Anisotropic confinement of chromophores induces second-order nonlinear optics in a nanoporous photonic metamaterial.

Second-order nonlinear optics is the base for a large variety of devices aimed at the active manipulation of light. However, physical principles restrict its occurrence to non-centrosymmetric, anisotropic matter. This significantly limits the number of base materials exhibiting nonlinear optics. Here, we show that embedding chromophores in an array of conical channels 13 nm across in monolithic silica results in mesoscopic anisotropic matter and thus in a hybrid material showing second-harmonic generation. This nonlinear optics is compared to the one achieved in corona-poled polymer films containing the identical chromophores. It originates in the confinement-induced orientational order of the elongated guest molecules in the nanochannels. This leads to a non-centrosymmetric dipolar order and hence to a nonlinear light-matter interaction on the sub-wavelength, single-pore scale. Our study demonstrates that the advent of large-scale, self-organized nanoporosity in monolithic solids along with the confinement-controllable orientational order of chromophores at the single-pore scale provides a reliable and accessible tool to design materials with a nonlinear meta-optics.

Quantized Self-Assembly of Discotic Rings in a Liquid Crystal Confined in Nanopores.

Disklike molecules with aromatic cores spontaneously stack up in linear columns with high, one-dimensional charge carrier mobilities along the columnar axes, making them prominent model systems for functional, self-organized matter. We show by high-resolution optical birefringence and synchrotron-based x-ray diffraction that confining a thermotropic discotic liquid crystal in cylindrical nanopores induces a quantized formation of annular layers consisting of concentric circular bent columns, unknown in the bulk state. Starting from the walls this ring self-assembly propagates layer by layer towards the pore center in the supercooled domain of the bulk isotropic-columnar transition and thus allows one to switch on and off reversibly single, nanosized rings through small temperature variations. By establishing a Gibbs free energy phase diagram we trace the phase transition quantization to the discreteness of the layers' excess bend deformation energies in comparison to the thermal energy, even for this near room-temperature system. Monte Carlo simulations yielding spatially resolved nematic order parameters, density maps, and bond-orientational order parameters corroborate the universality and robustness of the confinement-induced columnar ring formation as well as its quantized nature.

The structural and surface properties of natural and modified coal gangue.

A novel application of coal gangue as inexpensive adsorbents is considered in this study. The structural and surface properties of natural and modified gangue were studied via nitrogen adsorption. Four types of samples were studied: natural, modified with H2NO3 and H2O2 and calcined at 250 °C and 600 °C. The specific surface area and porosity of the samples were determined using various methods. The raw material is mainly mesoporous with relatively small specific surface area. The chemical modification enlarged the total pore volume and the specific surface area. The calcination at 250 °C enlarged slightly the pore volume and lowered the specific surface area, but did not cause significant changes in the structural properties. The calcination at 600 °C resulted in a significant increase in pore volume and a decrease in specific surface area. These results suggest that the coal gangue studied here could be used as inexpensive adsorbent in industrial wastewater pretreatment.

Inhomogeneous relaxation dynamics and phase behaviour of a liquid crystal confined in a nanoporous solid.

We report filling-fraction dependent dielectric spectroscopy measurements on the relaxation dynamics of the rod-like nematogen 7CB condensed in 13 nm silica nanochannels. In the film-condensed regime, a slow interface relaxation dominates the dielectric spectra, whereas from the capillary-condensed state up to complete filling an additional, fast relaxation in the core of the channels is found. The temperature-dependence of the static capacitance, representative of the averaged, collective molecular orientational ordering, indicates a continuous, paranematic-to-nematic (P-N) transition, in contrast to the discontinuous bulk behaviour. It is well described by a Landau-de-Gennes free energy model for a phase transition in cylindrical confinement. The large tensile pressure of 10 MPa in the capillary-condensed state, resulting from the Young-Laplace pressure at highly curved liquid menisci, quantitatively accounts for a downward-shift of the P-N transition and an increased molecular mobility in comparison to the unstretched liquid state of the complete filling. The strengths of the slow and fast relaxations provide local information on the orientational order: the thermotropic behaviour in the core region is bulk-like, i.e. it is characterized by an abrupt onset of the nematic order at the P-N transition. By contrast, the interface ordering exhibits a continuous evolution at the P-N transition. Thus, the phase behaviour of the entirely filled liquid crystal-silica nanocomposite can be quantitatively described by a linear superposition of these distinct nematic order contributions.

