Search NASA⌕ Search

Engineering topics

Blackburn, Jeffrey L.

Publications and source records attributed to Blackburn, Jeffrey L..

47 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Linking optical spectra to free charges in donor/acceptor heterojunctions: cross-correlation of transient microwave and optical spectroscopy

The primary photoexcited species in excitonic semiconductors is a bound electron–hole pair, or exciton. An important strategy for producing separated electrons and holes in photoexcited excitonic semiconductors is the use of donor/acceptor heterojunctions, but the degree to which the carriers can escape their mutual Coulomb attraction is still debated for many systems. Here, we employ a combined pump–probe ultrafast transient absorption (TA) spectroscopy and time-resolved microwave conductivity (TRMC) study on a suite of model excitonic heterojunctions consisting of mono-chiral semiconducting single-walled carbon nanotube (s-SWCNT) electron donors and small-molecule electron acceptors. Comparison of the charge-separated state dynamics between TA and TRMC photoconductance reveals a quantitative match over the 0.5 microsecond time scale. Charge separation yields derived from TA allow extraction of s-SWCNT hole mobilities of ca. 1.5 cm 2 V -1 s -1 (at 9 GHz) by TRMC. We find that the correlation between the techniques conclusively demonstrates that photoinduced charge carriers separated across these heterojunctions do not form bound charge transfer states, but instead form free/mobile charge carriers.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Polyvinyl acetate-based polymer host for optical and far-infrared spectroscopy of individualized nanoparticles

Preparation techniques for producing films of individualized solution-dispersed nanoparticles (NPs) for optical spectroscopy are frequently technically challenging and tailored for a specific NP system. In this work, we present a rapid, easy, and economical technique for producing polyvinyl acetate (PVAc)-based NP-polymer films on the order of 100’s of micrometers thick that exhibit high uniformity, low aggregation, excellent optical transparency, and low terahertz absorption. In addition, we find that these films are robust at cryogenic temperatures and have a high laser damage threshold of 0.3 TW cm –2 , which make them suitable for pulsed laser measurements. We show that free-standing, flexible, PVAc films can incorporate both one-dimensional single-wall carbon nanotubes (SWCNTs) and zero-dimensional Au NPs. Using absorbance, Raman scattering, and photoluminescence excitation spectroscopy, we observe that SWCNT individualization is maintained, and minimized polymer strain imposed, when the nanotubes are transitioned from the solution to the polymer host. This PVAc-based polymer host presents researchers with a straightforward method for producing free-standing and flexible NP films with low aggregation.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Carbon nanotubes in high-performance perovskite photovoltaics and other emerging optoelectronic applications

Here, we take a look back at the successful integration of carbon nanotubes (CNT) into high-efficiency solar cells based on metal-halide perovskites (MHPs). In addition to these successes, we identify critical questions and issues that remain to be addressed for the functionality of CNTs in MHP-based solar cells. Finally, we look forward toward potential future opportunities for CNT/MHP interfaces, in both new types of photovoltaic devices and other emerging optoelectronic applications.

14 SOLAR ENERGY↗
DOE OSTI2021

Extracellular electron transfer across bio-nano interfaces for CO 2 electroreduction

Acetogenic bacteria represent a class of organisms capable of converting reducing equivalents and carbon dioxide into products with carbon–carbon bonds. Materials-based bio-electrochemical approaches are attractive for supplying biological organisms directly with grid-supplied electrons to convert carbon dioxide to value-added chemicals. Carbon nanotube-modified biocathodes have emerged as promising candidates for microbial electrosynthesis with high yields of carbon product formation, but a fundamental understanding of extracellular charge transfer at this electrode-biofilm interface is still lacking. Here, we utilize solid-state interfaces between semiconducting single-walled carbon nanotubes (s-SWCNT) and a model acetogenic bacterium for mechanistic studies of electro-catalytic CO 2 conversion to acetate. Studies of bacteria/s-SWCNT interactions in a transistor-based device suggest direct extracellular electron transfer (EET) at the bio-nano interface. Deuterium isotope labeling experiments confirmed that the availability of electrochemically produced H 2 as a redox mediator does not limit the efficiency of EET and CO 2 electro-reduction for C. ljungdahlii biofilms, suggesting the primary reducing equivalents are the electrons delivered across the electrode/bacterium interface or involvement of biological redox mediators. Additional isotope labeling studies demonstrate high Faradaic efficiency for CO 2 electro-reduction at the SWCNT/bacterium interface. These results provide important information about EET across the bacterium/material interface in a model biocathode.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2020

Perovskite Electronic Ratchets for Energy Harvesting

Electronic ratchets are energy-harvesting devices that can utilize spatially asymmetric potential distributions to convert nondirectional/random sources of energy into direct current. The potential asymmetry can be generated in a number of ways, but one purported mechanism is to redistribute ions directly within the active material. Utilizing the known propensity for ion migration in lead-halide perovskites (LHP), the first LHP flashing electronic ratchet is demonstrated by using a voltage stress to intentionally redistribute halide ions within a prototypical 2D perovskite. The resulting asymmetric potential distribution across the 2D perovskite allows for conversion of both electronic noise and unbiased square-wave potentials into current. Furthermore, simultaneous application of light illumination and voltage stress enhances the asymmetric potential distribution, enabling higher current than the nonilluminated device. This work presents an electronic ratchet system that exploits facile ion migration, which can be modified by both electrical and optical stimuli, providing a model system with the potential to test outstanding mechanistic questions for electronic ratchets.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Spatially Resolved Persistent Photoconductivity in MoS2–WS2 Lateral Heterostructures

