Temperature-dependent tilt angle in the smectic C phase of a liquid crystal
Liquid crystal smectic C phase temperature dependent tilt angle, using conoscopic observation and circularly polarized light
Arora, S. L.↗
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Smectic C Self‐Assembly in Mesogen‐Free Liquid Crystalline Chiral Polyethers with Sulfonylated Methyl‐Branched Side Chains
Abstract To realize advanced electrical applications for ferroelectric liquid crystalline polymers, high spontaneous polarization ( P s ) is highly desired. However, current ferroelectric liquid crystalline polymers usually exhibit a low P s . In this work, mesogen‐free, chiral polyethers containing sulfonylated methyl‐branched alkyl side chains with a (CH 2 ) 3 O spacer between the sulfonyl and the branched alkyl groups are designed and synthesized. In contrast to the linear n ‐alkyl side chains, the methyl‐branched alkyl side chains induce chain tilting in the smectic layers. When double chirality exists in both the main chain and the side chains, a crystalline structure is observed after mechanical stretching. Intriguingly, when single chirality exists in either the backbone or the side chains, a liquid crystalline smectic C phase is obtained. The electric displacement–electric field study, however, does not show typical ferroelectric switching, although the dielectric constants are relatively high for these liquid crystalline polymers. This is likely because the dipole–dipole interactions among neighboring sulfonyl groups along the main chain are so strong that the ferroelectric switching is hindered in the samples. For the future work, it is desired to weaken the dipole–dipole interaction to achieve ferroelectricity in these mesogen‐free liquid crystalline polymers.
36 MATERIALS SCIENCE↗
Effects of tacticity and chiral center-to-dipole distance on mesogen-free liquid crystalline self-assembly of sulfonyl-containing comb-like polymers
In this report, new approaches were implemented to achieve novel ferroelectric liquid crystalline self-assembly in mesogen-free comb-like isotactic polyoxypropylenes (iPOPs) bearing mono- or di-sulfonyl groups, which have potential to exhibit high spontaneous polarization for applications in advanced electronic devices. iPOPs with n-alkylsulfonylpentylthioether side chains (iPOP-SC 5 SO 2 C n , where C n is the alkyl tail with n being either 12 or 8) were prepared via a post-polymerization substitution reaction from isotactic poly[(R)-(–)-epichlorohydrin]. Here, the effects of main-chain tacticity, chiral center-to-dipole distance, number of sulfonyl dipoles per side chain, and n-alkyl tail length on the liquid crystalline self-assembly behavior were investigated by comparing iPOPs with their atactic counterparts. First, when the sulfonyl dipole was placed far away from the chiral center in iPOP-SC 5 SO 2 C n compared with our previously reported isotactic polyethers with n-alkylsulfonyl side chains (iPOP-SO 2 C n ), the dipole–dipole interactions among the side chains decreased, which led to more liquid crystalline phases. Smectic E (SmE) and A (SmA) phases were observed after crystal melting; however, the main-chain chiral center was found to have an insignificant effect on the liquid crystalline assembly when compared to the atactic samples. Second, the longer C n tails increased the transition temperatures as a result of stronger van der Waals interactions. Third, after the thioether linkage in the side chain was oxidized into the sulfonyl group, the chiral center–dipole and dipole–dipole interactions in the resultant polymers (i.e., iPOP-SO 2 C 5 SO 2 C n ) enhanced. As a result, the liquid crystalline phase transitions (i.e., crystal → SmE → SmA → I) were pushed to higher temperatures. The knowledge gained in this study will help us further design and achieve the ferroelectric smectic C* phase in mesogen-free comb-like sulfonylated liquid crystalline polymers.
