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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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At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
NASA NTRS2002

Maximizing TDRS Command Load Lifetime

The GNC software onboard ISS utilizes TORS command loads, and a simplistic model of TORS orbital motion to generate onboard TORS state vectors. Each TORS command load contains five "invariant" orbital elements which serve as inputs to the onboard propagation algorithm. These elements include semi-major axis, inclination, time of last ascending node crossing, right ascension of ascending node, and mean motion. Running parallel to the onboard software is the TORS Command Builder Tool application, located in the JSC Mission Control Center. The TORS Command Builder Tool is responsible for building the TORS command loads using a ground TORS state vector, mirroring the onboard propagation algorithm, and assessing the fidelity of current TORS command loads onboard ISS. The tool works by extracting a ground state vector at a given time from a current TORS ephemeris, and then calculating the corresponding "onboard" TORS state vector at the same time using the current onboard TORS command load. The tool then performs a comparison between these two vectors and displays the relative differences in the command builder tool GUI. If the RSS position difference between these two vectors exceeds the tolerable lim its, a new command load is built using the ground state vector and uplinked to ISS. A command load's lifetime is therefore defined as the time from when a command load is built to the time the RSS position difference exceeds the tolerable limit. From the outset of TORS command load operations (STS-98), command load lifetime was limited to approximately one week due to the simplicity of both the onboard propagation algorithm, and the algorithm used by the command builder tool to generate the invariant orbital elements. It was soon desired to extend command load lifetime in order to minimize potential risk due to frequent ISS commanding. Initial studies indicated that command load lifetime was most sensitive to changes in mean motion. Finding a suitable value for mean motion was therefore the key to achieving this goal. This goal was eventually realized through development of an Excel spreadsheet tool called EMMIE (Excel Mean Motion Interactive Estimation). EMMIE utilizes ground ephemeris nodal data to perform a least-squares fit to inferred mean anomaly as a function of time, thus generating an initial estimate for mean motion. This mean motion in turn drives a plot of estimated downtrack position difference versus time. The user can then manually iterate the mean motion, and determine an optimal value that will maximize command load lifetime. Once this optimal value is determined, the mean motion initially calculated by the command builder tool is overwritten with the new optimal value, and the command load is built for uplink to ISS. EMMIE also provides the capability for command load lifetime to be tracked through multiple TORS ephemeris updates. Using EMMIE, TORS command load lifetimes of approximately 30 days have been achieved.

Brown, Aaron J.↗
DOE OSTI2026

Defect-Limited Carrier Lifetime in Epitaxially Strained Germanium-On-Silicon Heterostructures

Epitaxially strained germanium-on-silicon (Ge-on-Si) heterostructures are central to next-generation photonic and electronic devices, yet their performance remains strongly constrained by defect-limited carrier lifetimes. In this work, we investigate the impact of defects on the carrier lifetime in relaxed Ge-on-Si and strained Ge-on-Si heterostructures. High-resolution X-ray diffraction quantifies the strain-state in Ge and reveals signatures of strain relaxation due to lattice mismatch. Cross-sectional and plan-view transmission electron microscopy analyses enable direct visualization of interfacial defects and quantification of threading dislocation densities (TDDs) within the Ge layer. However, the presence of a dense misfit dislocation network obscures the threading dislocation signatures, preventing reliable TDD determination by plan-view transmission electron microscopy in strained-Ge (..epsilon..-Ge). To assess the defect density in this case, etch-pit density measurements were performed, providing an alternative means of quantifying the TDDs in the ..epsilon..-Ge layer. Carrier lifetime measurements by microwave-reflection photoconductive decay reveal a clear relationship with TDDs ranging from 5 x 103 cm-2 to 2 x 1010 cm-2, confirming Shockley-Read-Hall recombination as the limiting mechanism at lower defect densities, with TDD-dominated recombination at higher defect densities. The Ge-on-Si relaxed heterostructure exhibited lifetimes much lower (~12 ns) than the lattice-matched Ge on gallium arsenide (GaAs) (~158 ns) heterostructure. Introducing controlled tensile strain reduces defect formation, suppresses strain-relaxation pathways, and leads to measurable improvements in minority carrier lifetime from 12 ns to 171 ns. These results establish a direct relation between defect suppression and carrier recombination dynamics in both relaxed Ge-on-Si grown directly on Si and strained Ge-on-Si heterostructures incorporating compound-semiconductor buffer layers, offering a materials-driven pathway for engineering Ge with improved carrier lifetime for photonic applications.

