Supramolecular Organic Ferroelectric Materials from Donor-Acceptor Systems.

Organic ferroelectric (FE) materials, though known for more than a century, are yet to reach close to the benchmark of inorganic or hybrid materials in terms of the magnitude of polarization. Amongst the different classes of organic systems, donor (D)-acceptor (A) charge-transfer (CT) complexes are recognized as promising for ferroelectricity owing to their neutral-to-ionic phase transition at low temperature. This review presents an overview of different supramolecular D-A systems that have been explored for FE phase transitions. The discussion begins with a general introduction of ferroelectricity and its different associated parameters. Then it moves on to show early examples of CT cocrystals that have shown FE properties at sub-ambient temperature. Subsequently, recent developments in the field of room temperature (RT) ferroelectricity, exhibited by H-bond-stabilized lock-arm supramolecular-ordering (LASO) in D-A co-crystals or other FE CT-crystals devoid of neutral-ionic phase transition are discussed. Then the discussion moves on to emerging reports on other D-A soft materials such as gel and foldable polymers; finally it shows very recent developments in ferroelectricity in supramolecular assemblies of single-component dipolar or ambipolar π-systems, exhibiting intra-molecular charge transfer. The effects of structural nuances such as H-bonding, balanced charge transfer and chirality on the observed ferroelectricity is described with the available examples. Finally, piezoelectricity in recently reported ambipolar ADA-type systems are discussed to highlight the future potential of these soft materials in micropower energy harvesting.

A Hierarchical (Macro)molecular Assembly Assisted by Donor-Acceptor Charge-Transfer Interactions Exhibiting Room-Temperature Ferroelectricity.

This communication reveals co-assembly of an electron-deficient naphthalene-diimide (NDI)-appended polyurethane (P1) and electron-rich pyrene (Py), forming an organogel with prominent room-temperature ferroelectricity. In a non-polar medium, intra-chain hydrogen-bonding among the urethane groups of P1 produces a folded structure with an array of the NDIs in the periphery, which intercalate Py by charge-transfer (CT)-interaction. Such CT-complexation enables slow crystallization of the peripheral hydrocarbons, causing gelation with nanotubular morphology, in which the wall consists of the alternating NDI-Py stack. Such D-A assembly exhibits ferroelectricity (saturation polarization Ps ≈0.8 µC cm-2 and coercive field Ec ≈8 kV cm-1 at 500 V and 10 Hz frequency) with Curie temperature (Tc ) of ≈350 K, which can be related to the disassembly of the CT-complex. In the absence of Py, P1 forms spherical aggregates, showing dielectric behaviour.

Vertically aligned zinc oxide nanowires electrodeposited within porous polycarbonate templates for vibrational energy harvesting.

A piezoelectric nanogenerator has been fabricated using a simple, fast and scalable template-assisted electrodeposition process, by which vertically aligned zinc oxide (ZnO) nanowires were directly grown within a nanoporous polycarbonate (PC) template. The nanowires, having average diameter 184 nm and length 12 µm, are polycrystalline and have a preferred orientation of the [100] axis parallel to the long axis. The output power density of a nanogenerator fabricated from the as-grown ZnO nanowires still embedded within the PC template was found to be 151 ± 25 mW m(-3) at an impedance-matched load, when subjected to a low-level periodic (5 Hz) impacting force akin to gentle finger tapping. An energy conversion efficiency of ∼4.2% was evaluated for the electrodeposited ZnO nanowires, and the ZnO-PC composite nanogenerator was found to maintain good energy harvesting performance through 24 h of continuous fatigue testing. This is particularly significant given that ZnO-based nanostructures typically suffer from mechanical and/or environmental degradation that otherwise limits their applicability in vibrational energy harvesting. Our template-assisted synthesis of ZnO nanowires embedded within a protective polymer matrix through a single growth process is thus attractive for the fabrication of low-cost, robust and stable nanogenerators.

Evidence of superior ferroelectricity in structurally welded ZnSnO3 nanowire arrays.

