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The merging of the materials science paradigms of liquid crystals and 2D materials promises superb new opportunities for the advancement of the fields of optoelectronics and photonics. In this review, we summarise the development of 2D material liquid crystals by two different methods: dispersion of 2D materials in a liquid crystalline host and the liquid crystal phase arising from dispersions of 2D material flakes in organic solvents. The properties of liquid crystal phases that make them attractive for optoelectronics and photonics applications are discussed. The processing of 2D materials to allow for the development of 2D material liquid crystals is also considered. An emphasis is placed on the applications of such materials; from the development of films, fibers and membranes to display applications, optoelectronic devices and quality control of synthetic processes.
Ben graduated from the University of Bath in 2015 with a MSci in Natural Sciences. He is currently a postgraduate researcher within the EPSRC Centre for Doctoral Training in Metamaterials at the University of Exeter, UK, working in the Optoelectronic Systems Group lead by Prof. Baldycheva. His research focuses on the synthesis, characterisation and application to devices of novel optoelectronic and photonic 2D liquid crystal materials incorporating metamaterial structures.
Dr Evgeniya Kovalska is a Postdoctoral Research Fellow in the Laboratory of Smart Materials and Devices at Bilkent University of Ankara, Turkey. Her current research pertains to synthesis and application of graphene, transfer printing processes, patterning methods, developing new micro/nano-scale devices, chemical and electrooptical characterization, and microfabrication techniques. She obtained her PhD degree in chemistry with specialty in the physics and chemistry of surfaces in the Department of Physical Chemistry of Carbon Materials at Chuiko Institute of Surface Chemistry of the NAS of Ukraine, Kyiv.
Monica Craciun is a Professor in Nanoscience and Nanotechnology. She received her PhD from Kavli Institute of Nanoscience, Delft University of Technology, The Netherlands and held a prestigious Fellowship of the Japanese Society for the Promotion of Science at The University of Tokyo, Japan. Her research is focused on two-dimensional materials for emerging technologies. She has published more than 80 papers in reputed journals such as Nature Nanotechnology, Science Advances, Advanced Materials, and Nano Letters. She was awarded an early career fellowship from the U.K. Engineering and Physical Sciences Research Council and was investigator on more than 30 funded research projects.
Prof. Anna Baldycheva completed her BSc(Hons) at Saint-Petersburg University in 2008 and PhD at Trinity College Dublin in 2012. She is currently leading a highly interdisciplinary research group, Opto-Electronic Systems Laboratory, at the Centre for Graphene Science at the University of Exeter. Prof. Baldycheva's research group works in the areas of Si photonics, and flexible and fluid opto-electronics. Her research interests span from the development of the new photonic composite materials to the engineering of integrated hybrid electronic-photonic devices for application in communications, energy harvesting, and bio-chemical sensing. Since 2011 she has over 50 peer-reviewed publications, invited talks and conference proceedings.
Two-dimensional (2D) nanocomposite materials with dynamically tunable liquid crystalline properties have recently emerged as a highly-promising class of novel functional materials, opening new routes within a wide variety of potential applications from the deposition of highly uniform layers and heterostructures, to novel display technologies. Here, we will introduce the underlying concepts that underpin this recent technological advance; provide an overview of the synthetic routes towards such 2D nanocomposite materials; and review recent advances in the application and applicability of these materials within the fields of optoelectronics and photonics.
The liquid crystal phase is a phase of matter that exists for a variety of molecules and materials, depending on their geometric and chemical properties, with characteristics intermediate to those of a conventional crystalline solid and a liquid.6,7 Liquid crystals (LCs) have found use in a variety of applications through the years (Fig. 1). The liquid crystal phase was initially described by Austrian botanist Friedrich Reinitzer in 1888 when looking at the properties of cholesterol derivatives,8,9 although some credit also goes to Julius Planer, who reported similar observations 27 years prior.10,11 This new and distinct state of matter was then identified as the “liquid crystal phase” by Otto Lehmann in 1890 and in 1904 the first commercially available LCs were produced by Merck-AG.12 Over the following 18 years, scientists established the existence of three distinct liquid crystalline phases (nematic, smectic and cholesteric)12 but, with no applications of note forthcoming, the study of LCs was halted. For the next 30 years, the scientific community ignored LC materials, considering them as an interesting curiosity. However, following a renaissance in liquid crystal science in the 1950s, the previously scientific curiosity has become a ubiquitous part of the modern technology landscape.