36 MATERIALS SCIENCE↗
NASA NTRS2014

Model Evaluation of Methods for Estimating Surface Emissions and Chemical Lifetimes from Satellite Data

Column densities from satellite retrievals can provide valuable information for estimating emissions and chemical lifetimes objectively across the globe. To better understand the uncertainties associated with these estimates, we test four methods using simulated column densities from a point source: a box model approach, a 2D Gaussian fit, an Inverse Radius fit and an Exponentially-Modified Gaussian fit. The model results were simulated using the WRF and CAMx models for the year 2005, for a single point source outside Atlanta in Georgia, USA with specified emissions and three chemical scenarios: no chemical reactions, 12 h chemical lifetime and 1 h chemical lifetime. No other sources were included in the simulations. We find that the box model provides reliable estimates irrespective of plume speed and plume direction, if the plume speed and the chemical lifetime are known accurately. The 2D Gaussian fit was found to be sensitive to plume speed and direction, and requires omnidirectional dispersion in order to have a decent fit. However, the 2D Gaussian fit is only an approximate fit to the data, and the discrepancies mean that the results are dependent on the geographical domain used for the optimization. An Inverse Radius fit is introduced to correct this issue, which is found to provide improved emissions and lifetime estimates. The Exponentially-Modified Gaussian fit also gave improved estimates. It is however dependent on accurate plume rotation such that reported chemical lifetimes with this method could be significantly underestimated.

Emission inventory↗
NASA NTRS2016

Effect of Atmospheric Organics on Bioavailable Fe Lifetime in the Oceans

The deposition of atmospheric aerosols is an important supply pathway of soluble iron (sol-Fe) to the global oceans influencing marine ecosystem processes and climate. Previous studies have shown that natural and anthropogenic acidic trace gases, when mixed with mineral dust, can lead to production of sol-Fe, leading to considerable increase in dust-Fe solubility. Recent studies have further highlighted the importance of atmospheric organic compounds/ligands in the production of sol-Fe during atmospheric transport and transformation of mineral aerosols. However, the actual scope of this aerosol sol-Fe for stimulating the primary productivity in the oceans is determined by both: the total atmospheric fluxes of sol-Fe and the lifetime of sol-Fe after its deposition to the ocean. In this study several atmospheric organic ligands were investigated for their effect on the lifetime of sol-Fe after mixing with seawater. Organic ligands were selected based on their abundance in the marine boundary layer and rainwater and their ability to form bidentate complexes with Fe. The results reveal that the tested organics had minor influence on Fe(II) lifetime in seawater. However, results also show that some organic acid considerably extended the lifetime of colloidal and aqueous Fe(III). Using these results we simulate aerosol sol-Fe lifetime in the ocean for different mineral dust deposition events in the presence and the absence of atmospheric organic ligands. The calculations suggest that when a large dust plume is assumed to contain Fe(II) alone, less than 15% of aerosol sol-Fe gets complexed with marine organic ligands. However, this fraction increases to over 90% when atmospheric Fe is allowed to bond with atmospheric organic acids prior to deposition to the oceans. Calculations also show that for the conditions when seawater organic ligands get titrated by Fe released from dust aerosol particles, retention of sol-Fe in the ocean depends on surface ocean mixing, i.e., replenishing rates for Fe-bonding ligands from below. This study suggests that in future ocean biogeochemistry models more attention should be devoted to better quantification of the role of atmospheric organic acids in the lifetime of aerosol sol-Fe after its deposition to the ocean and the improvements of upper ocean turbulence parameterizations.