36 MATERIALS SCIENCE↗
Liquid crystalline behavior and photoluminescence of lanthanide decanoate nanoparticles synthesized by microwave radiation
Luminescent lanthanide decanoate nanoparticles (LnC 10 NPs; Ln = Pr, Nd, Sm, Eu, Gd, Er) with spherical morphology (<100 nm) have been synthesized via a facile microwave (MWV) method using Ln(NO 3 ) 3 ·xH 2 O, ethanol/water, and decanoic acid. These hybrid nanomaterials adopt a lamellar structure consisting of inorganic Ln 3+ layers separated by a decanoate anion bilayer and exhibit liquid crystalline (LC) phases during melting. The particle size, crystalline structure, and LC behavior were characterized using transmission electron microscopy (TEM), differential scanning calorimetry (DSC), and powder X-ray diffraction (ambient and heated). Thermal analysis indicated the formation of Smectic A LC phases by LnC 10 nanoparticles, with the smaller lanthanides (Ln = Sm, Gd, Er) displaying additional solid intermediate and Smectic C phases. The formation of LC phases by the smaller Ln 3+ suggests that these nanoscale materials have vastly different thermal properties than their bulk counterparts, which do not exhibit LC behavior. In this work, photoluminescence spectroscopy revealed the LnC 10 NPs to be highly optically active, producing strong visible emissions that corresponded to expected electronic transitions by the various Ln 3+ ions. Under long-wave UV irradiation (λ = 365 nm), bright visible luminescence was observed for colloidal suspensions of Nd, Sm, Eu, Gd, and ErC 10 NPs. To the best of the authors’ knowledge, this is the first reported synthesis of nanoscale metal alkanoates, the first report of liquid crystalline behavior by any decanoate of lanthanides smaller than Nd, and the first observation of strong visible luminescence by non-vitrified lanthanide alkanoates.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Y-shaped tricatenar azobenzenes – functional liquid crystals with synclinic–anticlinic transitions and spontaneous helix formation
A series of achiral tricatenar rod-like molecules with a 3,5-disubstitution pattern at one end and a single alkyl chain at the other end of a rod-like azobenzene derived core is reported. Depending on temperature and alkyl chain length, these Y-shaped compounds self-assemble into different types of liquid crystalline (LC) phases, ranging from non-tilted and synclinic tilted hexatic, via non-tilted and anticlinic tilted smectic and bicontinuous cubic LC phases, to a spontaneous mirror symmetry broken isotropic liquid (Iso 1 [*]) or a related achiral liquid network phase (Iso 1 ). An additional tilted, but uniaxial smectic phase was observed at the transition between anticlinic and synclinic tilt correlation and was investigated by soft resonant X-ray scattering with respect to possible helix formation. This work provides a new concept for the design of technological interesting azobenzene based LC materials with anticlinic tilted smectic C phases (SmC a ) and with azobenzene units organized in the long range or short range helical network structures of bicontinuous cubic and chiral isotropic liquid phases, respectively. Core fluorination removes all lamellar phases, leaving only the cubic phase over wide temperature ranges, even at ambient temperature.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Biaxial liquid crystals
Liquid crystals biaxial smectic C phases tilt and optic axial angles determined from convergent light observations
Arora, S. L.↗
Rheological Properties of Quasi-2D Fluids in Microgravity
In recent years, research on complex fluids and fluids in restricted geometries has attracted much attention in the scientific community. This can be attributed not only to the development of novel materials based on complex fluids but also to a variety of important physical phenomena which have barely been explored. One example is the behavior of membranes and thin fluid films, which can be described by two-dimensional (2D) rheology behavior that is quite different from 3D fluids. In this study, we have investigated the rheological properties of freely suspended films of a thermotropic liquid crystal in microgravity experiments. This model system mimics isotropic and anisotropic quasi 2D fluids [46]. We use inkjet printing technology to dispense small droplets (inclusions) onto the film surface. The motion of these inclusions provides information on the rheological properties of the films and allows the study of a variety of flow instabilities. Flat films have been investigated on a sub-orbital rocket flight and curved films (bubbles) have been studied in the ISS project OASIS. Microgravity is essential when the films are curved in order to avoid sedimentation. The experiments yield the mobility of the droplets in the films as well as the mutual mobility of pairs of particles. Experimental results will be presented for 2D-isotropic (smectic-A) and 2D-nematic (smectic-C) phases.
