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.

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.

Crystallographic textures and morphologies of solution cast Ibuprofen composite films at solid surfaces.

The preparation of thin composite layers has promising advantages in a variety of applications like transdermal, buccal, or sublingual patches. Within this model study the impact of the matrix material on the film forming properties of ibuprofen-matrix composite films is investigated. As matrix materials polystyrene, methyl cellulose, or hydroxyl-ethyl cellulose were used. The film properties were either varied by the preparation route, i.e., spin coating or drop casting, or via changes in the relative ratio of the ibuprofen and the matrix material. The resulting films were investigated via X-ray diffraction and atomic force microscope experiments. The results show that preferred (100) textures can be induced via spin coating with respect to the glass surface, while the drop casting results in a powder-like behavior. The morphologies of the films are strongly impacted by the ibuprofen amount rather than the preparation method. A comparison of the various matrix materials in terms of their impact on the dissolution properties show a two times faster zero order release from methyl cellulose matrix compared to a polystyrene matrix. The slowest rate was observed within the hydroxyl ethyl cellulose as the active pharmaceutical ingredients (APIs) release is limited by diffusion through a swollen matrix. The investigation reveals that the ibuprofen crystallization and film formation is only little effected by the selected matrix material than that compared to the dissolution. A similar experimental approach using other matrix materials may therefore allow to find an optimized composite layer useful for a defined application.

Memory Effect by Melt Crystallization Observed in Polymorphs of a Benzothieno-Benzothiophene Derivative.

This work provides a comprehensive illustration of a crystalline melt memory effect recorded for three solvates of the 2,7-bis(2-(2-methoxyethoxy)ethoxy)benzo[b]benzo[4,5] thieno[2,3-d]thiophene (OEG-BTBT) molecule with dichloromethane (DCM) molecules. Combined optical microscopy and X-ray diffraction measurements at different temperatures are used to get an overview of the structural and morphological properties like melting points, isotropic transition temperatures, induction times, and crystallization kinetics of the three forms. An outstanding observation is made upon annealing the three polymorphs at temperatures well above their respective melting points as well as above the optical clearance temperature. After cooling back to room temperature, recrystallization results in the formation of the initial phase present before the annealing process. This melt memory effect is observed for all three solvates. These observations can be correlated to the strong interaction between the DCM molecules and the oligoethylene glycol side chains, even in the molten state. This conclusion rationalizes the experimental observation made upon solvent vapor annealing of the crystalline sample with DCM, which unambiguously transformed the system into a disordered state.

Polymorph screening at surfaces of a benzothienobenzothiophene derivative: discovering new solvate forms.

The discovery of new polymorphs opens up unique applications for molecular materials since their physical properties are predominantly influenced by the crystal structure type. The deposition of molecules at surfaces offers great potential in the variation of the crystallization conditions, thereby allowing access to unknown polymorphs. With our surface crystallization approach, four new phases are found for an oligoethylene glycol-benzothienobenzothiophene molecule, and none of these phases could be identified via classical polymorph screening. The corresponding crystal lattices of three of the new phases were obtained via X-ray diffraction (XRD). Based on the volumetric considerations together with X-ray fluorescence and Raman spectroscopy data, the phases are identified as solvates containing one, two or three solvent molecules per molecule. The strong interaction of dichloromethane with the oligoethylene glycol side chains of the molecules may be responsible for the formation of the solvates. Temperature-dependent XRD reveals the low thermal stability of the new phases, contrary to the thermodynamically stable bulk form. Nevertheless, the four solvates are stable under ambient conditions for at least two years. This work illustrates that defined crystallization at surfaces enables access to multiple solvates of a given material through precise and controlled variations in the crystallization kinetics.

Thin Film Growth of a Charge Transfer Cocrystal (DCS/TFPA) for Ambipolar Thin Film Transistors.

The highly luminescent dicyanodistyrylbenzene-based charge-transfer (CT) cocrystal based on isometric donor and acceptor molecules with a mixing ratio of 2:1 is characterized in the thin film regime. Physical vapor deposited films prepared at different substrate temperatures are analyzed in terms of their thin film structure and transistor performance. The thin film morphologies and crystallographic properties including microstrain and mosaic spread strongly dependent on the substrate temperature. Enhanced crystal growth with rising temperatures leads to a better transistor performance reaching its maximum at 90 °C with a hole and electron mobility of 1.6 × 10-3 and 2.3 × 10-5 cm2 V-1 s-1, respectively. At higher temperatures performance decreases limited by percolation pathways between the enlarged crystals.