Thermotropic interface and core relaxation dynamics of liquid crystals in silica glass nanochannels: a dielectric spectroscopy study.

We report dielectric relaxation spectroscopy experiments on two rod-like liquid crystals of the cyanobiphenyl family (5CB and 6CB) confined in tubular nanochannels with 7 nm radius and 340 micrometer length in a monolithic, mesoporous silica membrane. The measurements were performed on composites for two distinct regimes of fractional filling: monolayer coverage at the pore walls and complete filling of the pores. For the layer coverage a slow surface relaxation dominates the dielectric properties. For the entirely filled channels the dielectric spectra are governed by two thermally-activated relaxation processes with considerably different relaxation rates: a slow relaxation in the interface layer next to the channel walls and a fast relaxation in the core region of the channel filling. The strengths and characteristic frequencies of both relaxation processes have been extracted and analysed as a function of temperature. Whereas the temperature dependence of the static capacitance reflects the effective (average) molecular ordering over the pore volume and is well described within a Landau-de Gennes theory, the extracted relaxation strengths of the slow and fast relaxation processes provide an access to distinct local molecular ordering mechanisms. The order parameter in the core region exhibits a bulk-like behaviour with a strong increase in the nematic ordering just below the paranematic-to-nematic transition temperature TPN and subsequent saturation during cooling. By contrast, the surface ordering evolves continuously with a kink near TPN. A comparison of the thermotropic behaviour of the monolayer with the complete filling reveals that the molecular order in the core region of the pore filling affects the order of the peripheral molecular layers at the wall.

Anomalous front broadening during spontaneous imbibition in a matrix with elongated pores.

During spontaneous imbibition, a wetting liquid is drawn into a porous medium by capillary forces. In systems with comparable pore length and diameter, such as paper and sand, the front of the propagating liquid forms a continuous interface. Sections of this interface advance in a highly correlated manner due to an effective surface tension, which restricts front broadening. Here we investigate water imbibition in a nanoporous glass (Vycor) in which the pores are much longer than they are wide. In this case, no continuous liquid-vapor interface with coalesced menisci can form. Anomalously fast imbibition front roughening is experimentally observed by neutron imaging. We propose a theoretical pore-network model, whose structural details are adapted to the microscopic pore structure of Vycor glass and show that it displays the same large-scale roughening characteristics as observed in the experiment. The model predicts that menisci movements are uncorrelated, indicating that despite the connectivity of the network the smoothening effect of surface tension on the imbibition front roughening is negligible. These results suggest a new universality class of imbibition behavior, which is expected to occur in any matrix with elongated, interconnected pores of random radii.

Thermotropic orientational order of discotic liquid crystals in nanochannels: an optical polarimetry study and a Landau-de Gennes analysis.

Optical polarimetry measurements of the orientational order of a discotic liquid crystal based on a pyrene derivative confined in parallelly aligned nanochannels of monolithic, mesoporous alumina, silica, and silicon as a function of temperature, channel radius (3-22 nm) and surface chemistry reveal a competition of radial and axial columnar orders. The evolution of the orientational order parameter of the confined systems is continuous, in contrast to the discontinuous transition in the bulk. For channel radii larger than 10 nm we suggest several, alternative defect structures, which are compatible both with the optical experiments on the collective molecular orientation presented here and with a translational, radial columnar order reported in previous diffraction studies. For smaller channel radii our observations can semi-quantitatively be described by a Landau-de Gennes model with a nematic shell of radially ordered columns (affected by elastic splay deformations) that coexists with an orientationally disordered, isotropic core. For these structures, the cylindrical phase boundaries are predicted to move from the channel walls to the channel centres upon cooling, and vice-versa upon heating, in accord with the pronounced cooling/heating hystereses observed and the scaling behavior of the transition temperatures with the channel diameter. The absence of experimental hints of a paranematic state is consistent with a biquadratic coupling of the splay deformations to the order parameter.

Self-Assembly of Ionic Superdiscs in Nanopores.