microgravity↗
An Integrated Theoretical and Experimental Approach to Achieve Highly Polarizable Relaxor Ferroelectric Liquid Crystalline Polymers
In this project, we have designed and synthesized a series of aliphatic sulfonlyated chiral and achiral polyether. The major objective is to achieve ferroelectric liquid crystalline polymers with a high spontaneous polarization (0.04-0.08 C/m2). Due to the strong dipole-dipole interaction among the sulfonyl side groups, which resembles that among water molecules, these polyethers can exhibit various liquid crystalline self-assemblies without any rigid mesogens. By tuning the position of the sulfonyl groups, single versus double sulfonyl groups, and spacer/tail length and methyl branches, the liquid crystalline phases include smectic A, smectic C, and hexagonal columnar phases. When the single sulfonyl group is next to the main chain or disulfonyl groups are separated by a short C3 spacer, the dipolar interaction is too strong to allow any dipole switching. As a result, the linear dielectric behavior is observed with a low dielectric constant of 5-7. When the single sulfonyl groups are away from the main chain, the paraelectric behavior is obtained with a high dielectric constant around 20. From this study, we predict that by further tailoring the intermolecular interactions among the disulfonyl side groups, it is possible to achieve ferroelectric property for these liquid crystalline polymers. If successful, these ferroelectric liquid crystalline polymers can be used for efficient electrocaloric cooling applications.
36 MATERIALS SCIENCE↗
Achieving High Permittivity Paraelectric Behavior in Mesogen-Free Sulfonylated Chiral Polyethers with Smectic C Liquid Crystalline Self-Assembly
Ferroelectric liquid crystalline polymers (LCPs) with a high spontaneous polarization (P s ) are of great interest for the fabrication of advanced electronic devices. However, conventional ferroelectric LCPs typically exhibit low spontaneous polarization, only around 1 mC/m 2 . To increase the orientational polarization for ferroelectric LCPs, in this work, we designed mesogen-free comb-shaped LCPs based on isotactic polyepichlorohydrin, which contained highly dipolar sulfonyl groups (dipole moment of 4.5 Debye) in the side chains. The goal was to increase dipole density and induce ferroelectric switching. In this new series of mesogen-free LCPs, the sulfonyl groups were first moved away from the main chain to mitigate strong dipole–dipole interactions. Second, methyl-branched alkyl side chains were implemented to decrease the crystallizability and induce the Smectic C (SmC) self-assembly. Intriguingly, these SmC samples, for the first time, exhibited typical paraelectric behavior (i.e., slim S-shaped single hysteresis loops) with a high dielectric constant in the range of 20–30. Finally, learning from the knowledge obtained from this study, we will be able to design new mesogen-free LCPs with tailor-made dipole–dipole interactions and realize ferroelectricity.
