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Kaul, Anupama B.

Publications and source records attributed to Kaul, Anupama B..

At least 19 records

Solution-processed tungsten diselenide as an inorganic hole transport material for moisture-stable perovskite solar cells in the n-i-p architecture

Some of the obstacles to the commercialization of perovskite solar cells (PSCs) are their long-term moisture stability and material cost of the constituent layers, such as the commonly used spiro-OMeTAD hole transport layer (HTL). Replacing the spiro-OMeTAD with low-cost inorganic hole transport materials (HTMs) are important to further elevate the attractiveness of PSCs for commercialization. Perovskite-compatible, solution-exfoliated two-dimensional (2D) transition metal dichalcogenides (TMDCs) are being considered as viable candidates for inorganic HTMs. We consider one such TMDC, WSe 2 which was chemically exfoliated using dichlorobenzene (DCB), a perovskite-compatible solvent, as it was integrated with triple cation perovskite absorbers within the solar cell stack. Here, the WSe 2 HTL required heat treatment processes to be maintained below 100°C in order to preserve the integrity of the underlying perovskite; despite this lower temperature post treatment process, the structural morphology of the film revealed its dense and pinhole-free nature. Temperature-dependent transport studies conducted on the WSe 2 film provided evidence of its semiconducting character and its ability to extract holes well from the underlying triple-cation Cs 0.05 FA 0.79 MA 0.16 PbI 2.45 Br 0.55 absorber. The inorganic HTL offered better environmental stability in moisture-rich environments of up to 60% relative humidity, in comparison to spiro-OMeTAD HTL-based devices which degraded faster as a result of pinholes

14 SOLAR ENERGY

Förster Resonance Energy Transfer and Enhanced Emission in Cs 4 PbBr 6 Nanocrystals Encapsulated in Silicon Nano-Sheets for Perovskite Light Emitting Diode Applications

Encapsulating Cs 4 PbBr 6 quantum dots in silicon nano-sheets not only stabilizes the halide perovskite, but also takes advantage of the nano-sheet for a compatible integration with the traditional silicon semiconductor. Here, we report the preparation of un-passivated Cs 4 PbBr 6 ellipsoidal nanocrystals and pseudo-spherical quantum dots in silicon nano-sheets and their enhanced photoluminescence (PL). For a sample with low concentrations of quantum dots in silicon nano-sheets, the emission from Cs 4 PbBr 6 pseudo-spherical quantum dots is quenched and is dominated with Pb 2+ ion/silicene emission, which is very stable during the whole measurement period. For a high concentration of Cs 4 PbBr 6 ellipsoidal nanocrystals in silicon nano-sheets, we have observed Förster resonance energy transfer with up to 87% efficiency through the oscillation of two PL peaks when UV excitation switches between on and off, using recorded video and PL lifetime measurements. In an area of a non-uniform sample containing both ellipsoidal nanocrystals and pseudo-spherical quantum dots, where Pb 2+ ion/silicene emissions, broadband emissions from quantum dots, and bandgap edge emissions (515 nm) appear, the 515 nm peak intensity increases five times over 30 min of UV excitation, probably due to a photon recycling effect. This irradiated sample has been stable for one year of ambient storage. Cs 4 PbBr 6 quantum dots encapsulated in silicon nano-sheets can lead to applications of halide perovskite light emitting diodes (PeLEDs) and integration with traditional semiconductor materials.

36 MATERIALS SCIENCE

Optically induced quantum transitions in direct probed mesoscopic NbSe 2 for prototypical bolometers

Superconducting transition-edge sensors (TES) have emerged as fascinating devices to detect broadband electromagnetic radiation with low thermal noise. The advent of metallic transition metal dichalcogenides, such as NbSe 2 , has also created an impetus to understand their low-temperature properties, including superconductivity. Interestingly, NbSe 2 -based sensor within the TES framework remains unexplored. In this work, direct-probed superconducting NbSe 2 absorbers led to a proof-of-concept demonstration for the transduction of incoming light to heat, where a thermodynamic superconducting phase transition in NbSe 2 was evident to switch it to the normal-state, when biased below its superconducting transition temperature. A wavelength-dependent response of its optical absorption properties was observed, based on the incident optical excitation source used. Furthermore, extensive optical characterization studies were conducted using Raman spectroscopy, where the in-plane and out-of-plane thermal conductivity was empirically determined. Our results open new possibilities for the use of NbSe 2 in superconducting radiation detectors, including in a TES framework