Oceans↗
DOE OSTI2025

Non-monotonic size-dependent exciton radiative lifetime in CsPbBr3 nanocrystals

Lead halide perovskite nanocrystals have attracted intense interest due to their desirable optical properties, diverse structural features, and size-tunable excitonic structure. Here we show that, under ambient conditions, a non-monotonic trend in radiative lifetime emerges from the interplay of size, lattice symmetry and excitonic structure. Small nanocrystals exhibit long radiative lifetimes due to weakly emissive excitons, but the oscillator strength increases and shortens the lifetime for nanocrystals approaching intermediate confinement. For larger nanocrystals with higher exciton density of states (DOS), the radiative lifetime is lengthened due to depopulation of the bright exciton manifold into thermally accessible dim states. A size-dependent structural symmetry lowering transition from cubic to orthorhombic is observed by XRD and MD simulations, and the non-monotonic radiative lifetime trend emerges only in lower symmetry structures with an increased dim exciton DOS. These findings shed light on the impact of nanocrystal size and structure on radiative lifetime and pave the way for tailored optical materials in various optical applications.

optical materials↗
DOE OSTI2026

Analytic rate theory of polariton relaxation that explains long polariton lifetime

Hybridization of a molecular exciton with a quantized photon creates a polariton. Despite extensive experimental investigations, the apparent lifetime of the exciton–polariton is not well-understood. For this work, we examined the steady-state population dynamics for a Holstein–Tavis–Cumming Hamiltonian to illuminate the long-term polaritonic dynamics and lifetime of the exciton–polariton in an optical cavity. For a realistic description of polariton relaxation, cavity loss and various exciton decay channels are included in the model. We found that in the presence of weak but finite exciton loss, the apparent lifetime of the lower polariton coincides with the out-of-cavity exciton lifetime and is independent of cavity-matter detuning. This is a simple explanation for the experimentally observed lifetimes for exciton polaritons and theoretically justifies the dark state reservoir hypothesis. Furthermore, if the upper polariton is initially populated, the system reaches the steady state very quickly, leading to single-exponential polariton relaxation. Starting from the lower polariton leads to a longer pre-steady-state time period, leading to double-exponential relaxation. Finally, we considered the effect of site orientational disorders and the exciton frequency disorderers. Under the collective limit, the effects of this disorder can be included in Fermi’s golden rule population dynamics without explicit sampling. For the exciton energy disorders, numerical calculations are needed. Our theoretical framework is applicable to interpret exciton–polariton experiments, especially related to the measured apparent lifetime of polaritons.

Chemical dynamics↗
DOE OSTI2024

Understanding Environmental Barrier Coating Lifetimes and Performance for Industrial Gas Turbines

Hydrogen or hydrogen blend fuels are expected to replace natural gas in land-based industrial gas turbines (IGTs) to support a greener power economy. Silicon carbide (SiC) base ceramic matrix composites (CMCs) are considered for replacement of Ni-based superalloys to facilitate future efficiency improvements. SiC CMCs require environmental barrier coatings (EBCs) to mitigate volatilization from high-temperature steam, thus making the EBC lifetime critical information for identifying CMC component lifetimes. Here, the goal of this project is to determine the maximum bond coating temperature underneath the EBC for achieving an IGT component lifetime goal of 25,000 h, which is far greater than current CMC component lifetime requirements for aeroturbine applications. To provide data for the lifetime model, laboratory testing used atmospheric plasma-sprayed rare-earth silicate EBCs on monolithic SiC substrates with an intermediate Si bond coating. Specimens exposed to 1-h thermal cycles in flowing air–steam environments and reaction kinetics were assessed from 700 °C to 1350 °C by measuring the thickness of the thermally grown silica scales. The silica growth and phase transformation appear critical in predicting EBC lifetime and several strategies have been explored to reduce the oxide growth rate and improve EBC durability at elevated temperatures. Advanced characterization using Raman spectroscopy has helped clarify this system.