36 MATERIALS SCIENCE↗
Non-covalent planarizing interactions yield highly ordered and thermotropic liquid crystalline conjugated polymers
Controlling the multi-level assembly and morphological properties of conjugated polymers through structural manipulation has contributed significantly to the advancement of organic electronics. In this work, a redox active conjugated polymer, TPT–TT, composed of alternating 1,4-(2-thienyl)-2,5-dialkoxyphenylene (TPT) and thienothiophene (TT) units is reported with non-covalent intramolecular S⋯O and S⋯H–C interactions that induce controlled main-chain planarity and solid-state order. As confirmed by density functional theory (DFT) calculations, these intramolecular interactions influence the main chain conformation, promoting backbone planarization, while still allowing dihedral rotations at higher kinetic energies (higher temperature), and give rise to temperature-dependent aggregation properties. Thermotropic liquid crystalline (LC) behavior is confirmed by cross-polarized optical microscopy (CPOM) and closely correlated with multiple thermal transitions observed by differential scanning calorimetry (DSC). This LC behavior allows us to develop and utilize a thermal annealing treatment that results in thin films with notable long-range order, as shown by grazing-incidence X-ray diffraction (GIXD). Specifically, we identified a first LC phase, ranging from 218 °C to 107 °C, as a nematic phase featuring preferential face-on π–π stacking and edge-on lamellar stacking exhibiting a large extent of disorder and broad orientation distribution. A second LC phase is observed from 107 °C to 48 °C, as a smectic A phase featuring sharp, highly ordered out-of-plane lamellar stacking features and sharp tilted backbone stacking peaks, while the structure of a third LC phase with a transition at 48 °C remains unclear, but resembles that of the solid state at ambient temperature. Furthermore, the significance of thermal annealing is evident in the ∼3-fold enhancement of the electrical conductivity of ferric tosylate-doped annealed films reaching 55 S cm −1 . More importantly, thermally annealed TPT–TT films exhibit both a narrow distribution of charge-carrier mobilities (1.4 ± 0.1) × 10 −2 cm 2 V −1 s −1 along with a remarkable device yield of 100% in an organic field-effect transistor (OFET) configuration. This molecular design approach to obtain highly ordered conjugated polymers in the solid state affords a deeper understanding of how intramolecular interactions and repeat-unit symmetry impact liquid crystallinity, solution aggregation, solution to solid-state transformation, solid-state morphology, and ultimately device applications.
Chemistry↗
Ion Transport in 2D Nanostructured $\pi$-Conjugated Thieno[3,2- b ]thiophene-Based Liquid Crystal
Leveraging the self-assembling behavior of liquid crystals designed for controlling ion transport is of both fundamental and technological significance. Here, we have designed and prepared a liquid crystal that contains (2,5-bis(5-(2,5,8,11-tetraoxatridecan-13-yl)thiophen-2yl)thieno[3,2-b]thiophene (BTTT) as mesogenic core and conjugated segment and symmetric tetra(ethylene oxide) (EO4) as polar side chains for ionic conducting regions. Driven by the crystallization of the BTTT cores, BTTT/dEO4 exhibits well-ordered smectic phases below 71.5 °C as confirmed by differential scanning calorimetry, polarized optical microscope, temperature dependent wide-angle X-ray scattering and grazing incidence wide-angle X-ray scattering (GIWAXS). We adopted a combination of experimental GIWAXS and molecular dynamics (MD) simulations to better understand the molecular packing of BTTT/dEO4 films, particularly when loaded with the ion conducting salt, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). Ionic conduction of BTTT/dEO4 is realized by the addition of LiTFSI, with the material able to maintain smectic phases up to r = [Li + ]/[EO] = 0.1. In this work, The highest ionic conductivity of 8 × 10 -3 S/cm was attained at an intermedium salt concentration of r = 0.05. It was also found that ion conduction in BTTT/dEO4 is enhanced by forming a smectic layered structure with irregular interfaces between the BTTT and EO4 layers and by the lateral film expansion upon salt addition. This can be explained by the enhancement of the misalignment and configurational entropy of the side chains, which increase their local mobility and that of the solvated ions. Our molecular design thus illustrates how, beyond the favorable energetic interactions that drive the assembly and ion solvating domains, modulation of entropic effects can also be favorably harnessed to improve ion conduction.