47 OTHER INSTRUMENTATION

Thermal-Strain-Enabled Enhanced Emission from UV Laser-Induced Defect Levels near the Surface of Multilayer MoS 2

Monolayer two-dimensional (2D) materials have been intensively studied while research on multilayers is still in its infancy. Here, we induce defects inside bulk MoS 2 through thermal annealing and near the surface of multilayer MoS 2 using 375 nm laser irradiation, and investigate their photoluminescence (PL) and fluorescence lifetime imaging (FLIM). Enhanced emission is limited within a certain MoS 2 thickness. The observed enhanced emission is evidenced by a threshold behavior in super-linear PL intensity increase, strong polarization effects, and increased lifetime of defect peak. The laser power threshold for enhanced emission is much smaller in defects near the surface than that inside the bulk of multilayer MoS 2 . The mechanical strain from a wrinkle of the sample further lowers the laser power threshold for enhanced emission. By exciting with a 639 nm laser that is close to the fundamental gap between the conduction band minimum and the valence band maximum, the lifetime of defect enhanced emission increased by 5 times. Furthermore, one of the competing indirect bandgap emissions disappears, and the defect emission peak dominates the PL spectrum in the wrinkle area with a strain. Furthermore, the discovered principle can be applied to future studies on the integration of enhanced emission and single photon emission involving selectively depopulating the conduction band of the host crystal to defect levels for quantum emitters.

2D materials

Thermally-Resilient, Broadband Optical Absorber from UV-to-IR Derived from Carbon Nanostructures and Method of Making the Same

A monolithic optical absorber and methods of making same. The monolithic optical absorber uses an array of mutually aligned carbon nanotubes that are grown using a PECVD growth process and a structure that includes a conductive substrate, a refractory template layer and a nucleation layer. Monolithic optical absorbers made according to the described structure and method exhibit high absorptivity, high site densities (greater than 10.sup.9 nanotubes/cm.sup.2), very low reflectivity (below 1%), and high thermal stability in air (up to at least 400.degree. C.). The PECVD process allows the application of such absorbers in a wide variety of end uses.

Kaul, Anupama B.

Methods for Gas Sensing with Single-Walled Carbon Nanotubes

Methods for gas sensing with single-walled carbon nanotubes are described. The methods comprise biasing at least one carbon nanotube and exposing to a gas environment to detect variation in temperature as an electrical response.

Kaul, Anupama B.

A Bottom-Up Engineered Broadband Optical Nanoabsorber for Radiometry and Energy Harnessing Applications

Optical absorbers based on vertically aligned multi-walled carbon nanotubes (MWCNTs), synthesized using electric-field assisted growth, are described here that show an ultra-low reflectance, 100X lower compared to Au-black from wavelength lamba approximately 350 nm - 2.5 micron. A bi-metallic Co/Ti layer was shown to catalyze a high site density of MWCNTs on metallic substrates and the optical properties of the absorbers were engineered by controlling the bottom-up synthesis conditions using dc plasma-enhanced chemical vapor deposition (PECVD). Reflectance measurements on the MWCNT absorbers after heating them in air to 400deg showed negligible changes in reflectance which was still low, approximately 0.022 % at lamba approximately 2 micron. In contrast, the percolated structure of the reference Au-black samples collapsed completely after heating, causing the optical response to degrade at temperatures as low as 200deg. The high optical absorption efficiency of the MWCNT absorbers, synthesized on metallic substrates, over a broad spectral range, coupled with their thermal ruggedness, suggests they have promise in solar energy harnessing applications, as well as thermal detectors for radiometry.

optical absorbers

Applications and Methods of Operating a Three-dimensional Nano-electro-mechanical Resonator and Related Devices

Carbon nanofiber resonator devices, methods for use, and applications of said devices are disclosed. Carbon nanofiber resonator devices can be utilized in or as high Q resonators. Resonant frequency of these devices is a function of configuration of various conducting components within these devices. Such devices can find use, for example, in filtering and chemical detection.