Synthesis of a conjugated pyrrolopyridazinedione-benzodithiophene (PPD-BDT) copolymer and its application in organic and hybrid solar cells.

ABSTRACT: Herein, we describe the synthesis and characterization of a conjugated donor-acceptor copolymer consisting of a pyrrolopyridazinedione (PPD) acceptor unit, and a benzodithiophene (BDT) donor unit. The polymerization was done via a Stille cross-coupling polycondensation. The resulting PPD-BDT copolymer revealed an optical bandgap of 1.8 eV and good processability from chlorobenzene solutions. In an organic solar cell in combination with PC70BM, the polymer led to a power conversion efficiency of 4.5%. Moreover, the performance of the copolymer was evaluated in polymer/nanocrystal hybrid solar cells using non-toxic CuInS2 nanocrystals as inorganic phase, which were prepared from precursors directly in the polymer matrix without using additional capping ligands. The PPD-BDT/CuInS2 hybrid solar cells showed comparably high photovoltages and a power conversion efficiency of 2.2%.

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.

Morphologies of Phenytoin Crystals at Silica Model Surfaces: Vapor Annealing versus Drop Casting.

The controlled preparation of different crystal morphologies with varying preferential orientation with respect to the substrate is of crucial importance in many fields of applications. In this work, the controlled preparation of different phenytoin morphologies and the dependency of the preferential orientation of those crystallites is related with the preparation method (solvent annealing vs drop casting), as well as the physical-chemical interaction with the solvents in use. While solvent annealing induces the formation of particular structures that are partially dewetted, the drop casting technique from various solvent results in the formation of needle-like and elongated structures, with each having a distinct morphology. The morphologies are explained via the Hansen solubility parameters and correlated with the solvent vapor pressures. X-ray diffraction experiments reveal preferential orientations with respect to the solid substrate and indicate the surface-mediated stabilization of an unknown polymorph of phenytoin with an elongated unit cell in the b-axis.

Structural characterisation of alkyl amine-capped zinc sulphide nanoparticles.

Nanoparticles capped with amine ligands with different steric properties, dodecylamine and oleylamine, respectively, are investigated in the solid state as well as in solution. A combined X-ray diffraction, small angle X-ray scattering and electron microscopy investigation showed that the nanoparticles exhibit the sphalerite modification of ZnS as crystal phase with a diameter of 3-5 nm. A close packing of the monocrystalline nanoparticles in the solid state is observed. However, in the dodecylamine sample, besides spherical particles, a fraction of the nanoparticles is elongated. The nanoparticles are readily resoluble in apolar solvents like hexane. Dynamic light scattering (DLS) and SAXS investigations of the solutions reveal that the nanoparticles are dissolved as singular particles. In the case of oleylamine-capped ZnS, a defined core-shell structure with a ZnS core with a diameter of 4 nm and an organic shell with a thickness of approximately 2 nm have been found. Dodecylamine-capped nanoparticles slightly tend to form agglomerates with a diameter of approximately 40 nm.

Investigation of primary crystallite sizes in nanocrystalline ZnS powders: comparison of microwave assisted with conventional synthesis routes.

ZnS powders with primary crystallite sizes of only a few nanometers were prepared by three different synthesis routes at temperatures below 130 degrees C. The reaction of zinc acetate dihydrate with thioacetamide (TAA) in the presence of pyridine and triphenylphosphite (TPP) was carried out using either conventional heating or microwave heating. The obtained powders exhibit sphalerite structure as determined by X-ray diffraction (XRD). The primary crystallites have diameters between 1 and 7 nm obtained by XRD. Small angle X-ray scattering (SAXS) measurements were analyzed by the model-free inverse Fourier-transformation approach, as well as by a hard sphere-model from which particle size and polydispersity were extracted. The particle sizes by SAXS are in good agreement with the primary crystallite sizes obtained by XRD. It has been found that an increasing amount of sulfur and/or using microwave heating increases crystallite sizes. The presence of TPP decreases the particle sizes but no significant influence on the TPP concentration was observed. In the alternative third preparation route, hexamethyldisilathiane (HMDST) was used as precipitation reagent at ambient temperature, which leads to the smallest crystallite sizes of only 1 nm together with low polydispersities. Scanning electron microscopy, dynamic light scattering and UV-vis spectroscopy showed that all three synthesis routes lead to ZnS powders with aggregate sizes between 650 and 1200 nm. Both of the TAA-precipitation routes lead to spherical agglomerates which consist of spherical substructures, whereas the HMDST agglomerates are assembled from elongated objects.