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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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Leveraging the redox activities of cerium and dibenzotetrathiafulvalene to discover a photo-responsive magnetic material

Stimuli-responsive changes in lanthanide-based materials are a promising research direction. In this study, [DBTTF] 4 [Ce 2 Cl 10 ] DBTTF = dibenzotetrathiafulvalene (1) was synthesized by a light-induced crystallization, where photo-oxidation of DBTTF enables formation of the cerium dimer [Ce 2 Cl 10 ] 4− . Intermolecular interactions between the stacked organic units of the crystal result in charge transfer bands in the visible-NIR (near-infrared) region, evident in the solid-state absorption spectrum upon comparison with the solution spectrum. The assignments of the sublattice oxidation states were made with single-crystal X-ray diffraction (SC-XRD) structural characterization, Raman spectroscopy, X-ray absorption spectroscopy, and magnetometry. Continuous 532 nm laser irradiation of the microcrystalline solid modulates the redox states in 1, leading to ∼40% reduction in the observed magnetization at 2 K. Density functional theory PBE+U/HSE06 band structure calculations predict Mott insulating behavior in 1, with a bandgap of 0.54/0.81 eV, and further support the conjecture that the observed photo-induced change in magnetization results from electron transfer from the [Ce 2 Cl 10 ] 4− anions to the π-stacked [DBTTF] 2 2+ organic dimer subunits. An enhancement in conductivity is similarly observed upon 532 nm irradiation, determined by single-crystal transport measurements. The findings reveal that photo-responsive lanthanide-based materials can be achieved by integration of redox-active organic moieties with redox-active lanthanide cations for the realization of switchable, photo-magnetic materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Photo-response of the $N=Z$ nucleus $^{24}$Mg

The electric E1 and magnetic M1 dipole responses of the N = Z nucleus 24 Mg were investigated in an inelastic photon scattering experiment. The 13.0 MeV electrons, which were used to produce the unpolarised bremsstrahlung in the entrance channel of the 24 Mg(γ,γ') reaction, were delivered by the ELBE accelerator of the Helmholtz-Zentrum Dresden-Rossendorf. The collimated bremsstrahlung photons excited one J π = 1 – , four J π = 1 + , and six J π = 2 + states in 24 Mg. De-excitation γ rays were detected using the four high-purity germanium detectors of the γELBE setup, which is dedicated to nuclear resonance fluorescence experiments. In the energy region up to 13.0 MeV a total B(M1)↑ = 2.7(3) $μ$$^{2}_{N}$ is observed, but this N = Z nucleus exhibits only marginal E1 strength of less than ΣB(E1)↑≤ 0.61 × 10 –3 e 2 fm 2 . The B(Π1, $1$$^{π}_{i}$ → $2$$^{+}_{1}$)/B(Π1,$1$$^{π}_{i}$ → $0$$^{+}_{gs}$) branching ratios in combination with the expected results from the Alaga rules demonstrate that K is a good approximative quantum number for 24 Mg. The use of the known ρ 2 (E0, $0$$^{+}_{2}$ → $0$$^{+}_{gs}$) strength and the measured B(M1,1 + → $0$$^{+}_{2}$)/B(M1,1 + → $0$$^{+}_{gs}$) branching ratio of the 10.712 MeV 1 + level allows, in a two-state mixing model, an extraction of the difference Δ$β$$^{2}_{2}$ between the prolate ground-state structure and shape-coexisting superdeformed structure built upon the 6432-keV $0$$^{+}_{2}$ level.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Radiation Damage and Mitigation by Minority Carrier Injection in InAsSb/AlAsSb Heterojunction Barrier Mid-Wave Infrared Detector

Here, the effects of gamma and proton irradiation, and of forward bias minority carrier injection, on photo-response were investigated for InAsSb/AlAsSb pBn mid-wave infrared (MWIR) detectors with an engineered majority-carrier barrier. Room-temperature gamma irradiation had an insignificant effect on 77 K photo-response. Gamma irradiation at 77 K detector temperature, however, decreased in situ photo-response by 19% after a cumulative dose of ~ 500 krad(Si). Subsequent forward bias minority carrier injection had no effect on photo-response. The 77 K detectors irradiated with 30 MeV protons up to 2 Mrad(Si) had photo-response degraded by up to 70%, but here forward bias minority carrier (hole) injection caused up to 12% recovery that persisted more than 30 min. These results suggest a mitigation strategy for maintaining the photo-response of similar detectors in radiation environments that cause displacement damage defects.