Kaul, Anupama B.

Characterization of Plasma Synthesized Vertical Carbon Nanofibers for Nanoelectronics Applications

We report on the material characterization of carbon nanofibers (CNFs) which are assembled into a three-dimensional (3D) configuration for making new nanoelectromechanical systems (NEMS). High-resolution scanning electron microscopy (SEM) and x-ray electron dispersive spectroscopy (XEDS) are employed to decipher the morphology and chemical compositions of the CNFs at various locations along individual CNFs grown on silicon (Si) and refractory nitride (NbTiN) substrates, respectively. The measured characteristics suggest interesting properties of the CNF bodies and their capping catalyst nanoparticles, and growth mechanisms on the two substrates. Laser irradiation on the CNFs seems to cause thermal oxidation and melting of catalyst nanoparticles. The structural morphology and chemical compositions of the CNFs revealed in this study should aid in the applications of the CNFs to nanoelectronics and NEMS.

carbon nanomaterials

Carbon nanotube vacuum gauges with wide-dynamic range and processes thereof

A miniature thermal conductivity gauge employs a carbon single-walled-nanotube. The gauge operates on the principle of thermal exchange between the voltage-biased nanotube and the surrounding gas at low levels of power and low temperatures to measure vacuum across a wide dynamic range. The gauge includes two terminals, a source of constant voltage to the terminals, a single-walled carbon nanotube between the terminals, a calibration of measured conductance of the nanotube to magnitudes of surrounding vacuum and a current meter in electrical communication with the source of constant voltage. Employment of the nanotube for measuring vacuum includes calibrating the electrical conductance of the nanotube to magnitudes of vacuum, exposing the nanotube to a vacuum, applying a constant voltage across the nanotube, measuring the electrical conductance of the nanotube in the vacuum with the constant voltage applied and converting the measured electrical conductance to the corresponding calibrated magnitude of vacuum using the calibration. The nanotube may be suspended to minimize heat dissipation through the substrate, increasing sensitivity at even tower pressures.

Manohara, Harish

Thermally Resilient, Broadband Optical Absorber from UV to IR Derived from Carbon Nanostructures

Optical absorber coatings have been developed from carbon-based paints, metal blacks, or glassy carbon. However, such materials are not truly black and have poor absorption characteristics at longer wavelengths. The blackness of such coatings is important to increase the accuracy of calibration targets used in radiometric imaging spectrometers since blackbody cavities are prohibitively large in size. Such coatings are also useful potentially for thermal detectors, where a broadband absorber is desired. Au-black has been a commonly used broadband optical absorber, but it is very fragile and can easily be damaged by heat and mechanical vibration. An optically efficient, thermally rugged absorber could also be beneficial for thermal solar cell applications for energy harnessing, particularly in the 350-2,500 nm spectral window. It has been demonstrated that arrays of vertically oriented carbon nanotubes (CNTs), specifically multi-walled-carbon- nanotubes (MWCNTs), are an exceptional optical absorber over a broad range of wavelengths well into the infrared (IR). The reflectance of such arrays is 100x lower compared to conventional black materials, such as Au black in the spectral window of 350-2,500 nm. Total hemispherical measurements revealed a reflectance of approximately equal to 1.7% at lambda approximately equal to 1 micrometer, and at longer wavelengths into the infrared (IR), the specular reflectance was approximately equal to 2.4% at lambda approximately equal to 7 micrometers. The previously synthesized CNTs for optical absorber applications were formed using water-assisted thermal chemical vapor deposition (CVD), which yields CNT lengths in excess of 100's of microns. Vertical alignment, deemed to be a critical feature in enabling the high optical absorption from CNT arrays, occurs primarily via the crowding effect with thermal CVD synthesized CNTs, which is generally not effective in aligning CNTs with lengths less than 10 m. Here it has been shown that the electric field inherent in a plasma yields vertically aligned CNTs at small length scales (less than 10 m), which still exhibit broadband, and high-efficiency optical absorption characteristics from the ultraviolet (UV) to IR. A thin and yet highly absorbing coating is extremely valuable for detector applications for radiometry in order to enhance sensitivity. A plasma-based process also increases the potential of forming the optical absorbers at lower synthesis temperatures in the future, increasing the prospects of integrating the absorbers with flexible substrates for low-cost solar cell applications, for example.

