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Coconut shell derived mesoporous carbon (CS-AC) is explored as prospective supercapacitor component in Li-ion and Na-ion capacitors (LIC and NIC) along with pre-lithiated/sodiated natural plant derived hard carbon (HC) as battery element. Though, there is no obvious variation from the capacitive properties of CS-AC, but an obvious difference is evident for battery component in single electrode configuration. Based on such performance, the mass loading has been adjusted during the fabrication of LIC and NIC. Prior to this, HC is pre-lithiated/sodiated for LIC/NIC assembly. The CS-AC and pre-treated HC based materials registered the maximum energy density of ∼121 and ∼82 Wh kg−1 for LIC and NIC assemblies, respectively. An excellent long-term cycleability of ∼83% retention is noted for LIC after 8000 cycles, whereas NIC showed inferior performance (∼60%) under similar testing conditions. Multilayer surface film is the main reason for such performance which has been clearly revealed from the impedance measurements. First, the CS-AC is prepared by hydrothermal carbonization and subsequent chemical activation with ZnCl2 to yield high specific surface area and pore volume of 1795 m2 g−1 and 2.2 cm3 g−1, respectively, in which 71% originated from mesoporous region.

Oxide-free silicon chemistry has been widely studied using wet-chemistry methods, but for emerging applications such as molecular electronics on silicon, nanowire-based sensors, and biochips, these methods may not be suitable as they can give rise to defects due to surface contamination, residual solvents, which in turn can affect the grafted monolayer devices for practical applications. Therefore, there is a need for a cleaner, reproducible, scalable, and environmentally benign monolayer grafting process. In this work, monolayers of alkylthiols were deposited on oxide-free semiconductor surfaces using supercritical carbon dioxide (SCCO2) as a carrier fluid owing to its favorable physical properties. The identity of grafted monolayers was monitored with Fourier transform infrared (FTIR) spectroscopy, high-resolution X-ray photoelectron spectroscopy (HRXPS), XPS, atomic force microscopy (AFM), contact angle measurements, and ellipsometry. Monolayers on oxide-free silicon were able to passivate the surface for more than 50 days (10 times than the conventional methods) without any oxide formation in ambient atmosphere. Application of the SCCO2 process was further extended by depositing alkylthiol monolayers on fragile and brittle 1D silicon nanowires (SiNWs) and 2D germanium substrates. With the recent interest in SiNWs for biological applications, the thiol-passivated oxide-free silicon nanowire surfaces were also studied for their biological response. Alkylthiol-functionalized SiNWs showed a significant decrease in cell proliferation owing to their superhydrophobicity combined with the rough surface morphology. Furthermore, tribological studies showed a sharp decrease in the coefficient of friction, which was found to be dependent on the alkyl chain length and surface bond. These studies can be used for the development of cost-effective and highly stable monolayers for practical applications such as solar cells, biosensors, molecular electronics, micro- and nano- electromechanical systems, antifouling agents, and drug delivery.

Polymers capable of forming hydration layers have gained increasing attention due to their ability to form environmentally friendly antifouling surfaces. Zwitterionic polymers are an important class of materials under this category. However, the effectiveness of many zwitterionic polymers for long-term applications is compromised because of their solubility in sea water, poor hydrolytic stability and deteriorating mechanical integrity upon wetting. This study reports on the preparation and characterization of electrospun fibers derived from novel polysulfobetaine and polysulfabetaines (PSBs) composed of polyvinylbenzyl backbones. The morphology of the electrospun nanofibers was elucidated with the help of a scanning electron microscope. Hydration studies were conducted in deionized water and artificial sea water. Antifouling performance of the electrospun nanofibers was evaluated by studying the adhesion and growth of bacteria in natural, and filtered sea water. Terminal restriction fragment length polymorphism (TRFLP) fingerprinting was performed to determine the nature of the bacterial community attached to the electrospun fibers. Some of the PSBs prevented bacterial growth without showing any biocidal nature. Thus the findings of this study are potentially relevant for current trends seeking environmentally friendly antifouling solutions.

