Parag Banerjee

Nanotubular metal-insulator-metal capacitor arrays for energy storage

Nanostructured devices have the potential to serve as the basis for next-generation energy systems that make use of densely packed interfaces and thin films. One approach to making such devices is to build multilayer structures of large area inside the open volume of a nanostructured template. Here, we report the use of atomic layer deposition to fabricate arrays of metal-insulator-metal nanocapacitors in anodic aluminium oxide nanopores. These highly regular arrays have a capacitance per unit planar area of approximately 10 microF cm-2 for 1-microm-thick anodic aluminium oxide and approximately 100 microF cm-2 for 10-microm-thick anodic aluminium oxide, significantly exceeding previously reported values for metal-insulator-metal capacitors in porous templates. It should be possible to scale devices fabricated with this approach to make viable energy storage systems that provide both high energy density and high power density.

Structural, electrical, and optical properties of atomic layer deposition Al-doped ZnO films

Al-doped ZnO (AZO) films of ∼100 nm thickness with various Al doping were prepared at 150 °C by atomic layer deposition on quartz substrates. At low Al doping, the films were strongly textured along the [100] direction, while at higher Al doping the films remained amorphous. Atomic force microscopy results showed that Al–O cycles when inserted in a ZnO film, corresponding to a few atomic percent Al, could remarkably reduce the surface roughness of the films. Hall measurements revealed a maximum mobility of 17.7 cm2/V s. Film resistivity reached a minima of 4.4×10−3 Ω cm whereas the carrier concentration reached a maxima of 1.7×1020 cm−3, at 3 at. % Al. The band gap of AZO films varied from 3.23 eV for undoped ZnO films to 3.73 eV for AZO films with 24.6 at. % Al. Optical transmittance over 80% was obtained in the visible region. The detrimental impact of increased Al resulting in decreased conductivity due to doping past 3.0 at. % is evident in the x-ray diffraction data, as an abrupt increase in the opti...

Plasmon-induced electrical conduction in molecular devices.

Metal nanoparticles (NPs) respond to electromagnetic waves by creating surface plasmons (SPs), which are localized, collective oscillations of conduction electrons on the NP surface. When interparticle distances are small, SPs generated in neighboring NPs can couple to one another, creating intense fields. The coupled particles can then act as optical antennae capturing and refocusing light between them. Furthermore, a molecule linking such NPs can be affected by these interactions as well. Here, we show that by using an appropriate, highly conjugated multiporphyrin chromophoric wire to couple gold NP arrays, plasmons can be used to control electrical properties. In particular, we demonstrate that the magnitude of the observed photoconductivity of covalently interconnected plasmon-coupled NPs can be tuned independently of the optical characteristics of the molecule-a result that has significant implications for future nanoscale optoelectronic devices.

High to ultra-high power electrical energy storage

High power electrical energy storage systems are becoming critical devices for advanced energy storage technology. This is true in part due to their high rate capabilities and moderate energy densities which allow them to capture power efficiently from evanescent, renewable energy sources. High power systems include both electrochemical capacitors and electrostatic capacitors. These devices have fast charging and discharging rates, supplying energy within seconds or less. Recent research has focused on increasing power and energy density of the devices using advanced materials and novel architectural design. An increase in understanding of structure-property relationships in nanomaterials and interfaces and the ability to control nanostructures precisely has led to an immense improvement in the performance characteristics of these devices. In this review, we discuss the recent advances for both electrochemical and electrostatic capacitors as high power electrical energy storage systems, and propose directions and challenges for the future. We asses the opportunities in nanostructure-based high power electrical energy storage devices and include electrochemical and electrostatic capacitors for their potential to open the door to a new regime of power energy.

TEM-based metrology for HfO2 layers and nanotubes formed in anodic aluminum oxide nanopore structures.

Nanotubes are fabricated by atomic layer deposition (ALD) into nanopore arrays created by anodic aluminum oxide (AAO). A transmission electron microscopy (TEM) methodology is developed and applied to quantify the ALD conformality in the nanopores (thickness as a function of depth), and the results are compared to existing models for ALD conformality. ALD HfO2 nanotubes formed in AAO templates are released by dissolution of the Al2O3, transferred to a grid, and imaged by TEM. An algorithm is devised to automate the quantification of nanotube wall thickness as a function of position along the central axis of the nanotube, by using a cylindrical model for the nanotube. Diffusion-limited depletion occurs in the lower portion of the nanotubes and is characterized by a linear slope of decreasing thickness. Experimentally recorded slopes match well with two simple models of ALD within nanopores presented in the literature. The TEM analysis technique provides a method for the rapid analysis of such nanostructures in general, and is also a means to efficiently quantify ALD profiles in nanostructures for a variety of nanodevice applications.

