Pramitha Vayalamkuzhi

Confined water layers in graphene oxide probed with spectroscopic ellipsometry

The confinement of water in quasi two-dimensional layers is intriguing because its physical properties can be significantly different when compared to those of the bulk fluid. This work describes spectroscopic ellipsometry study of confined water layers trapped between sheets of graphene oxide at varied thermal annealing temperatures. The wavelength-dependent refractive index of graphene oxide changes abruptly with annealing temperatures for Tann ≈ 125–160 °C, and we demonstrate that these changes are primarily governed by the expulsion of trapped water. This expulsion is associated with the decrease of interlayer separation of graphene oxide sheets from 7.8 A to 3.4 A. Graphene oxide annealed at high temperatures lacks trapped water layers and robust estimates of refractive index can be obtained within a Lorentz oscillator model. The trends in oscillator parameters are extended to lower annealing temperatures, where trapped water is present, in order to estimate the refractive index of confined water, wh...

Thickness-dependent Crack Propagation in Uniaxially Strained Conducting Graphene Oxide Films on Flexible Substrates

We demonstrate that crack propagation in uniaxially strained reduced graphene oxide (rGO) films is substantially dependent on the film thickness, for films in the sub-micron regime. rGO film on flexible polydimethylsiloxane (PDMS) substrate develop quasi-periodic cracks upon application of strain. The crack density and crack width follow contrasting trends as film thickness is increased and the results are described in terms of a sequential cracking model. Further, these cracks also have a tendency to relax when the strain is released. These features are also reflected in the strain-dependent electrical dc and ac conductivity studies. For an optimal thickness (3-coat), the films behave as strain-resistant, while for all other values it becomes strain-responsive, attributed to a favorable combination of crack density and width. This study of the film thickness dependent response and the crack propagation mechanism under strain is a significant step for rationalizing the application of layered graphene-like systems for flexible optoelectronic and strain sensing applications. When the thickness is tuned for enhanced extent of crack propagation, strain-sensors with gauge factor up to ∼470 are realized with the same material. When thickness is chosen to suppress the crack propagation, strain-resistive flexible TiO2- rGO UV photoconductor is realized.

Subwavelength transmission gratings for polarization separation in the infrared

Abstract. Subwavelength gratings exhibit attractive polarizing properties and have promising applications in communication, optical information processing, holography, and displays. The fabrication of subwavelength binary gratings for operation as polarizing beam splitters (PBS) at a wavelength of 1550 nm is presented. A simplified modal method was used for the design as well as to predict the efficiencies of the polarization components in each order. Electron beam lithography has been employed for patterning subwavelength grating structures on polymethyl methacrylate (PMMA) resist. The fixed beam moving stage patterning mode is used for patterning gratings with a period of 936 nm and width of 374 nm. The exposure and developing parameters are optimized to realize the grating with the designed feature sizes on PMMA resist. Gratings patterned using the optimized exposure and development parameters match well with the design, except for the height. The performance of the fabricated PBS grating has been evaluated by optical testing. The experimental results match well with the predictions.

Graphene: Polymer composites as moisture barrier and charge transport layer toward solar cell applications

Graphene: polymer composite based electrically conducting films are realized by a facile solution processable method. Ultraviolet Photoelectron Spectroscopy (UPS) measurements on the composite films, reveal a low work function of reduced graphene oxide (rGO) obtained from hydrazine hydrate reduction of graphene oxide (GO). We suggest that the low work function could potentially make rGO: PMMA composite suitable for electron conducting layer in perovskite solar cells in place of traditionally used expensive PCBM ([6,6]-phenyl-C61-butyric acid methyl ester) layer. Further, we demonstrate from the gravimetric experiments conducted on rGO: PMMA films, that the same coating is also resistant to moisture permeation. This latter property can be used to realize a protective coating layer for perovskite films, which are prone to moisture induced degradation. Thus, dual functionality of rGO-PMMA films is demonstrated towards integration with perovskite solar cells. Architecture of perovskite solar cell based on these concepts is proposed.Graphene: polymer composite based electrically conducting films are realized by a facile solution processable method. Ultraviolet Photoelectron Spectroscopy (UPS) measurements on the composite films, reveal a low work function of reduced graphene oxide (rGO) obtained from hydrazine hydrate reduction of graphene oxide (GO). We suggest that the low work function could potentially make rGO: PMMA composite suitable for electron conducting layer in perovskite solar cells in place of traditionally used expensive PCBM ([6,6]-phenyl-C61-butyric acid methyl ester) layer. Further, we demonstrate from the gravimetric experiments conducted on rGO: PMMA films, that the same coating is also resistant to moisture permeation. This latter property can be used to realize a protective coating layer for perovskite films, which are prone to moisture induced degradation. Thus, dual functionality of rGO-PMMA films is demonstrated towards integration with perovskite solar cells. Architecture of perovskite solar cell based on the...