thin film electrochemical impedance spectroscopy↗
Structure, Hydrodynamics, and Phase Transition of Freely Suspended Liquid Crystals
Smectic liquid crystals are phases of rod shaped molecules organized into one dimensionally (1D) periodic arrays of layers, each layer being between one and two molecular lengths thick. In the least ordered smectic phases, the smectics A and C, each layer is a two dimensional (2D) liquid. Additionally there are a variety of more ordered smectic phases having hexatic short range translational order or 2D crystalline quasi long range translational order within the layers. The inherent fluid-layer structure and low vapor pressure of smectic liquid crystals enable the long term stabilization of freely suspended, single component, layered fluid films as thin as 30A, a single molecular layer. The layering forces the films to be an integral number of smectic layers thick, quantizing their thickness in layer units and forcing a film of a particular number of layers to be physically homogeneous with respect to its layer structure over its entire area. Optical reflectivity enables the precise determination of the number of layers. These ultrathin freely suspended liquid crystal films are structures of fundamental interest in condensed matter and fluid physics. They are the thinnest known stable condensed phase fluid structures and have the largest surface-to-volume ratio of any stable fluid preparation, making them ideal for the study of the effects of reduced dimensionality on phase behavior and on fluctuation and interface phenomena. Their low vapor pressure and quantized thickness enable the effective use of microgravity to extend the study of basic capillary phenomena to ultrathin fluid films. Freely suspended films have been a wellspring of new liquid crystal physics. They have been used to provide unique experimental conditions for the study of condensed phase transitions in two dimensions. They are the only system in which the hexatic has been unambiguously identified as a phase of matter, and the only physical system in which fluctuations of a 2D XY system and Kosterlitz Thouless phase transition has been observed and 2D XY quasi long range order verified. Smectic films have enabled the precise determination of smectic layer electron density and positional fluctuation profile and have been used to show that the interlayer interactions in anti-ferroelectric tilted smectics do not extend significantly beyond nearest neighbors. The interactions which are operative in liquid crystals are generally weak in comparison to those in crystalline phases, leading to the facile manipulation of the order in liquid crystals by external agents such as applied fields and surfaces. Effects arising from weak ordering are significantly enhanced in ultrathin free films and filaments wherein the intermolecular coupling is effectively reduced by loss of neighbors. Over the past four years this research, which we now detail, has produced a host of exciting new discoveries and unexpected results, maintaining the position of the study of freely suspended liquid crystal structures as one of most exciting and fruitful areas of complex fluid physics. In addition, several potentially interesting microgravity free film experiments have been identified.
Clark, Noel A.↗
Structure and Dynamics of Freely Suspended Liquid Crystals
Smectic liquid crystals are phases of rod shaped molecules organized into one dimensionally (1 D) periodic arrays of layers, each layer being between one and two molecular lengths thick. In the least ordered smectic phases, the smectics A and C, each layer is a two dimensional (2D) liquid. Additionally there are a variety of more ordered smectic phases having hexatic short range translational order or 2D crystalline or quasi long range translational order within the layers. The inherent fluid-layer structure and low vapor pressure of smectic liquid crystals enables the long term stabilization of freely suspended, single component, layered fluid films as thin as 30A, a single molecular layer. The layering forces the films to be an integral number of smectic layers thick, quantizing their thickness in layer units and forcing a film of a particular number of layers to be physically homogeneous with respect to its layer structure over its entire area. Optical reflectivity enables the precise determination of the number of layers. These ultrathin freely suspended liquid crystal films are structures of fundamental interest in condensed matter and fluid physics. They are the thinnest known stable fluid structures and have the largest surface-to-volume ratio of any stable fluid preparation, making them ideal for the study of the effects of reduced dimensionality on phase behavior and on fluctuation and interface phenomena. Their low vapor pressure and quantized thickness enable the effective use of microgravity to extend the study of basic capillary phenomena to ultrathin fluid films. Freely suspended films have been a wellspring of new LC physics. They have been used to provide unique experimental conditions for the study of condensed phase transitions in two dimensions. They are the only system in which the hexatic has been unambiguously identified as a phase of matter, and the only physical system in which fluctuations of a 2D XY system and Kosterlitz Thouless phase transition has been observed and 2D XY quasi long range order verified. Smectic films have enabled the precise determination of smectic layer electron density and positional fluctuation profiles and have been used to show that the interlayer interactions in antiferroelectric tilted smectics do not extend significantly beyond nearest neighbors. Freely suspended films played a pivotal role in the recent discovery of macroscopic chiral-polar ordering in fluids of achiral molecules. The interactions which are operative in liquid crystals are generally weak in comparison to those in crystalline phases, leading to the facile manipulation of the order in liquid crystals by external agents such as applied fields and surfaces. Effects arising from weak ordering are significantly enhanced in ultrathin free films and filaments, in which the intermolecular coupling is effectively further reduced by loss of neighbors. Over the past four years this research, which we now detail, has produced a host of exciting new discoveries and unexpected results, maintaining the study of freely suspended liquid crystal structures as one of most exciting and fruitful areas of complex fluid physics. In addition, a class of experiments on the behavior of 1D interfaces in 2D films have been pursued with results that point to potentially quite interesting effects in microgravity.