Fig. 1 Timeline of the history of liquid crystal phase applications, from their discovery to the present day. 1888: the LC phase was first reported by Friedrich Reinitzer (image reproduced with permission from Mitov, ChemPhysChem, 2014,96 (©2014 Wiley-VCH)). 1950–1959: the development of the first cholesteric phase and LC thermometers. 1962: the switchable orientation of LC molecules was first utilised in laser devices. 1965: the first prototype LCD was developed by George H. Heilmeier before finding limited applications. 1969–1971: the first twisted nematic cell displays were developed from the initial work of Martin Schadt and incorporated in devices. 1980–1990s: LCDs found widespread application in small mobile devices as the display of choice. From the 1990s onwards, much larger LCDs have appeared while advances in the technology have allowed the production of high resolution small-scale displays. Beginning in the new millennium, LCs have emerged as desirable optoelectronic materials. They have, as such, been studied from natural sources such as can be found in beetles, as well as in polarisation-selective waveguiding and in holography. The discovery of graphene in 2004 opened up new avenues for LC science and, since 2010, the emergence of LCs combined with 2D materials has opened applications in developing 2D material fibers (reproduced with permission from Xu and Gao, Nat. Commun., 20114 (©2011 Nature Publishing Group)), reflective displays (reproduced from He et al., Nanoscale, 201452 with permission from The Royal Society of Chemistry ©2014), deposition of uniform layered structures (reproduced with permission from Jalili et al., ACS Nano, 201378 (©2013 American Chemical Society)) and as a platform for novel optofluidic devices (reproduced with permission from Hogan et al., Sci. Rep., 20173 (©2017 Nature Publishing Group)). The future of the field promises to revolutionise fields from CMOS photonics, to metastructures and metadevices and wearable technologies. All images utilised under a free-to-use creative commons license except where otherwise credited.
The possibility of the existence of a liquid crystal phase stems principally from the geometric structure of the molecules in the material as well as the functional groups present in the molecule. In lyotropic liquid crystals, mesogens are dispersed in a host solvent (typically water but other organic solvents can be used depending on the molecule).6,7,20 Lyotropic liquid crystals exhibit a liquid crystal phase within a certain range of temperatures but also require a concentration of the active mesogens that falls within a certain range. In the lyotropic phase, the fluidity of the material is induced by the solvent molecules rather than being intrinsic to the mesogens themselves. The mesogens contain immiscible solvophilic and solvophobic parts separated at opposing ‘ends’ or facets of the molecule, making them amphiphilic. As one end has a preferential interaction with the host solvent, ordering of the amphiphilic molecules occurs to maximise the solvophilic ‘head’ interaction with the host solvent while minimising that for the solvophobic ‘tail’. The structures formed by the mesogens are dependent on the relative volumes of the ‘head’ and ‘tail’ as well as the concentration of the molecules within the solvent.
At very low concentrations, there will be no ordering of the amphiphilic molecules dispersed in the solvent.6,7,20 As the concentration is increased, there will be a critical concentration at which micelles are spontaneously formed – however, the micelles do not order themselves so this still does not represent a liquid crystal phase. At higher concentrations, the micelles must order themselves as the inter-micelle interactions become energetically important above a critical micellular concentration within the solvent. Typically, a hexagonal columnar phase is formed where long cylindrical rods of amphiphilic mesogens arrange themselves into a hexagonal lattice structure but other structures are possible depending on the mesogen. As the concentration increases further, a lamellar phase will form, with layers of the mesogens separated by thin layers of solvent. In lyotropic liquid crystals, it is objects formed by the aggregations of amphiphiles that can then be ordered in the same ways as observed for thermotropic liquid crystals. Lyotropic liquid crystals possess significant tunability as the structural properties are highly sensitive to changes in concentration. For example, within in the hexagonal columnar phase, the lattice parameters can be varied by varying the solvent volume in the mixture.
Liquid crystals are of particular interest due to their inherent ordering while in the liquid phase and for their ability to align the director along an external field.21,22 Permanent electric dipoles can exist in the individual liquid crystal molecules when one part of the mesogen has a positive charge while another has a negative charge. When an external electric field is then applied to the liquid crystal, the dipoles orient along the direction of the field as the electric field exerts a force on the dipoles. Some liquid crystal molecules, however, do not form a permanent dipole but can still be influenced by an electric field. The shape anisotropy of many liquid crystal mesogens means that they are highly polarisable and as such an applied electric field can induce a dipole by relocating the electron density within the molecule. While not as strong as permanent dipoles, orientation of the induced dipoles with the external field still occurs. The effects of magnetic fields on liquid crystal molecules are analogous to electric fields with the molecules aligning with or against the magnetic field.