36 MATERIALS SCIENCE↗

Colossal switchable photocurrents in topological Janus transition metal dichalcogenides

Nonlinear optical properties, such as bulk photovoltaic effects, possess great potential in energy harvesting, photodetection, rectification, etc. To enable efficient light–current conversion, materials with strong photo-responsivity are highly desirable. In this work, we predict that monolayer Janus transition metal dichalcogenides (JTMDs) in the 1T' phase possess colossal nonlinear photoconductivity owing to their topological band mixing, strong inversion symmetry breaking, and small electronic bandgap. 1T'JTMDs have inverted bandgaps on the order of 10 meV and are exceptionally responsive to light in the terahertz (THz) range. By first-principles calculations, we reveal that 1T' JTMDs possess shift current (SC) conductivity as large as 2300 nm μA V -2 , equivalent to a photo-responsivity of 2800 mA/W. The circular current (CC) conductivity of 1T' JTMDs is as large as ~10 4 nm μA V -2 . These remarkable photo-responsivities indicate that the 1T' JTMDs can serve as efficient photodetectors in the THz range. We also find that external stimuli such as the in-plane strain and out-of-plane electric field can induce topological phase transitions in 1T' JTMDs and that the SC can abruptly flip their directions. The abrupt change of the nonlinear photocurrent can be used to characterize the topological transition and has potential applications in 2D optomechanics and nonlinear optoelectronics.

Chemistry↗

System and method for computed axial lithography (CAL) for 3D additive manufacturing

In one aspect the present disclosure relates to a system for forming a three dimensional (3D) object from a volume of photo-responsive material contained within a material container. A plurality of optical projection subsystems are adapted to be arranged circumferentially around a material container containing the volume of photo-responsive material, and are controlled by a controller. The optical projection subsystems direct optical projections at a plurality of angles θ through the volume of photo-responsive material. The optical projections are further directed about a z axis extending through the volume of photo-responsive material. The plurality of optical subsystems are further controlled by the controller to provide each of the optical projections with a calculated three-dimensional intensity distribution acting over a fixed temporal exposure period, which is sufficient to at least one of cure or remove selected portions of the volume of photo-responsive material, and leave other portions unmodified, to form a desired 3D part.

Kelly, Brett↗

System and method for computed axial lithography (CAL) for 3D additive manufacturing

In one aspect the present disclosure relates to a system for forming a three dimensional (3D) object from a volume of photo-responsive material contained within a material container. A plurality of optical projection subsystems are adapted to be arranged at least partially circumferentially around a material container containing the volume of photo-responsive material, and are controlled by a controller. The optical projection subsystems direct optical projections at a plurality of angles θ through the volume of photo-responsive material. The optical projections are further directed about a z axis extending through the volume of photo-responsive material. The plurality of optical subsystems are further controlled by the controller to provide each of the optical projections with a calculated three-dimensional intensity distribution acting over a fixed temporal exposure period, which is sufficient to at least one of cure or remove selected portions of the volume of photo-responsive material, and leave other portions unmodified, to form a desired 3D part.