Highly packed LN-type ZnSnO3 NW arrays are grown on ZnO:Al/Si substrates using a hybrid pulsed laser deposition and solvothermal process. Unique "welding" mechanism structurally joins adjacent ZnSnO3 NWs to form a nearly impervious 20 µm thick nanostructured film that shows high P r of 30 µC/cm(2) at a low E c of 25 kV/cm for the first time.

Achiral phosphonium induced remarkable circular polarized luminescence in a chiral cadmium(II) halide perovskite material.

Circular polarized luminescence (CPL) sensitive two-dimensional organic inorganic halide perovskites have versatile applications in optical displays, encrypted transmission and quantum communications. Here, a new chiral hybrid [MePh3P]2CdCl4 (PCC) single crystal (SC) is synthesized using an achiral phosphonium cation by a solvent evaporation process at room temperature (rt). SC x-ray study reveals a non-centrosymmetric point group 23, with 21-screw optical axes providing a chiral Sohncke space group. Hirshfeld surface analysis suggests long-range H-bonding and ionic interactions (~ 3-9 kJ mol-1) and short-range Van der Waals and dispersion interactions (∼0.4-4 kJ mol-1). Both the PCC thin films and SCs exhibit prominent circular dichroism (CD) and remarkably superior CPL activity at rt (|gCD| ≈ 5 × 10-3 and |glum| ≈ 4.3 × 10-2).

High-Performance Paper-Based Thermoelectric Generator from Cu2SnS3 Nanocubes and Bulk-Traced Bismuth.

Flexible paper-based thermoelectric generators (PTEGs) have drawn significant interest in recent years due to their various advantages such as flexibility, adaptability, environment friendliness, low cost, and easy fabrication process. However, the reported PTEG's output performance still lags behind the performance of other flexible devices as it is not so easy to obtain a compact film on a paper-based substrate with desirable power output with the standard thermoelectric (TE) materials that have been previously utilized. In this direction, Cu2SnS3 (CTS), an earth-abundant, ternary sulfide, can be a good choice p-type semiconductor, when paired with a suitable n-type TE material. In this article, CTS nanocubes are synthesized via a simple hot injection method and a thick film device on emery paper was prepared and optimized. Furthermore, a flexible, 20-pair PTEG is fabricated with p-type CTS legs and traced and pressed n-type bismuth legs assembled using Kapton tape that produced a significantly high output power of 2.18 µW (output power density ∼0.85 nW cm-2 K-1) for a temperature gradient of ΔT = 80 K. The TE properties are also supported by finite element simulation. The bending test conducted for the PTEG suggests device stability for up to 800 cycles with <0.05% change in the internal resistance. A proof-of-concept field-based demonstration for energy harvesting from waste heat of a motorbike exhaust is shown recovering an output power of ∼42 nW for ΔT = 20 K, corroborating the experimental and theoretical results.

Stable room temperature ferroelectricity in hydrogen-bonded supramolecular assemblies of ambipolar π-systems.

This article reports H-bonding driven supramolecular polymerization of naphthalimide (A)-thiophene (D)-naphthalimide (A) (AD n A, n = 1-4) conjugated ambipolar π-systems and its remarkable impact on room temperature ferroelectricity. Electrochemical studies confirm the ambipolar nature of these AD n A molecules with the HOMO-LUMO gap varying between 2.05 and 2.29 eV. Electron density mapping from ESP calculations reveals intra-molecular charge separation as typically observed in ambipolar systems. In the aggregated state, AD1A and AD2A exhibit bathochromically shifted absorption bands while AD3A and AD4A show typical H-aggregation with a hypsochromic shift. Polarization vs. electric field (P-E) measurements reveal stable room temperature ferroelectricity for these supramolecular assemblies, most prominent for the AD2A system, with a Curie temperature (T c) ≈ 361 K and saturation polarization (P s) of ∼2 µC cm-2 at a rather low coercive field of ∼2 kV cm-1. Control molecules, lacking either the ambipolar chromophore or the amide functionality, do not show any ferroelectricity, vindicating the present molecular and supramolecular design. Computational studies enable structural optimization of the stacked oligomer(s) of AD2A molecules and reveal a significant increase in the macro-dipole moment (in the range of 10-12 Debye) going from the monomer to the oligomer(s), which provides the rationale for the origin of ferroelectricity in these supramolecular polymers.