Graphene interfaced perovskite solar cells: Role of graphene flake size

Graphene interfaced inverted planar heterojunction perovskite solar cells are fabricated by facile solution method and studied its potential as hole conducting layer. Reduced graphene oxide (rGO) with small and large flake size and Polyethylenedioxythiophene:polystyrene sulfonate (PEDOT:PSS) are utilized as hole conducting layers in different devices. For the solar cell employing PEDOT:PSS as hole conducting layer, 3.8 % photoconversion efficiency is achieved. In case of solar cells fabricated with rGO as hole conducting layer, the efficiency of the device is strongly dependent on flake size. With all other fabrication conditions kept constant, the efficiency of graphene-interfaced solar cell improves by a factor of 6, by changing the flake size of graphene oxide. We attribute this effect to uniform coverage of graphene layer and improved electrical percolation network.Graphene interfaced inverted planar heterojunction perovskite solar cells are fabricated by facile solution method and studied its potential as hole conducting layer. Reduced graphene oxide (rGO) with small and large flake size and Polyethylenedioxythiophene:polystyrene sulfonate (PEDOT:PSS) are utilized as hole conducting layers in different devices. For the solar cell employing PEDOT:PSS as hole conducting layer, 3.8 % photoconversion efficiency is achieved. In case of solar cells fabricated with rGO as hole conducting layer, the efficiency of the device is strongly dependent on flake size. With all other fabrication conditions kept constant, the efficiency of graphene-interfaced solar cell improves by a factor of 6, by changing the flake size of graphene oxide. We attribute this effect to uniform coverage of graphene layer and improved electrical percolation network.

Breakdown of water super-permeation in electrically insulating graphene oxide films: role of dual interlayer spacing

Conventional graphene oxide (GO) is characterized by low sp2 content in a sp3 rich matrix, which is responsible both for electrical insulation and water super-permeation. Upon reduction, electrical conduction is achieved at the expense of water permeation ability. Here, we demonstrate that charge conduction and water permeation can be simultaneously restricted in a functionalized form of GO. Gravimetric studies reveal that diffusion of water vapor through a glassy polymer membrane is arrested by loading a hydrophobic form of GO (H-GO) in the polymer matrix, even as such, water inhibition cannot be realized by substantially increasing the thickness of the bare polymer. As an application, the ability of the coating to impede the degradation of methyl ammonium lead iodide films under high humidity conditions is demonstrated. At the same time the H-GO film has a resistance over 107 times higher when compared to thermally reduced GO of similar sp2 fraction. We attribute this unique behavior to the presence of a sub-micron matrix of GO with simultaneous presence of large (∼9.5 Å) and small (∼4.7 Å) interlayer spacing. This leads to disruption of the spatially distributed percolation pathways for electrical charge, and it also serves to block the nanocapillary networks for water molecules.

Anomalous charge transport in reduced graphene oxide films on a uniaxially strained elastic substrate

We investigate temperature-dependent charge transport in reduced graphene oxide (rGO) films coated on flexible polydimethylsiloxane (PDMS) substrates which are subject to uniaxial strain. Variable strain, up to 10%, results in an anisotropic morphology comprising of quasi-periodic linear array of deformations which are oriented perpendicular to the direction of strain. The anisotropy is reflected in the charge transport measurements, when conduction in the direction parallel and perpendicular to the applied strain are compared. Temperature dependence of resistance is measured for different values of strain in the temperature interval 80-300 K. While the resistance increases significantly upon application of strain, the temperature-dependent response shows anomalous decrease in resistance ratio R 80 K/R 300 K upon application of strain. This observation of favorable conduction processes under strain is further corroborated by reduced activation energy analysis of the temperature-dependent transport data. These anomalous transport features can be reconciled based on mutually competing effects of two processes: (i) thinning of graphene at the sites of periodic deformations, which tends to enhance the overall resistance by a purely geometrical effect, and (ii) locally enhanced inter-flake coupling in these same regions which contributes to improved temperature-dependent conduction.