Discotic ionic liquid crystals (DILCs) consist of self-assembled superdiscs of cations and anions that spontaneously stack in linear columns with high one-dimensional ionic and electronic charge mobility, making them prominent model systems for functional soft matter. Compared to classical nonionic discotic liquid crystals, many liquid crystalline structures with a combination of electronic and ionic conductivity have been reported, which are of interest for separation membranes, artificial ion/proton conducting membranes, and optoelectronics. Unfortunately, a homogeneous alignment of the DILCs on the macroscale is often not achievable, which significantly limits the applicability of DILCs. Infiltration into nanoporous solid scaffolds can, in principle, overcome this drawback. However, due to the experimental challenges to scrutinize liquid crystalline order in extreme spatial confinement, little is known about the structures of DILCs in nanopores. Here, we present temperature-dependent high-resolution optical birefringence measurement and 3D reciprocal space mapping based on synchrotron X-ray scattering to investigate the thermotropic phase behavior of dopamine-based ionic liquid crystals confined in cylindrical channels of 180 nm diameter in macroscopic anodic aluminum oxide membranes. As a function of the membranes' hydrophilicity and thus the molecular anchoring to the pore walls (edge-on or face-on) and the variation of the hydrophilic-hydrophobic balance between the aromatic cores and the alkyl side chain motifs of the superdiscs by tailored chemical synthesis, we find a particularly rich phase behavior, which is not present in the bulk state. It is governed by a complex interplay of liquid crystalline elastic energies (bending and splay deformations), polar interactions, and pure geometric confinement and includes textural transitions between radial and axial alignment of the columns with respect to the long nanochannel axis. Furthermore, confinement-induced continuous order formation is observed in contrast to discontinuous first-order phase transitions, which can be quantitatively described by Landau-de Gennes free energy models for liquid crystalline order transitions in confinement. Our observations suggest that the infiltration of DILCs into nanoporous solids allows tailoring their nanoscale texture and ion channel formation and thus their electrical and optical functionalities over an even wider range than in the bulk state in a homogeneous manner on the centimeter scale as controlled by the monolithic nanoporous scaffolds.

Electric-field-induced optical path length change in LiNbO3:MgO crystals: spatial anisotropy analysis.

In this paper we describe the methodology behind the calculation of the indicative surfaces (ISs) of the electric-field-induced optical path length change (EFIOPC) in anisotropic crystal materials accounting for the piezoelectric deformation. It is considered in detail for a particular case of 3m point group symmetry and applied to LiNbO(3) single crystals doped with 7 mol. % MgO (hereafter LiNbO(3):MgO). The contribution of the inverse piezoelectricity into EFIOPC appears to be considerable and, in many cases, modifying, for instance, the spherical coordinates of the extreme directions or even leading to the appearance of new directional maxima on relevant ISs. The ISs of EFIOPC are of considerable practical importance as they allow us to determine an optimal geometry for electro-optic coupling. The spatial anisotropic analysis of EFIOPC in LiNbO(3):MgO crystals suggests that the lowest effective driving voltage is provided by electro-optic cells representing the rectangular slabs of X/50° crystal cut. The modulation efficiency of such electro-optic cells is about 1.5 times better than ones fabricated in the usual way (i.e., as rectangular crystal slabs with the faces parallel to the principal crystallographic directions).

Nanoarhitectonics of Inorganic-Organic Silica-Benzil Composites: Synthesis, Nanocrystal Morphology and Micro-Raman Analysis.

The synthesis of nanosized organic benzil (C6H5CO)2 crystals within the mesoporous SiO2 host matrix was investigated via X-ray diffraction, transmission electron microscopy, Raman spectroscopy, and ab initio lattice dynamics analysis. Combining these methods, we have proved that the main structural properties of benzil nanocrystals embedded into SiO2 host membranes with pore diameters of 6.0, 7.8, 9.4, and 13.0 nm are preserved compared to a bulk benzil crystal. Space confinement has an insignificant impact on the lattice vibrational properties of benzil crystals implanted into the host matrices. The ab initio lattice dynamics calculation of the phonon spectrum in the Brillouin zone center shows the mechanical and dynamical stability of benzil lattice, revealing very low optical frequency of 11 cm-1 at point Γ.

Second harmonic generation on crystalline organic nanoclusters under extreme nanoconfinement in functionalized silica-benzil composites.

