Narendra Kurra

All-MXene (2D titanium carbide) solid-state microsupercapacitors for on-chip energy storage

On-chip energy storage is a rapidly evolving research topic, opening doors for the integration of batteries and supercapacitors at the microscale on rigid and flexible platforms. Recently, a new class of two-dimensional (2D) transition metal carbides and nitrides (so-called MXenes) has shown great promise in electrochemical energy storage applications. Here, we report the fabrication of all-MXene (Ti3C2Tx) solid-state interdigital microsupercapacitors by employing a solution spray-coating method, followed by a photoresist-free direct laser cutting method. Our prototype devices consisted of two layers of Ti3C2Tx with two different flake sizes. The bottom layer was stacked large-size MXene flakes (lateral dimensions of 3–6 μm) serving mainly as current collectors. The top layer was made of small-size MXene flakes (∼1 μm) with a large number of defects and edges as the electroactive layer responsible for energy storage. Compared to Ti3C2Tx micro-supercapacitors with platinum current collectors, the all-MXene devices exhibited a much lower contact resistance, higher capacitances and better rate-capabilities. Areal and volumetric capacitances of ∼27 mF cm−2 and ∼357 F cm−3, respectively, at a scan rate of 20 mV s−1 were achieved. The devices also demonstrated excellent cyclic stability, with 100% capacitance retention after 10 000 cycles at a scan rate of 50 mV s−1. This study opens up a plethora of possible designs for high-performance on-chip devices employing different chemistries, flake sizes and morphologies of MXenes and their heterostructures.

Field effect transistors and RC filters from pencil-trace on paper

We report the fabrication of Resistor-Capacitor (RC) filters and field effect transistors (FETs) based on pencil drawings on paper, which contain turbostratic graphite crystallites as evidenced from Raman analysis. Pencil drawings have been employed as resistor and an ion gel, 1-butyl-3-methylimidazolium octyl sulfate mixed with polydimethylsiloxane (PDMS) as dielectric, for the fabrication of RC filters with a cut-off frequency of 9 kHz. With ion gel as gate dielectric, an ambipolar electric field effect has been obtained from the pencil-trace at low operating voltages. The carrier mobilities were found to be ∼106 and 59 cm(2) V(-1) s(-1) for holes and electrons, respectively. The mobility value showed only 15% variation among the devices tested, truly remarkable given the simplicity of the fabrication process.

All conducting polymer electrodes for asymmetric solid-state supercapacitors

In this study, we report the fabrication of solid-state asymmetric supercapacitors (ASCs) based on conducting polymer electrodes on a plastic substrate. Nanostructured conducting polymers of poly(3,4-ethylenedioxythiophene), PEDOT, and polyaniline (PANI) are deposited electrochemically over Au-coated polyethylene naphthalate (PEN) plastic substrates. Due to the electron donating nature of the oxygen groups in the PEDOT, reduction potentials are higher, allowing it to be used as a negative electrode material. In addition, the high stability of PEDOT in its oxidised state makes it capable to exhibit electrochemical activity in a wide potential window. This can qualify PEDOT to be used as a negative electrode in fabricating asymmetric solid state supercapacitors with PANI as a positive electrode while employing polyvinyl alcohol (PVA)/H2SO4 gel electrolyte. The ASCs exhibit a maximum power density of 2.8 W cm−3 at an energy density of 9 mW h cm−3, which is superior to the carbonaceous and metal oxide based ASC solid state devices. Furthermore, the tandem configuration of asymmetric supercapacitors is shown to be capable of powering a red light emitting diode for about 1 minute after charging for 10 seconds.

A conducting polymer nucleation scheme for efficient solid-state supercapacitors on paper

In this study, a thin nucleation layer is used to tune the morphology of conducting polymer electrodes and to optimize the performance of paper based solid-state supercapacitors. It is found that using an acid-treated poly(3,4-ethylenedioxythiophene):polystyrenesulfonate (PEDOT:PSS) nucleation layer, prior to poly(3,4-ethylenedioxythiophene), PEDOT, electrochemical deposition, gives 5–6 times higher areal capacitance compared to a gold metal nucleation layer. Specifically, PEDOT supercapacitors with a high volumetric capacitance of 327 F cm−3, higher than any other PEDOT based supercapacitors reported in the literature, is achieved on the PEDOT:PSS nucleation layer; for the same devices, an areal capacitance of 242 mF cm−2 and an energy density of 14.5 mW h cm−3 at a power density of 350 mW cm−3 are obtained. Furthermore, these optimized PEDOT/PEDOT:PSS/paper electrodes are employed to fabricate solid-state supercapacitors using aqueous and ion gel electrolytes, with 32 and 11 mF cm−2 cell capacitance, respectively. The solid-state PEDOT device showed an energy density of 1.5 mW h cm−3 (normalised to the volume of the whole cell, including both the electrodes and the electrolyte), which is higher than the best reported ppy/paper (E = 1 mW h cm−3) and PAni/pencil/paper (E = 0.32 mW h cm−3) solid-state devices. The cycling performance showed that capacitance retention up to 80% is achieved after 10000 cycles.