Ferroelectricity in a hydrogen-bonded alternating donor-acceptor supramolecular copolymer.

This communication reports synergistic H-bonding and charge-transfer (CT) interaction-promoted alternating supramolecular copolymerization of amide-functionalized pyrene (Py) and naphthalene-diimide (NDI) building blocks and the emergence of ferroelectricity with saturation polarization ∼3.2 µC cm-2, Curie temperature ∼304 K, and coercive field ∼8.5 kV cm-1 at 100 Hz. The Py or NDI molecules on their own do not exhibit any ferroelectric hysteresis, indicating an essential role of both CT-interaction and H-bonding in ferroelectricity. Computational studies provide insight into the origin of the polarization and the importance of the NDI/Py ratio. This study, showing room temperature ferroelectricity in purely organic systems, is of high relevance for flexible electronics and sensors. It opens up new opportunities for soft FE-materials with ample scope for further structural optimization.

CdS:Mn nanorods: solvothermal synthesis and properties.

Manganese (0.05-9 mol.%) doped CdS nanorods were synthesized via solvothermal route using ethylenediamine (En) and a mixture of En and water as the solvents. The diameters and the lengths of the doped CdS nanorods varied from 40-100 nm and 600-2500 nm, respectively, with change in the composition of the solvents. The broad photoluminescence (PL) emission from the undoped CdS nanorods centered at approximately 535 nm is found to be blue shifted to 516 nm with the incorporation of Mn in the CdS crystal structure. Also increase in the intensity of the PL was noticed in the Mn doped CdS nanorods for both the solvent systems. Maximum PL intensity was observed for 1 mol.% Mn in case of En system and for 0.5 mol.% Mn in case of En/water system, above which quenching occurred as a result of Mn-Mn clustering. EPR study revealed six-line hyperfine splitting for low Mn concentration in both solvent systems. Increase in the Mn concentration caused EPR signal broadening due to Mn-Mn clustering.

Nanoscale electromechanical properties of template-assisted hierarchical self-assembled cellulose nanofibers.

Cellulose, a major constituent of our natural environment and a structured biodegradable biopolymer, has been shown to exhibit shear piezoelectricity with potential applications in energy harvesters, biomedical sensors, electro-active displays and actuators. In this regard, a high-aspect ratio nanofiber geometry is particularly attractive as flexing or bending will likely produce a larger piezoelectric response as compared to axial deformation in this material. Here we report self-assembled cellulose nanofibers (SA-CNFs) fabricated using a template-wetting process, whereby parent cellulose nanocrystals (CNCs) introduced into a nanoporous template assemble to form rod-like cellulose clusters, which then assemble into SA-CNFs. Annealed SA-CNFs were found to exhibit an anisotropic shear piezoelectric response as directly measured using non-destructive piezo-response force microscopy (ND-PFM). We interpret these results in light of the distinct hierarchical structure in our template-grown SA-CNFs as revealed by scanning electron microscopy (SEM) and high resolution transmission electron microscopy (TEM).

Fully Printed Organic-Inorganic Nanocomposites for Flexible Thermoelectric Applications.