08 HYDROGEN↗
DOE OSTI2024

Understanding EBC Lifetimes and Performance for Industrial Gas Turbines

Hydrogen or hydrogen blend fuels are expected to replace natural gas in land-based industrial gas turbines (IGTs) to support a greener power economy. Silicon carbide (SiC) base ceramic matrix composites (CMCs) are considered for replacement of Ni-based superalloys to facilitate future efficiency improvements. SiC CMCs require environmental barrier coatings (EBCs) to mitigate volatilization from high-temperature steam, thus making the EBC lifetime critical information for identifying CMC component lifetimes. The goal of this project is to determine the maximum bond coating temperature underneath the EBC for achieving an IGT component lifetime goal of 25,000 h, which is far greater than current CMC component lifetime requirements for aero-turbine applications. To provide data for the lifetime model, laboratory testing used plasma-sprayed rare-earth silicate EBCs on monolithic SiC substrates with an intermediate Si bond coating. Specimens exposed to 1-h thermal cycles in flowing air-steam environments and reaction kinetics were assessed from 700°-1350°C by measuring the thickness of the thermally grown silica scales. The silica growth and phase transformation appear critical in predicting EBC lifetime and several strategies have been explored to reduce the oxide growth rate and improve EBC durability at elevated temperatures. Advanced characterization using Raman spectroscopy has helped clarify this system.

Ridley, Mackenzie↗
DOE OSTI2025

Ultra-high Information-content Chemical Imaging with Broadband Coherent Anti-Stokes Raman and Two-photon Fluorescence Lifetime Microscopy

Raman fingerprint spectroscopy and fluorescence lifetime imaging are emerging tools for studying metabolic profiles of biological specimens. While Raman fingerprint spectroscopy detects intrinsic molecular vibrations that reflect the molecular composition and chemical environment of a sample, fluorescence lifetime imaging measures changes in the excited-state lifetime of fluorophores that are sensitive to their microenvironments. Here, we present a multimodal imaging platform combining broadband coherent anti-Stokes Raman scattering (BCARS) and two-photon fluorescence lifetime imaging (2p-FLIM) microscopy that can acquire biologically relevant Raman fingerprint spectra and fluorescence lifetime signals in vivo and simultaneously. The tremendous chemical information obtained from spatially co-registered BCARS and 2p-FLIM images allows us to characterize the subtle differences between sub-cellular compartments and verify the potential false-positive results generated by fluorescence imaging alone. This is demonstrated by directly comparing the BCARS, 2p-FLIM, and two-photon excitation fluorescence(TPEF) signals simultaneously obtained from the same dye-stained organelle in the live, intact C. elegans expressing a green fluorescent protein (GFP) marker. In this work, we introduce the BCARS/2p-FLIM/TPEF setup scheme, the image acquisition steps, data processing, and representative results showing that the cross-modality imaging method enables rigorous characterization and in vivo detection at sub-cellular resolution. Furthermore, this protocol provides a framework for simultaneous chemical and fluorescence lifetime imaging to improve the accuracy of biological interpretation in complex living systems.

Xu, Haoyu [Georgia Institute of Technology, Atlant↗
NASA NTRS1976

Distribution of lifetimes for coronal soft X-ray bright points

The lifetime 'spectrum' of X-ray bright points (XBPs) is measured for a sample of 300 such features using soft X-ray images obtained with the S-054 X-ray spectrographic telescope aboard Skylab. 'Spectrum' here is defined as a function which gives the relative number of XBPs having a specific lifetime as a function of lifetime. The results indicate that a two-lifetime exponential can be fit to the decay curves of XBPs, that the spectrum is heavily weighted toward short lifetimes, and that the number of features lasting 20 to 30 hr or more is greater than expected. A short-lived component with an average lifetime of about 8 hr and a long-lived 1.5-day component are consistently found along with a few features lasting 50 hr or more. An examination of differences among the components shows that features lasting 2 days or less have a broad heliocentric-latitude distribution while nearly all the longer-lived features are observed within 30 deg of the solar equator.