Charge storage in mesoscopic graphitic islands fabricated using AFM bias lithography

Electrochemical oxidation and etching of highly oriented pyrolytic graphite (HOPG) has been achieved using biased atomic force microscopy (AFM) lithography, allowing patterns of varying complexity to be written into the top layers of HOPG. The graphitic oxidation process and the trench geometry after writing were monitored using intermittent contact mode AFM. Electrostatic force microscopy reveals that the isolated mesoscopic islands formed during the AFM lithography process become positively charged, suggesting that they are laterally isolated from the surrounding HOPG substrate. The electrical transport studies of these laterally isolated finite-layer graphitic islands enable detailed characterization of electrical conduction along the c-direction and reveal an unexpected stability of the charged state. Utilizing conducting-atomic force microscopy, the measured I(V) characteristics revealed significant non-linearities. Micro-Raman studies confirm the presence of oxy functional groups formed during the lithography process.

Nanocarbon-Scanning Probe Microscopy Synergy: Fundamental Aspects to Nanoscale Devices

Scanning probe techniques scanning tunneling microscopy (STM) and atomic force microscopy (AFM) have emerged as unique local probes for imaging, manipulation, and modification of surfaces at the nanoscale. Exercising the fabrication of atomic and nansocale devices with desired properties have demanded rapid development of scanning probe based nanolithographies. Dip pen nanolithography (DPN) and local anodic oxidation (LAO) have been widely employed for fabricating functional patterns and prototype devices at nanoscale. This review discusses the progress in AFM bias lithography with focus on nanocarbon species on which many functional quantum device structures have been realized using local electrochemical and electrostatic processes. As water meniscus is central to AFM bias lithography, the meniscus formation, estimation and visualization is discussed briefly. A number of graphene-based nanodevices have been realized on the basis AFM bias lithography in the form of nanoribbons, nanorings and quantum dots with sufficiently small dimensions to show quantum phenomena such as conductance fluctuations. Several studies involving graphitic surfaces and carbon nanotubes are also covered. AFM based scratching technique is another promising approach for the fabrication of nanogap electrodes, important in molecular electronics.

Enhanced high temperature thermoelectric response of sulphuric acid treated conducting polymer thin films

We report the high temperature thermoelectric properties of solution processed untreated and sulphuric acid treated poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (or PEDOT:PSS) films. The acid treatment is shown to simultaneously enhance the electrical conductivity and the Seebeck coefficient of the metal-like films, resulting in a five-fold increase in the thermoelectric power factor (from 0.01 to 0.052 W m−1 K−1) at 460 K, compared to the untreated film. By using atomic force micrographs, Raman and impedance spectra and using a series heterogeneous model for electrical conductivity, we demonstrate that acid treatment results in the removal of PSS from the films, leading to the quenching of accumulated charge-induced energy barriers, facilitating metal-like conduction. The continuous removal of PSS and changes in morphology of the PEDOT grains upon acid treatment may alter the local band structure of PEDOT:PSS, in such a way as to simultaneously enhance the Seebeck coefficient.

A two-step annealing process for enhancing the ferroelectric properties of poly(vinylidene fluoride) (PVDF) devices

We report a simple two-step annealing scheme for the fabrication of stable non-volatile memory devices employing poly(vinylidene fluoride) (PVDF) polymer thin-films. The proposed two-step annealing scheme comprises the crystallization of the ferroelectric gamma-phase during the first step and enhancement of the PVDF film dense morphology during the second step. Moreover, when we extended the processing time of the second step, we obtained good hysteresis curves down to 1 Hz, the first such report for ferroelectric PVDF films. The PVDF films also exhibit a coercive field of 113 MV m−1 and a ferroelectric polarization of 5.4 μC cm−2.

Micro-Pseudocapacitors with Electroactive Polymer Electrodes: Toward AC-Line Filtering Applications

In this study, we investigate the frequency response of micro-pseudocapacitors based on conducting polymer electrodes such as poly(3,4-ethylenedioxythiophene) (PEDOT), polypyrrole, and polyaniline. It is shown that by proper choice of polymeric material and device structure, miniaturized micro-pseudocapacitors can match the frequency response of commercial bulky electrolytic capacitors. Specifically, we show that PEDOT-based micro-pseudocapacitors exhibit phase angle of -80.5° at 120 Hz, which is comparable to commercial bulky electrolytic capacitors, but with an order of magnitude higher capacitance density (3 FV/cm(3)). The tradeoff between the areal capacitance (CA) and frequency response in the two-dimensional architecture (CA = 0.15 mF/cm(2), phase angle of -80.5° at 120 Hz) is improved by designing three-dimensional thin-film architecture (CA = 1.3 mF/cm(2), phase angle of -60° at 120 Hz). Our work demonstrates that fast frequency response can be achieved using electroactive polymer electrodes.

Field-Effect Transistors Based on Thermally Treated Electron Beam-Induced Carbonaceous Patterns

Electron beam-induced carbonaceous deposition (EBICD) derived from residual hydrocarbons in the vacuum chamber has many fascinating properties. It is known to be chemically complex but robust, structurally amorphous, and electrically insulating. The present study is an attempt to gain more insight into its chemical and electrical nature based on detailed measurements such as Raman, XPS, TEM, and electrical. Interestingly, EBIC patterns are found to be blue fluorescent when excited with UV radiation, a property which owes much to sp(2) carbon clusters amidst sp(3) matrix. Temperature-dependent Raman and electrical measurements have confirmed the graphitization of the EBICD through the decomposition of functional groups above 300 °C. Finally, graphitized EBIC patterns have been employed as active p-type channel material in the field-effect transistors to obtain mobilities in the range of 0.2-4 cm(2)/V s.