Fig. 2 Liquid phase exfoliation of 2D materials. (a) Starting material (e.g., graphite), (b) chemical wet dispersion, (c) ultrasonication and (d) final dispersion after the ultracentrifugation process. Reproduced with permission from Bonaccorso and Sun, Opt. Mater. Exp., 201431 (©2014, The Optical Society).
Amongst materials discussed further here, graphene can be exfoliated from bulk graphite owing to the weak van der Waals interactions between layers in graphite.54 Graphene is an allotrope of carbon consisting of a two-dimensional hexagonal lattice with a single carbon atom at each vertex. The carbon atoms in graphene are sp2 hybridised in-plane with these sp2 electrons forming three carbon–carbon bonds. The final p orbital is unhybridised and directed out of the plane. For a graphene sheet these out of plane p orbitals hybridise to form the delocalised π and π* bands which are responsible for graphene's exceptional electronic properties; these exceptional properties make graphene of significant interest as a material for forming electrical contacts, films and fibers.
Graphene oxide is the 2D material produced by the exfoliation of graphite oxide.55 Maximum oxidation of graphite results in a carbon to oxygen ratio between 2.1 and 2.9. Graphite oxide retains the layered structure of graphite but the interlayer spacing is increased and no longer regular for bulk graphite oxide. The oxidation of graphite introduces three types of oxygen containing functional groups to the structure: epoxy bridges (oxygen bridging between two carbons on the surface of a graphitic sheet), hydroxyl groups (on either the surface or the edges) and carboxyl groups (on the edges of the graphitic sheets).56 Graphene oxide can be exfoliated from bulk graphite oxide analogously to graphene from graphite.54,55 However, the intercalation of the graphitic carbon sheets by oxygenated functional groups results in graphene oxide being more readily exfoliatable. This means that graphene oxide can be exfoliated to few layers and even monolayer in large quantities without the use of additional surfactant molecules.33,35 Graphene oxide possesses nonlinear optical properties of significant interest for applications in ultrafast photonics and optoelectronics. The saturable absorption can be used for pulse compression, mode locking and Q-switching of laser systems.57 The large observed Kerr effect introduces possibilities in all-optical switching and signal regeneration and hence optical communications devices.58 The nonlinear optical properties of graphene oxide can be tuned by controlling the carbon to oxygen ratio of the material,59 this tuning has been achieved using laser irradiance to reduce the material.
Fig. 3 (a) Polarized light microscopic images between crossed polarizers of GO aqueous dispersions in planar cells with increasing maximum mass fractions from 1 to 6. Green arrows indicate disclinations of the liquid crystal phase, and the scale bars represent distances of 200 μm. (b) Macroscopic images between crossed polarizers of GO aqueous dispersions in test tubes with increasing maximum mass fractions from 1 to 7. Reproduced with permission from Xu and Gao, ACS Nano, 201147 (©2011, American Chemical Society).
Fig. 4 Phase diagram of graphene oxide aqueous dispersions in terms of osmotic pressure, volume fraction of GO and salt concentration in the solution. Reproduced with permission from Konkena and Vasudevan, J. Phys. Chem. C, 201475 (©2014, American Chemical Society).
Fig. 5 Schlieren textures observed in dispersions of graphene oxide in a range of organic solvents under microscopy using crossed polarisers. Reproduced with permission from Jalili et al., ACS Nano, 201378 (©2013 American Chemical Society).
The self-assembling nature of liquid crystalline materials has led to the use of graphene oxide dispersions for the formation of well-ordered layers and stacks of 2D materials. Behabtu et al.,27 demonstrated that graphite spontaneously exfoliates into single-layer graphene in chlorosulfonic acid, and spontaneously forms liquid-crystalline phases at high concentrations. Transparent, conducting films were produced from the liquid crystalline dispersions. Jalili et al.78 showed that self-assembly of graphene oxide sheets is possible in a wide range of organic solvents. The prepared dispersions were employed to achieve self-assembled layer-by-layer multifunctional 3D hybrid architectures comprising SWNTs and GO with promising mechanical properties (Fig. 6). More recently, the same group has showed that similar self-assembly can be achieved using liquid crystalline dispersions of molybdenum disulfide.50 Layers of these materials have been combined with other materials for a variety of diverse applications such as photovoltaics81 and improving the mechanical properties of composite materials,82 the more homogeneous layers produced from the liquid crystalline dispersions are of significant interest to applications of these natures. The use of liquid crystalline dispersions of graphene oxide to produce uniform layers has been used as a precursor to forming similarly uniform structures of graphene through the reduction of the graphene oxide.4,49 Akbari et al. demonstrate that the discotic nematic phase of GO can be shear aligned to form highly ordered, continuous films of multi-layered GO on a supporting membrane. The highly ordered graphene sheets in the plane of the membrane make organized channels and give greater permeability. The nanoporous membranes may find application in a variety of filtering applications.83 Fu et al. demonstrate the use of graphene oxide liquid crystals can be applied as composite inks for the formation of electrodes in 3D printing applications84 due to the intrinsic self-assembly that means they retain ordering of the GO platelets on drying of the solvent.