Clark, Noel A.↗
Nanolayered Features of Collagen-like Peptides
We have been investigating collagen-like model oligopeptides as molecular bases for complex ordered biomimetic materials. The collagen-like molecules incorporate aspects of native collagen sequence and secondary structure. Designed modifications to native primary and secondary structure have been incorporated to control the nanostructure and microstructure of the collagen-like materials produced. We find that the collagen-like molecules form a number of lyotropic rod liquid crystalline phases, which because of their strong temperature dependence in the liquid state can also be viewed as solvent intercalated thermotropic liquid crystals. The liquid crystalline phases formed by the molecules can be captured in the solid state by drying off solvent, resulting in solid nanopatterned (chemically and physically) thermally stable (to greater than 100 C) materials. Designed sequences which stabilize smectic phases have allowed a variety of nanoscale multilayered biopolymeric materials to be developed. Preliminary investigations suggest that chemical patterns running perpendicular to the smectic layer plane can be functionalized and used to localize a variety of organic, inorganic, and organometallic moieties in very simple multilayered nanocomposites. The phase behavior of collagen-like oligopeptide materials is described, emphasizing the correlation between mesophase, molecular orientation, and chemical patterning at the microscale and nanoscale. In many cases, the textures observed for smectic and hexatic phase collagens are remarkably similar to the complex (and not fully understood) helicoids observed in biological collagen-based tissues. Comparisons between biological morphologies and collagen model liquid crystalline (and solidified materials) textures may help us understand the molecular features which impart order and function to the extracellular matrix and to collagen-based mineralized tissues. Initial studies have utilized synthetic collagen-like peptides while future work will also focus on similar sequences generated via genetic engineering methods.
Valluzzi, Regina↗
New examples of ferroelectric nematic materials showing evidence for the antiferroelectric smectic-Z phase
Abstract We present a new ferroelectric nematic material, 4-((4′-((trans)-5-ethyloxan-2-yl)-2′,3,5,6′-tetrafluoro-[1,1′-biphenyl]-4-yl)difluoromethoxy)-2,6-difluorobenzonitrile (AUUQU-2-N) and its higher homologues, the molecular structures of which include fluorinated building blocks, an oxane ring, and a terminal cyano group, all contributing to a large molecular dipole moment of about 12.5 D. We observed that AUUQU-2-N has three distinct liquid crystal phases, two of which were found to be polar phases with a spontaneous electric polarization P s of up to 6 µC cm –2 . The highest temperature phase is a common enantiotropic nematic (N) exhibiting only field-induced polarization. The lowest-temperature, monotropic phase proved to be a new example of the ferroelectric nematic phase (N F ), evidenced by a single-peak polarization reversal current response, a giant imaginary dielectric permittivity on the order of 10 3 , and the absence of any smectic layer X-ray diffraction peaks. The ordinary nematic phase N and the ferroelectric nematic phase N F are separated by an antiferroelectric liquid crystal phase which has low permittivity and a polarization reversal current exhibiting a characteristic double-peak response. In the polarizing light microscope, this antiferroelectric phase shows characteristic zig-zag defects, evidence of a layered structure. These observations suggest that this is another example of the recently discovered smectic Z A (SmZ A ) phase, having smectic layers with the molecular director parallel to the layer planes. The diffraction peaks from the smectic layering have not been observed to date but detailed 2D X-ray studies indicate the presence of additional short-range structures including smectic C-type correlations in all three phases—N, SmZ A and N F —which may shed new light on the understanding of polar and antipolar order in these phases.