Kaul, Anupama B.

Carbon Nanofiber-Based, High-Frequency, High-Q, Miniaturized Mechanical Resonators

High Q resonators are a critical component of stable, low-noise communication systems, radar, and precise timing applications such as atomic clocks. In electronic resonators based on Si integrated circuits, resistive losses increase as a result of the continued reduction in device dimensions, which decreases their Q values. On the other hand, due to the mechanical construct of bulk acoustic wave (BAW) and surface acoustic wave (SAW) resonators, such loss mechanisms are absent, enabling higher Q-values for both BAW and SAW resonators compared to their electronic counterparts. The other advantages of mechanical resonators are their inherently higher radiation tolerance, a factor that makes them attractive for NASA s extreme environment planetary missions, for example to the Jovian environments where the radiation doses are at hostile levels. Despite these advantages, both BAW and SAW resonators suffer from low resonant frequencies and they are also physically large, which precludes their integration into miniaturized electronic systems. Because there is a need to move the resonant frequency of oscillators to the order of gigahertz, new technologies and materials are being investigated that will make performance at those frequencies attainable. By moving to nanoscale structures, in this case vertically oriented, cantilevered carbon nanotubes (CNTs), that have larger aspect ratios (length/thickness) and extremely high elastic moduli, it is possible to overcome the two disadvantages of both bulk acoustic wave (BAW) and surface acoustic wave (SAW) resonators. Nano-electro-mechanical systems (NEMS) that utilize high aspect ratio nanomaterials exhibiting high elastic moduli (e.g., carbon-based nanomaterials) benefit from high Qs, operate at high frequency, and have small force constants that translate to high responsivity that results in improved sensitivity, lower power consumption, and im - proved tunablity. NEMS resonators have recently been demonstrated using topdown, lithographically fabricated ap - proaches to form cantilever or bridgetype structures. Top-down approaches, however, rely on complicated and expensive e-beam lithography, and often require a release mechanism. Reso - nance effects in structures synthesized using bottom-up approaches have also recently been reported based on carbon nanotubes, but such approaches have relied on a planar two-dimensional (2D) geometry. In this innovation, vertically aligned tubes synthesized using a bottom- up approach have been considered, where the vertical orientation of the tubes has the potential to increase integration density even further. The simulation of a vertically oriented, cantilevered carbon nanotube was performed using COMSOL Multi - physics, a finite element simulation package. All simulations were performed in a 2D geometry that provided consistent results and minimized computational complexity. The simulations assumed a vertically oriented, cantilevered nanotube of uniform density (1.5 g/cu cm). An elastic modulus was assumed to be 600 GPa, relative permittivity of the nanotube was assumed to be 5.0, and Poisson s ratio was assumed to be 0.2. It should be noted that the relative permittivity and Poisson s ratio for the nanotubes of interest are not known accurately. However, as in previous simulations, the relative permittivity and Poisson s ratios were treated as weak variables in the simulation, and no significant changes were recognized when these variables were varied.

Kaul, Anupama B.

High-Sensitivity, Broad-Range Vacuum Gauge Using Nanotubes for Micromachined Cavities

A broad-range vacuum gauge has been created by suspending a single-walled carbon nanotube (SWNT) (metallic or semiconducting) in a Schottky diode format or in a bridge conductor format, between two electrically charged mesas. SWNTs are highly sensitive to molecular collisions because of their extremely small diameters in the range of 1 to 3 nanometers. The measurement parameter will be the change in conductivity of SWNT due to decreasing rate of molecular collisions as the pressure inside a chamber decreases. The rate of heat removal approaches a saturation limit as the mean free path (m.f.p.) lengths of molecules increase due to decreasing pressure. Only those sensing elements that have a long relaxation time can produce a measureable response when m.f.p. of molecules increases (or time between two consecutive collisions increases). A suspended SWNT offers such a capability because of its one-dimensional nature and ultrasmall diameter. In the initial approach, similar architecture was used as that of a SWNT-Schottky diode that has been developed at JPL, and has its changing conductivity measured as the test chamber is pumped down from atmospheric pressure to high vacuum (10(exp -7) Torr). Continuous response of decreasing conductivity has been measured as a function of decreasing pressure (SWNT is a negative thermal coefficient material) from atmosphere to less than 10(exp -6) Torr. A measureable current change in the hundreds of nA range has been recorded in the 10(exp -6) Torr regime.