Fig. 6 (a) Photograph of a flexible free-standing paper of LC GO made by a cast drying method. (b) SEM image of the cross section of as-cast dried LC GO paper. (c) SEM image of the surface of the layer-by-layer composite, marked as region (i) in (b). (d–f) Cross section of composite paper at different. Reproduced with permission from Jalili et al., ACS Nano, 201378 (©2013 American Chemical Society).
Fig. 7 (a) Four-metre-long wound GO fibre. SEM images of the fibre (b), and a typical tighten knot (c). (d) The morphology of the GO fibre after tensile tests. All scale bars 50 μm. Reproduced with permission from Xu and Gao, Nat. Commun., 20114 (©2011 Nature Publishing Group).
Liquid crystalline nanocomposites incorporating 2D material particles show great promise for optoelectronic applications due to their field induced tunability and enhanced functionality stemming from the plethora of properties displayed by the range of exfoliatable materials. For example, dispersions of liquid crystalline graphene oxide have been shown to undergo electro-optical switching with low threshold voltage requirements.90 Kim et al. show that GO LCs possess an extremely large Kerr coefficient, making them attractive for low power consumption optoelectronic devices. By stabilising a suspension of reduced GO using surfactants, they demonstrated increased time stability and drastically improved electro-optic properties with an induced birefringence twice as large at the same field strength as that with an unreduced GO suspension.
Zhu et al.91 have shown that the preparation of poly(N-isopropylacrylamide)/GO nanocomposite hydrogels with macroscopically oriented LC structures, after polymerisation, can be readily achieved under assistance from a flow-field – induced by vacuum degassing. Nanocomposites prepared with a GO concentration of 5.0 mg mL−1 exhibit macroscopically aligned LC structures, which endow the gels with anisotropic optical properties. Furthermore, they show that the oriented LC structures are not damaged during switching of the hydrogels, and hence their behaviour undergoes reversible changes. Additionally, they show that the oriented LC structures in the hydrogels can be permanently maintained after drying the nanocomposite samples. The liquid crystalline properties of such nanocomposites facilitate their applicability to switching in optoelectronic devices.
Kim et al.92 have demonstrated significant improvement of the electro-optic performance of a polymer-stabilized liquid crystalline blue phase using a reduced graphene oxide (RGO) enriched polymer network. The conductivity of the nanocomposite system is increased by the inclusion of the RGO. Furthermore, reductions in the operational voltage (∼32%), response time (∼51%) and hysteresis (∼53%) compared to that of a conventional polymer-stabilized BPLC signify great potential for the use of 2D materials in enhancing novel electro-optic device applications of conventional LC systems.
Recently, Hogan et al. proposed that by tuning the liquid crystal director by means of an applied field, one could induce the formation of metastructures formed of the dispersed 2D material particles as they are repositioned. In particular, they show that nanocomposites of nematic phase liquid crystals with dispersed graphene oxide particles can be integrated with CMOS photonics devices as a back-end process as part of microfluidic systems and that the integrated nanocomposites can be readily controlled by use of either an electric field or laser light to reposition and rearrange the dispersed particles3 (Fig. 8). They present a novel characterisation method based on Raman spectroscopy to allow determination of the spatial positioning of the integrated 2D material particles, allowing precise monitoring of metastructure formation.
Fig. 8 (a) Control of liquid crystal dispersed 2D material particle using laser light. (b and c) SEM images of GO flakes integrated in microfluidic channels with a nematic liquid crystal host. (d) SEM image of GO flakes integrated into a microfluidic waveguide after removal of host fluid. (e) A CMOS photonic circuit coupled to a microfluidic layer integrating dynamically reconfigurable 2D material metastructures by exploiting liquid crystal technology. Adapted with permission from Hogan et al., Sci. Rep., 20173 (©2017 Nature Publishing Group).