We demonstrated the functionalization of one dimensional (1-D) zinc oxide nanorods (ZnO NRs) using bi-functional organic molecules to create hybrid structures with surface functionalities and tuneable organic/inorganic interface. Bi-functional molecules with carboxylic acid, thiol and silane end groups and amine termination had been employed to functionalize the NRs by forming carboxylate, thiolate and hydroxylation bonds, respectively, with ZnO. The surface textures of NRs were preserved even after functionalization. The functionalized NRs were decorated with gold nanoparticles (AuNPs) and the hybrid structures exhibited a quenched blue shift ultraviolet emission which depended on the distance between the ZnO surface and the AuNPs. The NR functionalization with bi-functional molecules and decoration of NPs, and surface morphologies were analyzed using x-ray photoelectron spectroscopy, field emission scanning electron microscopy and transmission electron spectroscopy. These hybrid structures can play a vital role in tuning the interface properties and have potential applications in future photovoltaics, chemical sensors, biomarkers, and wavelength based biosensors. Refereed/Peer-reviewed

We first report the possibility of using spinel LiNi0.5Mn1.5O4 (LNM) nanofibers as cathode for constructing high (∼3.2 V) and low (∼1.2 V) voltage “rocking-chair” type Li-ion cells with spinel Li4Ti5O12 (LTO) by utilizing Li-insertion into tetrahedral (Ni2+/4+) and octahedral (Mn4+/3+) sites of LNM. We also explored the possibility of constructing symmetric cells (LNM/LNM) with a working potential of ∼1.8 V. Among the three configurations investigated, LNM/LTO (electrochemically prelithiated) is found superior in terms of high rate capability, cyclability, and good capacity retention characteristics. High performance spinel LNM nanofibers are prepared via a scalable electrospinning technique and their Li-insertion properties are evaluated in half-cell assembly. The half-cell studies are used for adjusting the mass balance while fabricating “rocking-chair” Li-ion cells.

Formation of dense monolayers with proven atmospheric stability using simple fabrication conditions remains a major challenge for potential applications such as (bio)sensors, solar cells, surfaces for growth of biological cells, and molecular, organic, and plastic electronics. Here, we demonstrate a single-step modification of organophosphonic acids (OPA) on 1D and 2D structures using supercritical carbon dioxide (SCCO2) as a processing medium, with high stability and significantly shorter processing times than those obtained by the conventional physisorption-chemisorption method (2.5 h vs 48-60 h).The advantages of this approach in terms of stability and atmospheric resistivity are demonstrated on various 2D materials, such as indium-tin-oxide (ITO) and 2D Si surfaces. The advantage of the reported approach on electronic and sensing devices is demonstrated by Si nanowire field effect transistors (SiNW FETs), which have shown a few orders of magnitude higher electrical and sensing performances, compared with devices obtained by conventional approaches. The compatibility of the reported approach with various materials and its simple implementation with a single reactor makes it easily scalable for various applications.

Oxide-free Si and Ge surfaces have been passivated and modified with organic molecules by forming covalent bonds between the surfaces and reactive end groups of linear alkanes and aromatic species using single-step deposition in supercritical carbon dioxide (SCCO2). The process is suitable for large-scale manufacturing due to short processing times, simplicity, and high resistance to oxidation. It also allows the formation of monolayers with varying reactive terminal groups, thus enabling formation of nanostructures engineered at the molecular level. Ballistic electron emission microscopy (BEEM) spectra performed on the organic monolayer on oxide-free silicon capped by a thin gold layer reveals for the first time an increase in transmission of the ballistic current through the interface of up to three times compared to a control device, in contrast to similar studies reported in the literature suggestive of oxide-free passivation in SCCO2. The SCCO2 process combined with the preliminary BEEM results opens up new avenues for interface engineering, leading to molecular electronic devices.