Kelly, Brett↗

Dual-step photocarrier injection by mixture layer of ZnO QDs and MoS 2 NPs on hybrid PdAu NPs

Hybrid UV-photodetector (PD) design consisted of various compatible nano-material systems are drawing significant research interests due to their improved device tunability and functionality. A hybrid ZnO–MoS 2 /HNP UV-PD design is demonstrated by the mixture layer of zinc oxide (ZnO) quantum dot (QD) and molybdenum di-sulfate (MoS 2 ) nanoparticles (NPs) on the plasmonic hybrid PdAu NP template. The proposed design exhibits an excellent photocurrent of 1.45×10 -3 A under the 54.9 mW/mm2 at ± 10 V due to a dual step enhancement of photo-carrier injection. It then leads to the significantly improved performance factors of photo-responsivity 1430 mA/mm 2 and detectivity 4.50 × 10 10 jones at 0.34 mW/mm 2 . The rise time (T r ) and fall time (T f ) of 3.37 and 0.35 s are obtained for the ZnO–MoS 2 /HNP PD. Finally, the demonstrated performance factors indicate that the hybrid ZnO–MoS 2 /HNP UV-PD platform is one of the best UV-PDs as summarized in Table 1.

36 MATERIALS SCIENCE↗

Fluorescence Enhancement in the Solid State by Isolating Perylene Fluorophores in Metal–Organic Frameworks

Polycyclic aromatic hydrocarbons such as perylene, pyrene, and their derivatives are highly emissive fluorophores in solution. Furthermore, the practical applications of these materials in the field of molecular electronic and light emitting devices are often hindered by self-quenching effects due to the formation of non-fluorescent aggregates in concentrated solutions or in the solid state. Herein, we demonstrate that aggregation caused quenching of perylenes can be minimalized by molecular incorporation into metalorganic frameworks (MOFs). This study utilized a stable Zr 6 cluster-based MOF, UiO-67, as a matrix. Linear linkers containing the photo-responsive moieties were designed and incorporated into the parent UiO-67 scaffold through the partially replacement of the non-fluorescent linkers of a similar length, forming mixed-linker MOFs. Here, the average distance between perylene moieties was tuned by changing the linker ratios, thus controlling the fluorescence intensity, emission wavelength, and quantum yield. Molecular modeling was further adopted to correlate the number of isolated perylene linkers within the framework to the ratio between the two linkers, therefore rationalizing the change in the observed fluorescent properties. Taking advantage of the tunable fluorescence, inherent porosity, and high chemical stability of this MOF platform, it was applied as a fluorescent sensor for oxygen detection in the gas phase, a model reaction, showing fast response and good recyclability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Lead-Free Cs 4 CuSb 2 Cl 12 Layered Double Perovskite Nanocrystals

Concerns about the toxicity of lead-based perovskites have aroused great interest for the development of alternative lead-free perovskite-type materials. Recently, theoretical calculations predict that Pb 2+ cations can be substituted by a combination of Cu 2+ and Sb 3+ cations to form a vacancy-ordered layered double perovskite structure with superior optoelectronic properties. However, accessibilities to this class of perovskite-type materials remain inadequate, hindering their practical implementations in various applications. Here, we report the first colloidal synthesis of Cs 4 CuSb 2 Cl 12 perovskite-type nanocrystals (NCs). The resulting NCs exhibit a layered double perovskite structure with ordered vacancies and a direct bandgap of 1.79 eV. A composition-structure-property relationship has been established by investigating a series of Cs 4 Cu x Ag 2-2x Sb 2 Cl 12 perovskite-type NCs (0 ≤ x ≤ 1). The composition-induced crystal structure transformation, thus the electronic bandgap evolution has been explored by experimental observations and further confirmed by theoretical calculations. Taking advantages of both the unique electronic structure and solution processability, we demonstrate that the Cs 4 CuSb 2 Cl 12 NCs can be solution-processed as high-speed photodetectors with ultrafast photo-response and narrow bandwidth. We anticipate that our study will prompt future research to design and fabricate novel and high-performance lead-free perovskite-type NCs for a range of applications.