36 MATERIALS SCIENCE↗
Liquid Crystals Derived from 2-phenyl-isoindoles: Synthesis and Characterization
2-Phenyl-isoindole was investigated as the rigid core unit in a series of asymmetric mesogenic molecules. When the 2-phenyl-isoindole core was terminated with a hexyl tail, no mesophase formation could be observed. When 4-n-(tridecafluorohexyl) was used, however, we observed both monotropic and enantiotropic phase behavior. We found that most functionalities at the anhydride 5-position results in the formation of smectic A (SmA) phases in the temperature range of 70-180 C. Functionalities at the anhydride 4-position suppress mesophase formation. Large substituents (-Br, -NO2) and symmetric substitution patterns (5,6-dichloro, 4,7-dichloro and 4,5,6,7-tetrachloro) on the anhydride moiety increase the melting point and destabilize the mesophase. Temperature dependent X-ray diffraction experiments suggest an interdigitated SmA packing for this family of compounds.
Jow, Kenny G.↗
Programming liquid crystal elastomers for multistep ambidirectional deformability
Ambidirectionality, which is the ability of structural elements to move beyond a reference state in two opposite directions, is common in nature. However, conventional soft materials are typically limited to a single, unidirectional deformation unless complex hybrid constructs are used. We exploited the combination of mesogen self-assembly, polymer chain elasticity, and polymerization-induced stress to design liquid crystalline elastomers that exhibit two mesophases: chevron smectic C (cSmC) and smectic A (SmA). Inducing the cSmC-SmA–isotropic phase transition led to an unusual inversion of the strain field in the microstructure, resulting in opposite deformation modes (e.g., consecutive shrinkage or expansion and right-handed or left-handed twisting and tilting in opposite directions) and high-frequency nonmonotonic oscillations. Further, this ambidirectional movement is scalable and can be used to generate Gaussian transformations at the macroscale.
36 MATERIALS SCIENCE↗
Dynamic processes in transient phases during self-assembly of organic semiconductor thin films
Understanding and manipulating crystallization processes has been an important challenge for solution-processed organic thin films, both for fundamental studies and for fabricating thin films with near-intrinsic charge transport properties. We report an in situ X-ray scattering study of the crystallization of 2-decyl-7-phenyl-[1]benzothieno[3,2-b][1]benzothiophene (Ph-BTBT-C 10 ) during its deposition from solution. At temperatures modestly below the smectic-E/crystalline phase boundary, the crystallization goes through a transient liquid crystal state before reaching the final stable crystalline phase. Significant dynamics occur in the first few seconds of the transition, which are observed through fluctuations in the X-ray scattering intensity, and are correlated with the time interval that the transient thin film coexists with the evaporating solvent. The transition to the stable crystalline phase takes minutes or even hours under these conditions, which may be a result of the asymmetry of the molecule. Transient phases are of potential interest for applications, since they can act as a route to self-assembly of organic thin films. However, our observations show that the long-lived monolayer-stacked intermediate state does not act as a template for the bilayer-stacked crystalline phase. Rather, the grain structure is replaced through nucleation, where the nucleation free-energy barrier is related to a potential barrier that prevents molecules to flip their long axis by 180°.
36 MATERIALS SCIENCE↗