We demonstrate a series of organic-inorganic nanocomposite materials combining the mesoporous silica (PS) and benzil (BZL) nanocrystals embedded into its nanochannels (6.0-13.0 nm in diameter) by capillary crystallization. One aims to design novel, efficient nonlinear optical composite materials in which inactive amorphous host PS-matrix provides a tubular scaffold structure, whereas nonlinear optical functionality results from specific properties of the deposited guest BZL-nanocrystals. A considerable contraction of the BZL melt during its crystallization inside the silica nanochannels results in a formation of the texture consisting of (221)- and (003)-oriented BZL nanoclusters (22 nm in length), separated by voids. Specificity of the textural morphology similarly to the spatial confinement significantly influences the nonlinear optical features of composite PS:BZL materials being explored in the second harmonic generation (SHG) experiment. The light polarization anisotropy of the SHG response appears to be considerably reduced at channel diameters larger than 7 nm apparently due to the multiple scattering and depolarization of the light on randomly distributed and crystallographically oriented BZL-nanoclusters. The normalized SHG response decreases nonlinearly by more than one order of magnitude as the channel diameter decreases from 13.0 to 6.0 nm and vanishes when spatial cylindrical confinement approaches the sizes of a few molecular layers suggesting that the embedded BZL clusters indeed are not uniformly crystalline but are characterized by more complex morphology consisting of a disordered SHG-inactive amorphous shell, covering the channel wall, and SHG-active crystalline core. Understanding and controlling of the textural morphology in inorganic-organic nanocrystalline composites as well as its relationships with nonlinear optical properties can lead to the development of novel efficient nonlinear optical materials for the light energy conversion with prospective optoelectronic and photonic applications.

Absorption and fluorescence spectra of heterocyclic isomers from long-range-corrected density functional theory in polarizable continuum approach.

Long-range-corrected (LC) DFT/TDDFT methods may provide adequate description of ground and excited state properties; however, accuracy of such an approach depends much on a range separation (exchange screening) representing adjustable model parameter. Its relation to a size or specific of molecular systems has been explored in numerous studies, whereas the effect of solvent environment is usually ignored during the evaluation of state properties. To benchmark and assess the quality of the LC-DFT/TDDFT formalism, we report the optical absorption and fluorescence emission energies of organic heterocyclic isomers, DPIPQ and PTNA, calculated by LC-BLYP DFT/TDDFT method in the polarizable continuum (PCM) approach. The calculations are compared with the optical absorption and fluorescence spectra measured in organic solvents of different polarity. Despite a considerable structural difference, both dyes exhibit quite similar range separations being somewhat different for the optical absorption and fluorescence emission processes. Properly parametrized LC-BLYP xc-potential well reproduces basic features of the optical absorption spectra including the electronic transitions to higher excited states. The DFT/TDDFT/PCM analysis correctly predicts the solvation trends although solvatochromic shifts of the electronic transition energies appear to be evidently underestimated in most cases, especially for the fluorescence emission. Considering the discrepancy between the experiment and theory, evaluated state dipole moments and solvation corrections to the exchange screening are analyzed. The results of the present study emphasize the importance of a solvent-dependent range separation in DFT/TDDFT/PCM calculations for investigating excited state properties.

On the issue of textured crystallization of Ba(NO3)2 in mesoporous SiO2: Raman spectroscopy and lattice dynamics analysis.

The lattice dynamics of preferentially aligned nanocrystals formed upon drying of aqueous Ba(NO3)2 solutions in a mesoporous silica glass traversed by tubular pores of approximately 12 nm are explored by Raman scattering. To interpret the experiments on the confined nanocrystals polarized Raman spectra of bulk single crystals and X-ray diffraction experiments are also performed. Since a cubic symmetry is inherent to Ba(NO3)2, a special Raman scattering geometry was utilized to separate the phonon modes of Ag and Eg species. Combining group-theory analysis and ab initio lattice dynamics calculations a full interpretation of all Raman lines of the bulk single crystal is achieved. Apart from a small confinement-induced line broadening, the peak positions and normalized peak intensities of the Raman spectra of the nanoconfined and macroscopic crystals are identical. Interestingly, the Raman scattering experiment indicates the existence of comparatively large,∼10-20 µm, single-crystalline regions of Ba(NO3)2 embedded in the porous host, near three orders of magnitude larger than the average size of single nanopores. This is contrast to the initial assumption of non-interconnected pores. It rather indicates an inter-pore propagation of the crystallization front, presumably via microporosity in the pore walls.

