the formation of cocrystals. Iminostilbene reduces the time scale of carbamazepine crystallization from several hours to minutes. Besides the change in crystallization dynamics, iminostilbene induces order to the carbamazepine crystallites, evident as a 110 texture. In situ data of intermixed solutions demonstrate that iminostilbene crystallization occurs first. The iminostilbene crystals then act as templates for carbamazepine growth, whereby fully epitaxial growth is suggested from the results. The findings motivate such an approach for other systems, as this solution-processed, intrinsic epitaxial behavior might be employed in up-scaled manufacturing processes.

Crystallization of Tyrian Purple (6,6'-Dibromoindigo) Thin Films: The Impact of Substrate Surface Modifications.

The pigment 6,6'-dibromoindigo (Tyrian purple) shows strong intermolecular hydrogen bonds and the film formation is, therefore, expected to be influenced by the polar character of the substrate surface. Thin films of Tyrian purple were prepared by physical vapor deposition on a variety of substrates with different surface energies: from highly polar silicon dioxide surfaces to hydrophobic polymer surfaces. The crystallographic properties were investigated by X-ray diffraction techniques such as X-ray reflectivity and grazing incidence X-ray diffraction. In all cases, crystallites with "standing" molecules relative to the substrate surface were observed independently of the substrate surface energy. In the case of polymer surfaces, additional crystallites are formed containing "lying" molecules with their aromatic planes parallel to the substrate surface. Small differences in the crystallographic lattice constants were observed as a function of substrate surface energy, the corresponding small changes in the molecular packing are explained by a variation of the hydrogen bond geometries. This work reveals that despite the limited influence of the surface energy on the molecular orientation, the crystalline packing of Tyrian purple within thin films is altered and slightly different structures form.

Charge-transfer crystallites as molecular electrical dopants.

Ground-state integer charge transfer is commonly regarded as the basic mechanism of molecular electrical doping in both, conjugated polymers and oligomers. Here, we demonstrate that fundamentally different processes can occur in the two types of organic semiconductors instead. Using complementary experimental techniques supported by theory, we contrast a polythiophene, where molecular p-doping leads to integer charge transfer reportedly localized to one quaterthiophene backbone segment, to the quaterthiophene oligomer itself. Despite a comparable relative increase in conductivity, we observe only partial charge transfer for the latter. In contrast to the parent polymer, pronounced intermolecular frontier-orbital hybridization of oligomer and dopant in 1:1 mixed-stack co-crystallites leads to the emergence of empty electronic states within the energy gap of the surrounding quaterthiophene matrix. It is their Fermi-Dirac occupation that yields mobile charge carriers and, therefore, the co-crystallites-rather than individual acceptor molecules-should be regarded as the dopants in such systems.

Idiosyncrasies of Physical Vapor Deposition Processes from Various Knudsen Cells for Quinacridone Thin Film Growth on Silicon Dioxide.

Thin films of quinacridone deposited by physical vapor deposition on silicon dioxide were investigated by thermal desorption spectroscopy (TDS), mass spectrometry (MS), atomic force microscopy (AFM), specular and grazing incidence X-ray diffraction (XRD, GIXD), and Raman spectroscopy. Using a stainless steel Knudsen cell did not allow the preparation of a pure quinacridone film. TDS and MS unambiguously showed that in addition to quinacridone, desorbing at about 500 K (γ-peak), significant amounts of indigo desorbed at about 420 K (ß-peak). The existence of these two species on the surface was verified by XRD, GIXD, and Raman spectroscopy. The latter spectroscopies revealed that additional species are contained in the films, not detected by TDS. In the film mainly composed of indigo a species was identified which we tentatively attribute to carbazole. The film consisting of mainly quinacridone contained in addition p-sexiphenyl. The reason for the various decomposition species effusing from the metal Knudsen cell is the comparably high sublimation temperature of the hydrogen bonded quinacridone. With special experimental methods and by using glass Knudsen-type cells we were able to prepare films which exclusively consist of molecules either corresponding to the ß-peak or the γ-peak. These findings are of relevance for choosing the proper deposition techniques in the preparation of quinacridone films in the context of organic electronic devices.

Surface-Induced Polymorphism as a Tool for Enhanced Dissolution: The Example of Phenytoin.

Polymorphism and morphology can represent key factors tremendously limiting the bioavailability of active pharmaceutical ingredients (API), in particular, due to solubility issues. Within this work, the generation of a yet unknown surface-induced polymorph (SIP) of the model drug, 5,5-diphenylimidazolidin-2,4-dion (phenytoin), is demonstrated in thin films through altering the crystallization kinetics and the solvent type. Atomic force microscopy points toward the presence of large single-crystalline domains of the SIP, which is in contrast to samples comprising solely the bulk phase, where extended dendritic phenytoin networks are observed. Grazing incidence X-ray diffraction reveals unit cell dimensions of the SIP significantly different from those of the known bulk crystal structure of phenytoin. Moreover, the aqueous dissolution performance of the new polymorph is benchmarked against a pure bulk phase reference sample. Our results demonstrate that the SIP exhibits markedly advantageous drug release performance in terms of dissolution time. These findings suggest that thin-film growth of pharmaceutical systems in general should be explored, where poor aqueous dissolution represents a key limiting factor in pharmaceutical applications, and illustrate the experimental pathway for determining the physical properties of a pharmaceutically relevant SIP.

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 ß-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.

Substrate-induced phase of a [1]benzothieno[3,2-b]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-b]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.

Polymorphism of dioctyl-terthiophene within thin films: The role of the first monolayer.

The origins of specific polymorphic phases within thin films are still not well understood. The polymorphism of the molecule dioctyl-terthiophene is investigated during the presence of a silicon-oxide surface during the crystallisation process. It is found that a monolayer of molecules forms two-dimensional crystals on the surface. In the case of thicker films crystalline islands are formed, a comparison of the three polymorphic phases observed within thin films and the thermodynamically more stable single crystal phases reveals distinct differences which can be related to an adaption of the molecular packing with the flat surface of the substrate.