MnO2/TiN heterogeneous nanostructure design for electrochemical energy storage

MnO(2)/TiN nanotubes are fabricated using facile deposition techniques to maximize the surface area of the electroactive material for use in electrochemical capacitors. Atomic layer deposition is used to deposit conformal nanotubes within an anodic aluminium oxide template. After template removal, the inner and outer surfaces of the TiN nanotubes are exposed for electrochemical deposition of manganese oxide. Electron microscopy shows that the MnO(2) is deposited on both the inside and outside of TiN nanotubes, forming the MnO(2)/TiN nanotubes. Cyclic voltammetry and galvanostatic charge-discharge curves are used to characterize the electrochemical properties of the MnO(2)/TiN nanotubes. Due to the close proximity of MnO(2) with the highly conductive TiN as well as the overall high surface area, the nanotubes show very high specific capacitance (662 F g(-1) reported at 45 A g(-1)) as a supercapacitor electrode material. The highly conductive and mechanically stable TiN greatly enhances the flow of electrons to the MnO(2) material, while the high aspect ratio nanostructure of TiN creates a large surface area for short diffusion paths for cations thus improving high power. Combining the favourable structural, electrical and energy properties of MnO(2) and TiN into one system allows for a promising electrode material for supercapacitors.

Surface engineered CuO nanowires with ZnO islands for CO2 photoreduction.

Large arrays of massively parallel (10(8) cm(-2)) CuO nanowires were surface engineered with dense ZnO islands using a few pulsed cycles of atomic layer deposition (ALD). These nanowires were subjected to UV-vis radiation-based CO2 photoreduction under saturated humidity (CO2 + H2O mixture) conditions. We monitored CO2 to CO conversion, indicating the viability of these nanostructures as potential photocatalysts. High-resolution transmission electron microscopy and atomic force microscopy indicated an island growth mechanism of ZnO epitaxially depositing on pristine, single crystal CuO nanowire surface. Photoluminescence and transient absorption spectroscopy showed a very high density of defects on these ZnO islands which trapped electrons and enhanced their lifetimes. Peak CO conversion (1.98 mmol/g-cat/hr) and quantum efficiency (0.0035%) were observed in our setup when the ZnO islands impinged each other at 1.4 nm (8 cycles of ALD) diameter; at which point ZnO island perimeter lengths maximized as well. A mechanism whereby simultaneous H2O oxidation and CO2 reduction occurred in the active perimeter region between CuO nanowire and ZnO islands is proposed to explain the observed photoconversion of CO2 to CO.

Profile Evolution for Conformal Atomic Layer Deposition over Nanotopography

The self-limiting reactions which distinguish atomic layer deposition (ALD) provide ultrathin film deposition with superb conformality over the most challenging topography. This work addresses how the shapes (i.e., surface profiles) of nanostructures are modified by the conformality of ALD. As a nanostructure template, we employ a highly scalloped surface formed during the first anodization of the porous anodic alumina (PAA) process, followed by removal of the alumina to expose a scalloped Al surface. SEM and AFM reveal evolution of surface profiles that change with ALD layer thickness, influenced by the way ALD conformality decorates the underlying topography. The evolution of surface profiles is modeled using a simple geometric 3D extrusion model, which replicates the measured complex surface topography. Excellent agreement is obtained between experimental data and the results from this model, suggesting that for this ALD system conformality is very high even on highly structured, sharp features of the initial template surface. Through modeling and experimentation, the benefits of ALD to manipulate complex surface topographies are recognized and will play an important role in the design and nanofabrication of next generation devices with increasingly high aspect ratios as well as nanoscale features.

Star-shaped hole transport materials with indeno[1,2-b] thiophene or fluorene on a triazine core for efficient perovskite solar cells

New star-shaped hole transport materials including a 1,3,5-triazine core have been successfully synthesized and investigated for high performance perovskite solar cells. A maximum power conversion efficiency of 13.2% has been achieved by employing 2,2′,2′′-(1,3,5-triazine-2,4,6-triyl)tris(N,N-bis(4-methoxyphenyl)-4,4-dimethyl-4H-indeno[1,2-b]thiophen-6-amine). The power conversion efficiencies of hole transport materials were comparable to that of the standard spiro-OMeTAD (13.8%).

Unravelling transient phases during thermal oxidation of copper for dense CuO nanowire growth

Direct evidence of cupric ion outdiffusion through grain boundaries during thermal oxidation of high purity Cu is obtained using Raman spectroscopy. This diffusion feeds the growth of CuO nanowires on the surface while forming a Cu1+xO phase in the grain boundaries of the underlying Cu2O film. On complete Cu consumption, counter indiffusion of O2− ions converts the entire structure to a CuO film, while viable CuO nanowires still remain on the surface.