Thermoelectric materials, capable of interconverting heat and electricity, are attractive for applications in thermal energy harvesting as a means to power wireless sensors, wearable devices, and portable electronics. However, traditional inorganic thermoelectric materials pose significant challenges due to high cost, toxicity, scarcity, and brittleness, particularly when it comes to applications requiring flexibility. Here, we investigate organic-inorganic nanocomposites that have been developed from bespoke inks which are printed via an aerosol jet printing method onto flexible substrates. For this purpose, a novel in situ aerosol mixing method has been developed to ensure uniform distribution of Bi2Te3/Sb2Te3 nanocrystals, fabricated by a scalable solvothermal synthesis method, within a poly(3,4-ethylenedioxythiophene) polystyrene sulfonate matrix. The thermoelectric properties of the resulting printed nanocomposite structures have been evaluated as a function of composition, and the power factor was found to be maximum (∼30 µW/mK2) for a nominal loading fraction of 85 wt % Sb2Te3 nanoflakes. Importantly, the printed nanocomposites were found to be stable and robust upon repeated flexing to curvatures up to 300 m-1, making these hybrid materials particularly suitable for flexible thermoelectric applications.

Solvothermal synthesis of CdS nanorods: role of basic experimental parameters.

CdS nanorods with varying dimensions were synthesized by solvothermal process. It was observed that the anions present with the Cd-salts play an important role in determining the dimensions of the CdS nanorods. The crystalline nature of the sources was found to play a crucial role in determining the phase of the products. The nature of the sulfur source, molar ratio of the precursors, filling fraction of the solvent, and the synthesis temperature play important role in defining the size and shape of the products. By controlling the experimental parameters it was possible to control the dimension of the CdS nanorods within a certain range (diameter of the nanorods could be varied within a wide range from approximately 7 to 100 nm by varying the temperature within 100-250 degrees C). Optical absorption, photoluminescence, and Raman studies of these samples were carried out to characterize the CdS nanorods.

Multicolor luminescence from transition metal ion (Mn2+ and Cu2+) doped ZnS nanoparticles.

Mn and Cu doped ZnS nanoparticles in powder form were prepared by a simple solvothermal route. Particle size and crystal structure of the products were investigated through X-ray diffraction study revealing the formation of cubic ZnS nanoparticles of average diameter 2.5 nm. Particle size was also verified by the high resolution transmission electron microscopic images. Blue emission at approximately 445 nm was observed from the undoped sample, which was attributed to the presence of large surface defects. With increasing doping concentration the defect related emission gradually quenches and subsequently the impurity related emissions appeared. Mn doped samples exhibited orange emission at approximately 580 nm which may be attributed to the transition between (4)T1 and (6)A1 energy levels of the Mn2+ 3d states. Whereas, the Cu doped ZnS nanoparticles exhibited a red shifted strong blue emission at approximately 466 nm which is attributed to the transition of the electrons from the surface states to the 't2' levels of Cu impurities.

Mapping piezoelectric response in nanomaterials using a dedicated non-destructive scanning probe technique.

There has been tremendous interest in piezoelectricity at the nanoscale, for example in nanowires and nanofibers where piezoelectric properties may be enhanced or controllably tuned, thus necessitating robust characterization techniques of piezoelectric response in nanomaterials. Piezo-response force microscopy (PFM) is a well-established scanning probe technique routinely used to image piezoelectric/ferroelectric domains in thin films, however, its applicability to nanoscale objects is limited due to the requirement for physical contact with an atomic force microscope (AFM) tip that may cause dislocation or damage, particularly to soft materials, during scanning. Here we report a non-destructive PFM (ND-PFM) technique wherein the tip is oscillated into "discontinuous" contact during scanning, while applying an AC bias between tip and sample and extracting the piezoelectric response for each contact point by monitoring the resulting localized deformation at the AC frequency. ND-PFM is successfully applied to soft polymeric (poly-l-lactic acid) nanowires, as well as hard ceramic (barium zirconate titanate-barium calcium titanate) nanowires, both previously inaccessible by conventional PFM. Our ND-PFM technique is versatile and compatible with commercial AFMs, and can be used to correlate piezoelectric properties of nanomaterials with their microstructural features thus overcoming key characterisation challenges in the field.

Structure and Thermoelectric Properties of Bi2-xSbxTe3 Nanowires Grown in Flexible Nanoporous Polycarbonate Templates.