The optical and electronic properties of 2D semiconductors are intrinsically linked via the strong interactions between optically excited bound species and free carriers. Here we use near-field scanning microwave microscopy (SMM) to image spatial variations in photoconductivity in MoS 2 –WS 2 lateral multijunction heterostructures using photon energy-resolved narrowband illumination. We find that the onset of photoconductivity in individual domains corresponds to the optical absorption onset, confirming that the tightly bound excitons in transition metal dichalcogenides can nonetheless dissociate into free carriers. These photogenerated carriers are most likely n-type and are seen to persist for up to days. Informed by finite element modeling we reveal that they can increase the carrier density by up to 200 times. This persistent photoconductivity appears to be dominated by contributions from the multilayer MoS 2 domains, and we attribute the flake-wide response in part to charge transfer across the heterointerface. Spatial correlation of our SMM imaging with photoluminescence (PL) mapping confirms the strong link between PL peak emission photon energy, PL intensity, and the local accumulated charge. This work reveals the spatially and temporally complex optoelectronic response of these systems and cautions that properties measured during or after illumination may not reflect the true dark state of these materials but rather a metastable charged state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Size- and Temperature-Dependent Suppression of Phonon Thermal Conductivity in Carbon Nanotube Thermoelectric Films

Heat transport in nanoscale carbon materials such as carbon nanotubes and graphene is normally dominated by phonons. Here, measurements of in-plane thermal conductivity, electrical conductivity, and thermopower are presented from 77–350 K on two films with thickness <100 nm formed from semiconducting single-walled carbon nanotubes. These measurements are made with silicon–nitride membrane thermal isolation platforms. The two films, formed from disordered networks of tubes with differing tube and bundle size, have very different thermal conductivity. One film matches a simple model of heat conduction assuming constant phonon velocity and mean free path, and 3D Debye heat capacity with a Debye temperature of 770 K. The second film shows a more complicated temperature dependence, with a dramatic drop in a relatively narrow window near 200 K where phonon contributions to thermal conductivity essentially vanish. This causes a corresponding large increase in thermoelectric figure-of-merit at the same temperature. A better understanding of this behavior can allow significant improvement in thermoelectric efficiency of these low-cost earth-abundant, organic electronic materials. Finally, heat and charge conductivity near room temperature is also presented as a function of doping, which provides further information on the interaction of dopant molecules and phonon transport in disordered nanotube films.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Disentangling Oxygen and Water Vapor Effects on Optoelectronic Properties of Monolayer Tungsten Disulfide

By understanding how the environmental composition impacts the optoelectronic properties of transition metal dichalcogenide monolayers, we demonstrate that simple photoluminescence (PL) measurements of tungsten disulfide (WS 2 ) monolayers can differentiate relative humidity environments. In this paper, we examine the PL and photoconductivity of chemical vapor deposition grown WS 2 monolayers under three carefully controlled environments: inert gas (N 2 ), dry air (O 2 in N 2 ), and humid nitrogen (H 2 O vapor in N 2 ). The WS 2 PL is measured as a function of 532 nm laser power and exposure time and can be decomposed into the exciton, trion, and lower energy state(s) contributions. Under continuous illumination in either O 2 or H 2 O vapor environment, we find dramatic (and reversible) increases in PL intensity relative to the PL in an inert environment. The PL bathochromically shifts in an O 2 environment and is dominated by increased trion emission and diminished exciton emission. In contrast, the WS 2 PL increase in a H 2 O environment results from an overall increase in emission from all spectral components where the exciton contribution dominates. The drastic increases in PL are anticorrelated with corresponding decreases in photoconductivity, as measured by time-resolved microwave conductivity. The results suggest that both O 2 and H 2 O react photochemically with the WS 2 monolayer surface, modifying the optoelectronic properties, but do so via distinct pathways. Thus, we use these optoelectronic differences to differentiate the amount of humidity in the air, which we show with 0%, 40%, and 80% relative humidity environments. This deeper understanding of how ambient conditions impact WS 2 monolayers enables novel humidity sensors as well as a better understanding of the correlation between TMDC surface chemistry, light emission, and photoconductivity. Moreover, these WS 2 measurements highlight the importance of considering the impact of the local environment on reported results.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Improvement in Power Output for CNT Polymer Hybrid Film and Accompanying Thermoelectric Generator: Cooperative Research and Development (CRADA CRD-15-596 Final Report)

NREL personnel will enhance International ThermoDyne's (ITD) understanding of the controlling factors for power output within a process for the manufacturing of high-performance carbon nanotube (CNT) thermoelectric generator (TEG) structure (alternative areas of p and n type semiconductor) and provide ITD with samples ('Deliverables') demonstrating these advances in power output that can used. The Deliverables will have performance characteristics outlined in Table 1, for use in ITD's PowerFelt product. The initial goals of this project are to achieve thermoelectric p and n films with power factors of at least 600uW/mK2 made through NREL's process for TEG paper manufacture with high conductivity and low thermal conductivity and eventually achieving higher performance of > 900 uW/mK2.

36 MATERIALS SCIENCE↗