Golub, L.↗
NASA NTRS1978

Lifetime and diffusion length measurements on silicon material and solar cells

Experimental methods were evaluated for the determination of lifetime and diffusion length in silicon intentionally doped with potentially lifetime-degrading impurities found in metallurgical grade silicon, impurities which may be residual in low-cost silicon intended for use in terrestrial flat-plate arrays. Lifetime measurements were made using a steady-state photoconductivity method. Diffusion length determinations were made using short-circuit current measurements under penetrating illumination. Mutual consistency among all experimental methods was verified, but steady-state photoconductivity was found preferable to photoconductivity decay at short lifetimes and in the presence of traps. The effects of a number of impurities on lifetime in bulk material, and on diffusion length in cells fabricated from this material, were determined. Results are compared with those obtained using different techniques. General agreement was found in terms of the hierarchy of impurities which degrade the lifetime.

Othmer, S.↗
NASA NTRS1991

Photoluminescence lifetime measurements in InP wafers

A simple apparatus to measure the minority carrier lifetime in InP has been developed. The technique stimulates the sample with a short pulse of light from a diode laser and measures the photoluminescence decay to extract the minority carrier lifetime. The photoluminescence lifetime in InP as a function of doping on both n- and p-type material is examined. The results also show a marked difference in the lifetime of n-type InP and p-type InP of similar doping levels. N-type InP shows a lifetime considerably longer than the expected radiative limited lifetime.

Landis, Geoffrey A.↗
NASA NTRS1998

Perimeter Governed Minority Carrier Lifetimes in 4H-SiC p+n Diodes Measured by Reverse Recovery Switching Transient Analysis

Minority carrier lifetimes in epitaxial 4H-SiC p-n junction diodes were measured via an analysis of reverse recovery switching characteristics. Behavior of reverse recovery storage time (t(sub s)) as a function of initial ON-state forward current (I(sub f)) and OFF-state reverse current (I(sub R)) followed well-documented trends which have been observed for decades in silicon p-n rectifiers. Average minority carrier (hole) lifetimes (tau(sub p)) calculated from plots of t(sub s) vs I(sub R)/I(sub F) strongly decreased with decreasing device area. Bulk and perimeter components of average hole lifetimes were separated by plotting tau(sub p) as a function of device perimeter-to-area ratio (P/A). This plot reveals that perimeter recombination is dominant in these devices, whose areas are all less than 1 square mm. The bulk minority carrier (hole) lifetime extracted from the 1/Tau(sub p) vs P/A plot is approximately 0.7 microns, well above the 60 ns to 300 ns average lifetimes obtained when perimeter recombination effects are ignored in the analysis. Given the fact that there has been little previous investigation of bipolar diode and transistor performance as a function of perimeter-to-area ratio, this work raises the possibility that perimeter recombination may be partly responsible for poor effective minority carrier lifetimes and limited performance obtained in many previous SiC bipolar junction devices.

Neudeck, Philip G.↗
NASA NTRS1998

The Postshock Chemical Lifetimes of Outflow Tracers and a Possible New Mechanism to Produce Water Ice Mantles