Manohara, Harish

Carbon Nanofibers Synthesized on Selective Substrates for Nonvolatile Memory and 3D Electronics

A plasma-enhanced chemical vapor deposition (PECVD) growth technique has been developed where the choice of starting substrate was found to influence the electrical characteristics of the resulting carbon nanofiber (CNF) tubes. It has been determined that, if the tubes are grown on refractory metallic nitride substrates, then the resulting tubes formed with dc PECVD are also electrically conducting. Individual CNFs were formed by first patterning Ni catalyst islands using ebeam evaporation and liftoff. The CNFs were then synthesized using dc PECVD with C2H2:NH3 = [1:4] at 5 Torr and 700 C, and approximately equal to 200-W plasma power. Tubes were grown directly on degenerately doped silicon <100> substrates with resistivity rho approximately equal to 1-5 meterohm-centimeter, as well as NbTiN. The approximately equal to 200-nanometer thick refractory NbTiN deposited using magnetron sputtering had rho approximately equal to 113 microohm-centimeter and was also chemically compatible with CNF synthesis. The sample was then mounted on a 45 beveled Al holder, and placed inside a SEM (scanning electron microscope). A nanomanipulator probe stage was placed inside the SEM equipped with an electrical feed-through, where tungsten probes were used to make two-terminal electrical measurements with an HP 4156C parameter analyzer. The positive terminal nanoprobe was mechanically manipulated to physically contact an individual CNF grown directly on NbTiN as shown by the SEM image in the inset of figure (a), while the negative terminal was grounded to the substrate. This revealed the tube was electrically conductive, although measureable currents could not be detected until approximately equal to 6 V, after which point current increased sharply until compliance (approximately equal to 50 nA) was reached at approximately equal to 9.5 V. A native oxide on the tungsten probe tips may contribute to a tunnel barrier, which could be the reason for the suppressed transport at low biases. Currents up to approximately 100 nA could be cycled, which are likely to propagate via the tube surface, or sidewalls, rather than the body, which is shown by the I-V in figure (a). Electrical conduction via the sidewalls is a necessity for dc NEMS (nanoelectromechanical system) applications, more so than for the field emission applications of such tubes. During the tests, high conductivity was expected, because both probes were shorted to the substrate, as shown by curve 1 in the I-V characteristic in figure (b). When a tube grown on NbTiN was probed, the response was similar to the approximately equal to 100 nA and is represented by curve 2 in figure (b), which could be cycled and propagated via the tube surface or the sidewalls. However, no measureable currents for the tube grown directly on Si were observed as shown by curve 3 in figure (b), even after testing over a range of samples. This could arise from a dielectric coating on the sidewalls for tubes on Si. As a result of the directional nature of ion bombardment during dc PECVD, Si from the substrate is likely re-sputtered and possibly coats the sidewalls.

Kaul, Anupama B.

Monolithically Integrated, Mechanically Resilient Carbon-Based Probes for Scanning Probe Microscopy

Scanning probe microscopy (SPM) is an important tool for performing measurements at the nanoscale in imaging bacteria or proteins in biology, as well as in the electronics industry. An essential element of SPM is a sharp, stable tip that possesses a small radius of curvature to enhance spatial resolution. Existing techniques for forming such tips are not ideal. High-aspect-ratio, monolithically integrated, as-grown carbon nanofibers (CNFs) have been formed that show promise for SPM applications by overcoming the limitations present in wet chemical and separate substrate etching processes.

Kaul, Anupama B.