2D material liquid crystals can be used in back-illuminated liquid crystal display applications as they exhibit electro-optic switching. The large Kerr coefficient of graphene oxide liquid crystals observed by Shen et al.,53 for example, facilitates this application. However, the slow switching times reported by Kim and Kim (>1 s)93 must be considered, although Ahmad et al.94 report that this can be improved by approximately an order of magnitude by careful selection of the size of graphene oxide mesogens.
More promisingly, 2D material liquid crystals have also been proposed for application in liquid crystal displays – particularly in so-called ‘e-ink’ displays – without requiring the polarising optics typically necessary for these applications.52,76 He et al.52 demonstrate a process by which graphene oxide liquid crystals can be used for reflective displays without the need for polarizing optics (Fig. 9). By using flow-induced mechanical alignment, they prepared graphene oxide in different orientational orders and demonstrated that the ordered graphene oxide liquid crystals can be used as a rewritable display medium. The surface of the graphene oxide liquid crystal can be switched from a bright, reflective state to a dark, transmissive state using, for example, a wire to manually draw patterns on the surface. They explain that the contrast between the two states arises due to the anisotropic response of the flakes due to the inherent high aspect ratio of the 2D material.
Fig. 9 Images of a defined structure in a liquid crystalline e-ink of graphene oxide dispersed in water in (a and d) reflection with unpolarised light, (b and e) transmission with unpolarised light and (c and f) transmission between crossed polarisers. Reproduced from He et al., Nanoscale, 201452 with permission from The Royal Society of Chemistry ©2014.
Inducing the onset of a liquid crystal phase in a dispersion of graphene oxide has been used for size selection of the graphene oxide particles.95 Lee et al. introduce a method for facile size selection of large-size graphene oxide particles by exploiting liquid crystallinity. They show that in a biphasic graphene oxide dispersion where both isotropic and liquid crystalline phases are in equilibrium, large-size GO flakes (>20 μm) are spontaneously concentrated within the liquid crystalline phase. Selectivity of large flake sizes without the need of filtering presents several advantages for photonics and optoelectronics applications; primarily larger flakes allow for greater uniformity of device characteristics over wider areas and can help to increase the uniformity of depositions.
2D materials encompass a fascinating range of diverse properties with a myriad of possible applications in optoelectronics and photonics. The development of liquid crystalline nanocomposite materials incorporating 2D materials represents a significant advance in the opportunities for integration and exploitation of 2D materials within these fields. However, there remain a large number of questions that demand further investigation before 2D material liquid crystals can find wider application. Primarily, there remain many candidate 2D materials for which a liquid crystal phase is theoretically possible but not yet shown; the discovery of further 2D material liquid crystals would broaden the range of utilisable properties available. Similarly to that observed for graphene oxide, observation of this liquid crystallinity should require a combination of careful solvent selection, tuning of the 2D material particle sizes and control of the concentration of the particles. Additionally, the use of surfactant molecules may be necessary to stabilise the liquid crystalline phase of the dispersions by maximising the aligning forces acting on the dispersed particles. However, this raises the additional question of the exploration – both theoretical and experimental – of the conditions required for the existence of the liquid crystal phase, an area in which little work has far been explored for the specific systems of interest here. A significant part of such work remains to be done in the comparison of the different synthetic routes towards the LC phase, and how the synthesis can affect the observed properties.
Additionally, dispersion of 2D materials in conventional liquid crystal host fluids presents superb new possibilities in optofluidic systems; from light generation to dynamic sensing applications. This is owing to the dramatic improvements that can be observed in the operational parameters of the nanocomposite systems in comparison to the conventional LC systems currently used in optoelectronics and photonics. Such nanocomposites, can not only improve properties such as switching times and threshold voltages, but can also add further functionality, for example by metastructuring of nanoparticle dispersions. For these nanocomposite systems, the most important advances to be made are in the fundamental understanding of the basis for improvements in their intrinsic properties; and in the exploration of predicting metastructuring as well as experimental observation.
Overall, the existence of liquid crystal phase 2D material dispersions presents fantastic opportunities in the exploration of novel optoelectronic and photonic systems, allowing new highly-scalable production processes for thin film integration and novel fiber systems amongst numerous other applications.
We acknowledge financial support from the Engineering and Physical Sciences Research Council (EPSRC) of the United Kingdom via the EPSRC Centre for Doctoral Training in Electromagnetic Metamaterials (Grant No. EP/L015331/1) and via Grant No. EP/N035569/1, EP/G036101/1 and EP/M002438/1.
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