We have used a coupled time-dependent chemical and dynamical model to investigate the lifetime of the chemical legacy in the wake of C-type shocks. We concentrate this study on the chemistry of H2O and O2, two molecules which are predicted to have abundances that are significantly affected in shock-heated gas. Two models are presented: (1) a three-stage model of preshock, shocked, and postshock gas; and (2) a Monte Carlo cloud simulation where we explore the effects of stochastic shock activity on molecular gas over a cloud lifetime. For both models we separately examine the pure gas-phase chemistry as well as the chemistry including the interactions of molecules with grain surfaces. In agreement with previous studies, we find that shock velocities in excess of 10 km/s are required to convert all of the oxygen not locked in CO into H2O before the gas has an opportunity to cool. For pure gas phase models the lifetime of the high water abundances, or "H2O legacy," in the postshock gas is approximately (4-7) x 10(exp 5) yr, independent of the gas density. A density dependence for the lifetime of H2O is found in gas-grain models as the water molecules deplete onto grains at the depletion timescale. Through the Monte Carlo cloud simulation we demonstrate that the time-average abundance of H2O, the weighted average of the amount of time gas spends in preshock, shock, and postshock stages, is a sensitive function of the frequency of shocks. Thus we predict that the abundance of H2O, and to a lesser extent O2, can be used to trace the history of shock activity in molecular gas. We use previous large-scale surveys of molecular outflows to constrain the frequency of 10 km/s shocks in regions with varying star formation properties and discuss the observations required to test these results. We discuss the postshock lifetimes for other possible outflow tracers (e.g., SiO and CH3OH) and show that the differences between the lifetimes for various tracers can produce potentially observable chemical variations between younger and older outflows. For gas-grain models we find that the abundance of water-ice on grain surfaces can be quite large and is comparable to that observed in molecular clouds. This offers a possible alternative method to create water mantles without resorting to grain surface chemistry: gas heating and chemical modification due to a C-type shock and subsequent depletion of the gas-phase species onto grain mantles.

Bergin, Edwin A.↗
NASA NTRS1994

(abstract) Distribution of Unimolecular Lifetimes in Ion-Molecule Association Reactions

The distribution of unimolecular lifetimes of ion-molecule complexes formed in association reactions has been measured by ion cyclotron double-resonance. The mean unimolecular lifetimes of (H(sub 2)C(sub 6)N(sub 2)(sup +))(sup *) and (CH(sub 3)CN.CH(sub 3)(sup +))(sup *) were determined to be 180 (micro)s and 140 (micro)s respectively. A theoretical examination of the distribution of lifetimes of (CH(sub 3)CN.CH(sub 3)(sup +))(sup *) was conducted using a RRKM model. The RRKM distribution, when modified by experimental constraints, was found to be a good approximation of the experimentally determined lifetime distribution. The lifetimes for unimolecular dissociation and radiative relaxation, and the absolute efficiency of collisional relaxation are also reported.

unimolecular lifetimes ion-molecule complexes RRKM↗
DOE OSTI2024

Coatings for CSP Lifetime

The feasibility and performance of tower-technology-based concentrated solar power (CSP) is highly dependent on the efficiency of the energy transformation from sun to heat at the receiver. The higher the solar absorptivity of the receiver coating, the higher the efficiency of the plant as a whole. BrightSource Energy (BSE) has developed a series of High-Performance Coating (HPC) systems in order to achieve high absorptivity over the plant lifetime (25-35 years). This requires stable coatings that are easily applicable on the large receiver surface and will maintain their optical properties under intense solar flux and thousands of heating and cooling cycles in desert conditions. Different coating formulations are required according to the differing plant conditions: receiver materials, operating conditions (temperatures, daily cycles, etc.), and environmental conditions. BSE also developed a coating for the next generation of CSP receivers, such as those being under DOE’s CSP Gen3 program, which will be operated with high temperature heat transfer fluids at temperatures of up to 800°C, which is significantly hotter than the operating temperature of current systems. Once the coating is formulated, the next challenge is evaluating its lifetime properties. BSE has found several independent failure modes that impact HPC absorptivity degradation: • Decrease in HPC optical properties due to oxidation in the receiver tubes surface below the HPC; • HPC film deterioration due to cycling of temperatures and humidity due to daily operation startup and shutdown as well as changing ambient conditions; • Mechanical degradation due to erosion by sand and wind. Existing test methods examine various aspects independently, but do not provide a combined accelerated lifetime result. Creating such a combined test suite, with a way to interpret the results to predict the coating’s projected lifetime, was the ultimate goal of this project. The project was divided into three major workstreams: lab testing (individual failure mode tests and combined failure mode tests); developing a theoretical model for aging; and validation of the test apparatus via on-sun testing in near real-world conditions at CIEMAT-PSA. Developing a test apparatus that accurately controlled the temperature while also introducing the desired solar flux proved more challenging than expected. While in the end we did succeed in creating a test apparatus that can control temperature, solar flux, and humidity, the results did not appear to accelerate the lifetime of the samples as desired. We suspect that to properly accelerate the samples we must also subject the samples to increased amounts of oxygen. Similarly, while we successfully created a combined model that is publicly available, we were unable to validate it sufficiently to feel comfortable recommending it as a general guideline.