A wide range of new materials for many applications can be formed by controlling the composition and order of constituents at the molecular level. For systems thus engineered, ensuring chemical, thermal and mechanical robustness is a major challenge. Consequently, polyimides and other imide-containing materials are attractive as matrices for functional materials. We investigate the construction of functional nanostructures in organic/polymeric matrices with clearly demonstrated chemical, thermal and mechanical stability. Surface functionalization, layer-by-layer (LBL) assembly in various media (including supercritical), incorporation of functional moieties, molecular orientation, and interfacial reactions are areas of interest. We demonstrate the robustness of ultrathin film structures containing polyimides and oligoimides formed by LBL molecular assembly with inter-layer covalent links. Covalent bonding between the layers provides strength, while utilizing a supercritical medium for the processing, results in the deployment of a solvent-free environment and avoids problems related to residual solvent, thereby improving film quality when compared to conventional films.

In the present work, vertical ZnO nanorods (NRs) were grown onto ITO substrates by a simple two step chemical process at relatively low temperature by using successive ionic layer absorption and reaction method (SILAR) and chemical bath deposition (CBD) method. The investigated on n- ZnO/ p-Polythiophene heterojunction device have been fabricated with ZnO nanorods. Structural analysis reveals that the grown ZnO NRs exhibit (002) reflection with higher intensity, indicating that the ZnO NRs grown in c-axis orientation. FESEM image shows the surface morphology of grown ZnO nanorods was of hexagonal wurtzite structure whose diameter varies from 200 nm to 1μm. Room temperature Photoluminescence exhibited strong UV emission at ∼386 nm and a negligible green band confirms the presence of very low concentration of oxygen vacancies in the well-aligned ZnO nanorods. The current–voltage (I –V) characteristics of the heterojunctions show good rectifying diode characteristics. These results indicate that hybrid device fabricated from solution process is a promising approach for future light-emitting diodes (LEDs) devices.

Prelithiated, electrospun α-Fe2O3 nanofibers display an exceptional cycleability when it is paired with commercial LiMn2O4 cathode in full-cell assembly. The performance of such α-Fe2O3 nanofibers is mainly due to the presence of unique morphology with porous structure, appropriate mass balance, and working potential. Also, synthesis technique cannot be ruled out for the performance. NRF (Natl Research Foundation, S’pore) Published version

We report for the first time the synthesis and extraordinary performance of a high voltage spinel LiNi(0.5)Mn(1.5)O4 fiber cathode in all one dimensional (1D) architecture. Structural and morphological features are analyzed by various characterization techniques. Li-insertion/extraction properties are evaluated in a half-cell assembly (Li/LiNi(0.5)Mn(1.5)O4) and subsequently in full-cell configuration with an anatase TiO2 fiber anode. In both half- and full-cell assemblies, gelled polyvinylidene fluoride-co-hexafluoropropylene (PVdF-HFP) is used as the separator-cum-electrolyte. All the one dimensional components used for fabricating Li-ion cells are prepared by a simple and scalable electrospinning technique. The full-cell, LiNi(0.5)Mn(1.5)O4/gelled PVdF-HFP/TiO2 delivered the reversible capacity of ∼ 102 mA h g(-1) at 0.1 C rate with an operating potential of ∼ 2.8 V. Excellent rate capability and stable cycling profiles are noted for such a full-cell assembly with a capacity retention of ∼ 86% after 400 cycles.

In this work, we demonstrate a facile method for fabricating hybrid organic/inorganic structures of vertically oriented 1-dimensional (1-D) ZnO nanorods (NR) coupled with regio-regular poly(3-(2-methoxyethoxy) ethoxymethyl) thiophene-2,5-diyl (PMEEMT). The NRs were synthesized by two-step solution processes and exhibited a hexagonal wurtzite structure with a lattice spacing of 0.248 nm. Cross-section analysis of field-emission scanning electron microscopy (FESEM) analysis confirmed the NRs were vertically oriented and densely packed with diameter of about 250 nm. The hybrid structures were formed by encapsulating the ZnO NRs with polythiophenes, thereby creating a direct heterojunction interface. These interfaces allowed easy electron transport along the NR avoiding loss of mobility due to grain boundary scattering; further, the large aspect ratio and surface area of NR increased the effective interface between polythiophene and the nanorods contributing to efficient charge separation. In addition, decoration of the ZnO hybrid structures by gold nanoparticles (AuNPs) induced enhanced luminescence properties. These functionalized organic/inorganic hybrid structures can pave the way for applications in photovoltaics and sensing. Refereed/Peer-reviewed