25 ENERGY STORAGE↗

Strain-engineered high-responsivity MoTe 2 photodetector for silicon photonic integrated circuits

In integrated photonics, specific wavelengths are preferred such as 1550 nm due to low-loss transmission and the availability of optical gain in this spectral region. For chip-based photodetectors, layered two-dimensional (2D) materials bear scientific and technologically relevant properties such as electrostatic tunability and strong light-matter interactions. However, no efficient photodetector in the telecommunication C-band has been realized with 2D transition metal dichalcogenide materials due to their large optical bandgap. Furthermore, we demonstrate a MoTe 2 -based photodetector featuring strong photoresponse (responsivity = 0.5 A/W -1 ) operating at 1550 nm in silicon photonics enabled by strain engineering the 2D material. Non-planarized waveguide structures show a locally-induced bandgap change of 0.2 eV inside MoTe 2 , resulting in large photo-response, in an otherwise photo-inactive medium when unstrained. Unlike Graphene-based photodetectors relying on a gapless band structure, this photodetector shows a ~100X improved dark current, enabling an efficient noise equivalent power of 90 pW/Hz -0.5 . Such strain-engineered integrated photodetector provides new opportunities for integrated optoelectronic systems.

47 OTHER INSTRUMENTATION↗

Photogating-driven enhanced responsivity in a few-layered ReSe 2 phototransistor

A wide variety of two-dimensional (2D) metal dichalcogenide compounds have recently attracted much research interest due to their very high photoresponsivities (R) making them excellent candidates for optoelectronic applications. High R in 2D photoconductors is associated with trap state dynamics leading to a photogating effect, which is often manifested by a fractional power dependence (γ) of the photocurrent (I ph ) at an effective illumination intensity (P eff ). Furthermore, we present photoconductivity studies as a function of gate voltages, over a wide temperature range (20 K to 300 K) of field-effect transistors fabricated using thin layers of mechanically exfoliated Rhenium Diselenide (ReSe 2 ). We obtain very high responsivities R ~ 16500 A/W and external quantum efficiency (EQE) ~ 3.2 × 106% (at 140 K, V g = 60 V and P eff = 0.2 nW). A strong correlation between R and γ was established by investigating the dependence of these two quantities at various gate voltages and over a wide range of temperatures. Such correlations indicate the importance of trap state mediated photogating and its role in promoting high photo-responsivities in these materials. We believe such correlations can offer valuable insights for the design and development of high-performance photoactive devices using 2D materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Revealing charge carrier dynamics and transport in Te-doped GaAsSb and GaAsSbN nanowires by correlating ultrafast terahertz spectroscopy and optoelectronic characterization

Recent advances in the growth of III-V semiconductor nanowires (NWs) hold great promise for nanoscale optoelectronic device applications. It is established that a small amount of nitrogen (N) incorporation in III-V semiconductor NWs can effectively red-shift their wavelength of operation and tailor their electronic properties for specific applications. Still, understanding the impact of N incorporation on non-equilibrium charge carrier dynamics and transport in semiconducting NWs is critical in achieving efficient semiconducting NW devices. In this work, ultrafast optical pump-terahertz probe spectroscopy has been used to study non-equilibrium carrier dynamics and transport in Te-doped GaAsSb and dilute nitride GaAsSbN NWs, with the goal of correlating these results with electrical characterization of their equilibrium photo-response under bias and low-frequency noise characteristics. Nitrogen incorporation in GaAsSb NWs led to a significant increase in the carrier scattering rate, resulting in a severe reduction in carrier mobility. Carrier recombination lifetimes of 33 ± 1 picoseconds (ps) and 147 ± 3 ps in GaAsSbN and GaAsSb NWs, respectively, were measured. The reduction in the carrier lifetime and photoinduced optical conductivities are due to the presence of N-induced defects, leading to deterioration in the electrical and optical characteristics of dilute nitride NWs relative to the non-nitride NWs. Finally, we observed a very fast rise time of ~2 ps for both NW materials, directly impacting their potential use as high-speed photodetectors.

36 MATERIALS SCIENCE↗