14 SOLAR ENERGY↗
DOE OSTI2025

Ambient Synthesis for Fe(II) Polypyridyl Complexes with an Order of Magnitude Increase in Charge-Transfer Excited-State Lifetimes over [Fe(bpy) 3 ] 2+

Replacing precious metals with abundant metals is an important research focus in photochemical energy conversion and storage to meet global energy demands. However, transition metal complexes (TMCs) based on abundant 3d metals typically possess photochemical disadvantages─such as short charge-transfer excited-state lifetimes─and molecular modifications have focused on optimizing the interplay of structure, dynamics, and energetics to overcome their limitations. One strategy to do so is the use of bespoke ligands that can extend the lifetimes of chemically useful excited states. Here, in this study, we report the synthesis and characterization of novel Fe(II) complexes featuring lengthy polypyridyl ligands that can be readily synthesized. Steady-state and transient absorption spectroscopies indicate that these complexes have desirable properties and their excited metal-to-ligand charge-transfer states live an order of magnitude longer than in the benchmark [Fe(bpy) 3 ] 2+ . This lifetime is largely preserved in the heteroleptic complexes, thereby enabling the preparation of asymmetric complexes. Additionally, we apply nonradiative transition theory to explain the long-time decay kinetics. In light of their ease of preparation and reasonable excited-state lifetimes, we suggest the use of these complexes in Fe(II) dye-sensitized solar cells, where the rate of charge injection would be competitive with increased lifetime.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Generalizing Reversible Triplet–Triplet Energy Transfer as a Strategy to Increase Excited-State Lifetime in Copper(I) Charge-Transfer Chromophores

In this work, we generalize reversible triplet–triplet energy transfer (TTET) as a strategy to achieve long (μs range) excited-state lifetimes in copper(I) photosensitizers of the general formula Cu(RNacNac)(CN-Ar) (RNacNac is a substituted β-diketiminate and CN-Ar is an aryl isocyanide). Six new complexes are presented where the isocyanide is substituted with a triplet–acceptor moiety─anthracene, naphthalene, or phenanthrene. In-depth photophysical analysis reveals that energetic matching of the charge-transfer ( 3 CT) and acceptor-localized 3 (π→π*) states is key to achieving long triplet excited-state lifetimes via reversible TTET. With 2-isocyanoanthracene as the acceptor ligand, 3 CT and 3(π→π*) are not energetically proximate, and irreversible quenching of 3 CT occurs. With a small 0.1–0.2 eV gap between the two triplet states, luminescence originates from the 3 CT state with a moderate excited-state lifetime of 250 or 283 ns observed. As key to the success of this approach, we demonstrate that altering the N-substituent on the RNacNac ligand modulates the energy of the 3 CT state, giving three complexes where the 3 CT and 3 (π→π*) energies are perfectly matched and the excited-state lifetimes are much longer, spanning 1.9–2.7 μs. As such, the key lesson of this work is that long triplet-state lifetimes in these compounds can be achieved by proper “mixing and matching” of the RNacNac ligand, which influences the 3 CT energy, and the triplet acceptor group which dictates the energy of the 3 (π→π*) state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