Inverted bulk heterojunction organic solar cells having device structure ITO/ZnO/poly(3-hexylthiophene) (P3HT):[6,6]-phenyl C61 butyric acid methyl ester (PCBM) /MoO3/Ag were fabricated with high photoelectric conversion efficiency and stability. Three types of devices were developed with varying electron transporting layer (ETL) ZnO architecture. The ETL in the first type was a sol-gel-derived particulate film of ZnO, which in the second and third type contained additional ZnO nanowires of varying concentrations. The length of the ZnO nanowires, which were developed by the electrospinning technique, extended up to the bulk of the photoactive layer in the device. The devices those employed a higher loading of ZnO nanowires showed 20% higher photoelectric conversion efficiency (PCE), which mainly resulted from an enhancement in its fill factor (FF). Charge transport characteristic of the device were studied by transient photovoltage decay and charge extraction by linearly increasing voltage techniques. Results show that higher PCE and FF in the devices employed ZnO nanowire plantations resulted from improved charge collection efficiency and reduced recombination rate. Refereed/Peer-reviewed

We report the extraordinary lithium storage performance of porous LiMn2O4 hollow nanofibers synthesized by electrospinning technique. The electrospun LiMn2O4 hollow nanofibers retained 87% of initial reversible capacity after 1250 cycles at the 1 C rate. Further, excellent cycling profiles at 55 °C and cubic spinel to tetragonal phase transformation are also noted.

We report a facile and simple means of synthesizing a macroscopic array of ZnO nanorods with high feature densities using a modified hydrothermal approach that involves the in situ introduction of polyelectrolyte. The ZnO nanorod arrays with heights of 1.5 μm and diameters of 350 nm were consistently reproducible and were bestowed with the advantage of in situ process tunability offered by employing polyethylenimine (PEI) as a surface modifying agent. The fabrication combines benefits from the hydrothermal approach in terms of process simplicity and flexibility and from the use polyelectrolyte that offers a better nanorod surface, quenched defect levels and enhancement of the UV band edge emission. Structural and elemental analysis of the PEI-modified and unmodified nanorods emphasize the fact that the intentional introduction of PEI results in a nanorod with better surface quality as evidenced by photoluminescence (PL) spectra. The tunability of the feature dimensions of the nanorods and an analysis of the bulk and surface (surface defect) responses to the PL point to significant promise of high density orthogonal nanorods in a number of optoelectronic applications. While the defects in the ZnO nanorods can point towards the application of ZnO nanorods in charge trap flash memory devices, highly crystalline, size tunable, high aspect ratio nanorods find applications as building components in solid state lighting.

In this work, we demonstrate a simple method of synthesizing nanoscale polythiophene-gold nanoparticle (AuNP) hybrid systems assembled by the Langmuir-Blodgett (LB) method. Regio-regular poly(3-(2-methoxyethoxy)ethoxymethyl)thiophene-2,5-diyl (PMEEMT) and poly(3-dodecylthiophene) (PDDT) were employed as the polymeric constituents. The presence of PDDT improved the amphiphilicity of PMEEMT by addressing the phase separation that occurred due to convective hydrodynamic instability on the substrate. 4 layer stacks of 90% and 99% PMEEMT films exhibited uniform film structure with a significant reduction in phase separation. A detailed mechanism for minimization of the surface effect has been proposed based on the interaction of polythiophenes with the substrate. For the first time, an ex situ approach has been adopted to incorporate AuNPs into LB films without affecting the film morphology and uniformity. The incorporation of AuNPs into the polythiophene matrix, aided by the affinity of sulphur for gold, was strongly dependent on the molecular arrangement of the matrix, which in turn depended on the composition of the matrix. The hybrid polythiophene films exhibited enhanced conductivity and can be applied in sensors, photovoltaics and memory devices.