Fabrication of Single, Vertically Aligned Carbon Nanotubes in 3D Nanoscale Architectures

Plasma-enhanced chemical vapor deposition (PECVD) and high-throughput manufacturing techniques for integrating single, aligned carbon nanotubes (CNTs) into novel 3D nanoscale architectures have been developed. First, the PECVD growth technique ensures excellent alignment of the tubes, since the tubes align in the direction of the electric field in the plasma as they are growing. Second, the tubes generated with this technique are all metallic, so their chirality is predetermined, which is important for electronic applications. Third, a wafer-scale manufacturing process was developed that is high-throughput and low-cost, and yet enables the integration of just single, aligned tubes with nanoscale 3D architectures with unprecedented placement accuracy and does not rely on e-beam lithography. Such techniques should lend themselves to the integration of PECVD grown tubes for applications ranging from interconnects, nanoelectromechanical systems (NEMS), sensors, bioprobes, or other 3D electronic devices. Chemically amplified polyhydroxystyrene-resin-based deep UV resists were used in conjunction with excimer laser-based (lambda = 248 nm) step-and-repeat lithography to form Ni catalyst dots = 300 nm in diameter that nucleated single, vertically aligned tubes with high yield using dc PECVD growth. This is the first time such chemically amplified resists have been used, resulting in the nucleation of single, vertically aligned tubes. In addition, novel 3D nanoscale architectures have been created using topdown techniques that integrate single, vertically aligned tubes. These were enabled by implementing techniques that use deep-UV chemically amplified resists for small-feature-size resolution; optical lithography units that allow unprecedented control over layer-to-layer registration; and ICP (inductively coupled plasma) etching techniques that result in near-vertical, high-aspect-ratio, 3D nanoscale architectures, in conjunction with the use of materials that are structurally and chemically compatible with the high-temperature synthesis of the PECVD-grown tubes. The techniques offer a wafer-scale process solution for integrating single PECVD-grown nanotubes into novel architectures that should accelerate their integration in 3D electronics in general. NASA can directly benefit from this technology for its extreme-environment planetary missions. Current Si transistors are inherently more susceptible to high radiation, and do not tolerate extremes in temperature. These novel 3D nanoscale architectures can form the basis for NEMS switches that are inherently less susceptible to radiation or to thermal extremes.

Kaul, Anupama B.

High-Throughput Top-Down and Bottom-Up Processes for Forming Single-Nanotube Based Architectures for 3D Electronics

We have developed manufacturable approaches to form single, vertically aligned carbon nanotubes, where the tubes are centered precisely, and placed within a few hundred nm of 1-1.5 micron deep trenches. These wafer-scale approaches were enabled by chemically amplified resists and inductively coupled Cryo-etchers for forming the 3D nanoscale architectures. The tube growth was performed using dc plasma-enhanced chemical vapor deposition (PECVD), and the materials used for the pre-fabricated 3D architectures were chemically and structurally compatible with the high temperature (700 C) PECVD synthesis of our tubes, in an ammonia and acetylene ambient. Tube characteristics were also engineered to some extent, by adjusting growth parameters, such as Ni catalyst thickness, pressure and plasma power during growth. Such scalable, high throughput top-down fabrication techniques, combined with bottom-up tube synthesis, should accelerate the development of PECVD tubes for applications such as interconnects, nano-electromechanical (NEMS), sensors or 3D electronics in general.

plasma-enhanced chemical vapor deposition (PECVD),

Electrostatic Switching in Vertically Oriented Nanotubes for Nonvolatile Memory Applications

We have demonstrated electrostatic switching in vertically oriented nanotubes or nanofibers, where a nanoprobe was used as the actuating electrode inside an SEM. When the nanoprobe was manipulated to be in close proximity to a single tube, switching voltages between 10 V - 40 V were observed, depending on the geometrical parameters. The turn-on transitions appeared to be much sharper than the turn-off transitions which were limited by the tube-to-probe contact resistances. In many cases, stiction forces at these dimensions were dominant, since the tube appeared stuck to the probe even after the voltage returned to 0 V, suggesting that such structures are promising for nonvolatile memory applications. The stiction effects, to some extent, can be adjusted by engineering the switch geometry appropriately. Nanoscale mechanical measurements were also conducted on the tubes using a custom-built anoindentor inside an SEM, from which preliminary material parameters, such as the elastic modulus, were extracted. The mechanical measurements also revealed that the tubes appear to be well adhered to the substrate. The material parameters gathered from the mechanical measurements were then used in developing an electrostatic model of the switch using a commercially available finite-element simulator. The calculated pull-in voltages appeared to be in agreement to the experimentally obtained switching voltages to first order.

plasma-enhanced chemical vapor deposition (PECVD).