Dynamic Kerr and Pockels electro-optics of liquid crystals in nanopores for active photonic metamaterials.

Photonic metamaterials with properties unattainable in base materials are already beginning to revolutionize optical component design. However, their exceptional characteristics are often static, as artificially engineered into the material during the fabrication process. This limits their application for in-operando adjustable optical devices and active optics in general. Here, for a hybrid material consisting of a liquid crystal-infused nanoporous solid, we demonstrate active and dynamic control of its meta-optics by applying alternating electric fields parallel to the long axes of its cylindrical pores. First-harmonic Pockels and second-harmonic Kerr birefringence responses, strongly depending on the excitation frequency and temperature, are observed in a frequency range from 50 Hz to 50 kHz. This peculiar behavior is quantitatively traced by a Landau-De Gennes free energy analysis to an order-disorder orientational transition of the rod-like mesogens and intimately related changes in the molecular mobilities and polar anchoring at the solid walls on the single-pore, meta-atomic scale. Thus, our study provides evidence that liquid crystal-infused nanopores exhibit integrated multi-physical couplings and reversible phase changes that make them particularly promising for the design of photonic metamaterials with thermo-electrically tunable birefringence in the emerging field of space-time metamaterials aiming at full spatio-temporal control of light.

Piezo-optic coefficients of MgO-doped LiNbO3 crystals.

We describe an interferometric technique suitable for determination of piezo-optic coefficients (POCs) in crystals. The method considers real nonparallelism of measured samples, thereby improving the measuring precision of POCs significantly. Corresponding equations are derived for the interferometric half-wave stress method. Using this technique we have determined a complete set of POCs of pure and MgO-doped LiNbO(3) crystals. The reliability of the data has been confirmed by comparing the effective POCs expressed through the combinations of measured POCs and the effective POCs determined independently using highly precise optical birefringence measurements. Pure and MgO-doped LiNbO(3) crystals reveal nearly the same magnitudes of POCs. However, LiNbO(3):MgO exhibits about 4 times higher resistance with respect to powerful light radiation, making it more suitable for application in acousto-optic devices that deal with superpowerful laser radiation.

Capillary rise of water in hydrophilic nanopores.

We report on the capillary rise of water in three-dimensional networks of hydrophilic silica pores with 3.5 nm and 5 nm mean radii, respectively (porous Vycor monoliths). We find classical square root of time Lucas-Washburn laws for the imbibition dynamics over the entire capillary rise times of up to 16 h investigated. Provided we assume two preadsorbed strongly bound layers of water molecules resting at the silica walls, which corresponds to a negative velocity slip length of -0.5 nm for water flow in silica nanopores, we can describe the filling process by a retained fluidity and capillarity of water in the pore center. This anticipated partitioning in two dynamic components reflects the structural-thermodynamic partitioning in strongly silica bound water layers and capillary condensed water in the pore center which is documented by sorption isotherm measurements.

Self-assembly of liquid crystals in nanoporous solids for adaptive photonic metamaterials.

Nanoporous media exhibit structures significantly smaller than the wavelengths of visible light and can thus act as photonic metamaterials. Their optical functionality is not determined by the properties of the base materials, but rather by tailored, multiscale structures, in terms of precise pore shape, geometry, and orientation. Embedding liquid crystals in pore space provides additional opportunities to control light-matter interactions at the single-pore, meta-atomic scale. Here, we present temperature-dependent 3D reciprocal space mapping using synchrotron-based X-ray diffraction in combination with high-resolution birefringence experiments on disk-like mesogens (HAT6) imbibed in self-ordered arrays of parallel cylindrical pores 17 to 160 nm across in monolithic anodic aluminium oxide (AAO). In agreement with Monte Carlo computer simulations we observe a remarkably rich self-assembly behaviour, unknown from the bulk state. It encompasses transitions between the isotropic liquid state and discotic stacking in linear columns as well as circular concentric ring formation perpendicular and parallel to the pore axis. These textural transitions underpin an optical birefringence functionality, tuneable in magnitude and in sign from positive to negative via pore size, pore surface-grafting and temperature. Our study demonstrates that the advent of large-scale, self-organised nanoporosity in monolithic solids along with confinement-controllable phase behaviour of liquid-crystalline matter at the single-pore scale provides a reliable and accessible tool to design materials with adjustable optical anisotropy, and thus offers versatile pathways to fine-tune polarisation-dependent light propagation speeds in materials. Such a tailorability is at the core of the emerging field of transformative optics, allowing, e.g., adjustable light absorbers and extremely thin metalenses.