We report the room-temperature growth of vertically aligned ternary Bi2-xSbxTe3 nanowires of diameter ~200 nm and length ~12 µm, within flexible track-etched nanoporous polycarbonate (PC) templates via a one-step electrodeposition process. Bi2-xSbxTe3 nanowires with compositions spanning the entire range from pure Bi2Te3 (x = 0) to pure Sb2Te3 (x = 2) were systematically grown within the nanoporous channels of PC templates from a tartaric-nitric acid based electrolyte, at the end of which highly crystalline nanowires of uniform composition were obtained. Compositional analysis showed that the Sb concentration could be tuned by simply varying the electrolyte composition without any need for further annealing of the samples. Thermoelectric properties of the Bi2-xSbxTe3 nanowires were measured using a standardized bespoke setup while they were still embedded within the flexible PC templates.

Template-Assisted Hydrothermal Growth of Aligned Zinc Oxide Nanowires for Piezoelectric Energy Harvesting Applications.

A flexible and robust piezoelectric nanogenerator (NG) based on a polymer-ceramic nanocomposite structure has been successfully fabricated via a cost-effective and scalable template-assisted hydrothermal synthesis method. Vertically aligned arrays of dense and uniform zinc oxide (ZnO) nanowires (NWs) with high aspect ratio (diameter ∼250 nm, length ∼12 µm) were grown within nanoporous polycarbonate (PC) templates. The energy conversion efficiency was found to be ∼4.2%, which is comparable to previously reported values for ZnO NWs. The resulting NG is found to have excellent fatigue performance, being relatively immune to detrimental environmental factors and mechanical failure, as the constituent ZnO NWs remain embedded and protected inside the polymer matrix.

Controlled Ti seed layer assisted growth and field emission properties of Pb(Zr0.52Ti0.48)O3 nanowire arrays.

We report on the directed upright growth of ferroelectric (FE) Pb(Zr0.52Ti0.48)O3 (PZT) nanowire (NW) arrays with large aspect ratios of >60 using a Ti seed layer assisted hydrothermal process over large surface areas on ITO/glass substrates. In a two-step growth process, Ti seed layer of low surface roughness with a thickness of ~500 nm and grain size of ~100 nm was first deposited by radio frequency (RF) sputtering which was subsequently used as substrates for the growth of highly dense, single crystalline PZT NWs by controlled nucleation. The electron emission properties of the PZT NWs were investigated using the as-grown NWs as FE cathodes. A low turn-on field of ~3.4 V/µm was obtained from the NW arrays, which is impressively lower than that from other reported values. The results reported in this work give direction to the development of a facile growth technique for PZT NWs over large surfaces and also are of interest to the generation of high current electron beam from FE NW based cathodes for field emitter applications.

Solution-based synthesis and low-temperature transport properties of CsBi4Te6.

The thermoelectric material CsBi(4)Te(6) was synthesized in nanometer thin flake-like form by a low temperature solvothermal approach. The crystals were then densified by spark plasma sintering (SPS), resulting in a polycrystalline specimen with layered and partially orientated grains. The orientation of the CsBi(4)Te(6) flakes reflects the anisotropic crystal structure of the material aided by the unidirectional pressure during SPS. Hall, resistivity, Seebeck coefficient, and thermal conductivity was measured on the polycrystalline specimen in evaluating the potential of this approach for thermoelectric applications.

Controlled growth of well-aligned GaS nanohornlike structures and their field emission properties.

Here, we report the synthesis of vertically aligned gallium sulfide (GaS) nanohorn arrays using simple vapor-liquid-solid (VLS) method. The morphologies of GaS nano and microstructures are tuned by controlling the temperature and position of the substrate with respect to the source material. A plausible mechanism for the controlled growth has been proposed. It is important to note that the turn-on field value of GaS nanohorns array is found to be the low turn-on field 4.2 V/µm having current density of 0.1 µA/cm(2). The striking feature of the field emission behavior of the GaS nanohorn arrays is that the average emission current remains nearly constant over long time without any degradation.