A ferroelectric liquid crystal confined in cylindrical nanopores: reversible smectic layer buckling, enhanced light rotation and extremely fast electro-optically active Goldstone excitations.

The orientational and translational order of a thermotropic ferroelectric liquid crystal (2MBOCBC) imbibed in self-organized, parallel, cylindrical pores with radii of 10, 15, or 20 nm in anodic aluminium oxide monoliths (AAO) are explored by high-resolution linear and circular optical birefringence as well as neutron diffraction texture analysis. The results are compared to experiments on the bulk system. The native oxidic pore walls do not provide a stable smectogen wall anchoring. By contrast, a polymeric wall grafting enforcing planar molecular anchoring results in a thermal-history independent formation of smectic C* helices and a reversible chevron-like layer buckling. An enhancement of the optical rotatory power by up to one order of magnitude of the confined compared to the bulk liquid crystal is traced to the pretransitional formation of helical structures at the smectic-A*-to-smectic-C* transformation. A linear electro-optical birefringence effect evidences collective fluctuations in the molecular tilt vector direction along the confined helical superstructures, i.e. the Goldstone phason excitations typical of the para-to-ferroelectric transition. Their relaxation frequencies increase with the square of the inverse pore radii as characteristic of plane-wave excitations and are two orders of magnitude larger than in the bulk, evidencing an exceptionally fast electro-optical functionality of the liquid-crystalline-AAO nanohybrids.

High-resolution dielectric study reveals pore-size-dependent orientational order of a discotic liquid crystal confined in tubular nanopores.

We report a high-resolution dielectric study on a pyrene-based discotic liquid crystal (DLC) in the bulk state and confined in parallel tubular nanopores of monolithic silica and alumina membranes. The positive dielectric anisotropy of the DLC molecule at low frequencies (in the quasistatic case) allows us to explore the thermotropic collective orientational order. A face-on arrangement of the molecular discs on the pore walls and a corresponding radial arrangement of the molecules is found. In contrast to the bulk, the isotropic-to-columnar transition of the confined DLC is continuous, shifts with decreasing pore diameter to lower temperatures, and exhibits a pronounced hysteresis between cooling and heating. These findings corroborate conclusions from previous neutron and x-ray-scattering experiments as well as optical birefringence measurements. Our study also indicates that the relative simple dielectric technique presented here is a quite efficient method in order to study the thermotropic orientational order of DLC-based nanocomposites.

Paranematic-to-nematic ordering of a binary mixture of rodlike liquid crystals confined in cylindrical nanochannels.

We explore the optical birefringence of the nematic binary mixtures 6CB_{1-x}7CB_{x} (0 ≤ x ≤ 1) embedded into parallel-aligned nanochannels of mesoporous alumina and silica membranes for channel radii of 3.4 ≤ R ≤ 21.0 nm. The results are compared with the bulk behavior and analyzed with a Landau-de Gennes model. Depending on the channel radius the nematic ordering in the cylindrical nanochannels evolves either discontinuously (subcritical regime, nematic ordering field σ<1/2) or continuously (overcritical regime, σ>1/2), but in both cases with a characteristic paranematic precursor behavior. The strength of the ordering field, imposed by the channel walls, and the magnitude of quenched disorder varies linearly with the mole fraction x and scales inversely proportionally with R for channel radii larger than 4 nm. The critical pore radius, R_{c}, separating a continuous from a discontinuous paranematic-to-nematic evolution varies linearly with x and differs negligibly between the silica and alumina membranes. We find no hints of preferred adsorption of one species at the channels walls. By contrast, a linear variation of the nematic-to-paranematic transition point T_{PN} and of the nematic ordering field σ versus x suggests that the binary mixtures of cyanobiphenyls 6CB and 7CB keep their homogeneous bulk stoichiometry also in nanoconfinement, at least for channel diameters larger than ∼7 nm.