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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 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Metal–Organic Framework as a Dual Support for Organic Photosensitizers and Single-Atom Catalysts

Metal–organic framework (MOF)-supported single-atom catalysts (SACs) possess integrated unique capabilities of both MOF and SACs, which represent a promising class of catalysts for photocatalytic applications. Herein, we report the incorporation of nickel (Ni) SACs onto its zirconium node and the functionalization of the organic linker of the zirconium MOF with perylene tetracarboxylic dianhydride (PDA), resulting in the formation of a hybrid MOF (denoted as Ni-PiU) with significantly enhanced light absorption ability in the visible region. Using the combination of time-resolved emission and X-ray absorption spectroscopy, we show that efficient charge separation occurs by electron transfer from incorporated PDA to Ni SACs with super slow charge recombination dynamics. As a result of these important photophysical properties, Ni-PiU MOF exhibits excellent photocatalytic activity and durability for the hydrogen evolution reaction. Finally, this work demonstrates the unique ability of MOFs as a dual platform to incorporate both SACs and a light absorption unit into their framework, providing a promising strategy for rational design of next-generation photocatalytic materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Ion-Assisted Ligand Exchange for Efficient and Stable Inverted FAPbI 3 Quantum Dot Solar Cells

Perovskite quantum dot (QD) has emerged as a promising material for photovoltaics with its superior stability compared to their three-dimensional bulk counterparts, owing to its thermodynamically stabilized photoactive phase. However, ligand management on perovskite QD surfaces is extremely difficult due to the ionic nature of the perovskite lattice, which often leads to either incomplete removal of the native insulating ligands or formation of trap states during the ligand-exchange process, greatly hampering the photovoltaic performances. In this work, we report an ion-assisted ligand-exchange method for FAPbI 3 QDs using AOAc (A = formamidinium (FA + ), guanidinium (GA + ), and phenethylammonium (PEA + ), OAc = acetate), with the A + and OAC - ions promoting the removal of native long-chain insulating ligands. Further, the more complete ligand exchange results in dense and well-oriented packing of QDs, together with the enhancement of electronic coupling and charge transport across QDs. In addition, the A + and OAC - ions can fill the surface A-/X-site vacancies, respectively, reducing the QD surface trap state density and hence suppressing charge recombination and iodide migration. The p-i-n inverted QD solar cells fabricated with this ligand-exchange method exhibit significant enhancement in shortcircuit current density (J SC ), reaching a PCE of 10.13%. Moreover, unencapsulated devices show impressive stabilities of more than 7300 h (10 months) storage time in a N 2 -filled glovebox.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Long-Lived Triplet Excited State in a Heterogeneous Modified Carbon Nitride Photocatalyst

Heterogeneous carbon nitrides have numerous advantages as photocatalysts, including strong light absorption, tunable band edges, and scalability, but their performance and continued development are limited by fast charge recombination and an under-developed mechanistic understanding of photodriven interfacial electron transfer. These shortcomings are a result of complex photophysics, leading to rate asynchrony between oxidation and reduction, as well as redox processes driven out of electronic trap states rather than excited states. We show that a well-defined triplet excited state in cyanamide-modified carbon nitride is realized with appropriately sized particles. The utility of this long-lived excited state is demonstrated by its ability to drive a hydroamidation photoredox cycle. By the tuning of the particle size of CN x , the oxidation–reduction photochemistry of carbon nitride may be balanced to achieve a redox-neutral closed photocatalytic cycle. Here, these results uncover a triplet excited state chemistry for appropriately sized CNx particles that preludes a rich energy and electron transfer photochemistry for these materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Driving Force Dependent Photoinduced Charge Transfer Dynamics in Polymer-Wrapped Semiconducting Single-Walled Carbon Nanotubes

Here, we investigate the thermodynamic driving-force dependences of photoinduced charge separation (CS) and subsequent charge transfer dynamics in single-walled carbon nanotube (SWNT)–perylenediimide (PDI) donor–acceptor (D–A) superstructures. Pump–probe spectroscopy reveals that [SWNT (•+)n ]-(PDI –• ) n CS states form on an ∼100 fs time scale following photoexcitation; these dynamics are invariant across an ∼400 mV driving force range, indicating that SWNT hole polaron formation time scales are determined by nanotube lattice and solvent relaxation. These CS states feature SWNT hole polarons adjacent to (geminate) and nearby (nongeminate) PDI radical anions. Analysis of the free energy dependence for charge recombination (CR) of [SWNT •+ ] geminate -(PDI –• ) CS states highlights an ∼2 meV value for D–A electronic coupling (HAB) and ∼0.93 eV for the total reorganization energy (λ T ). A corresponding driving force dependence of the CR dynamics for [SWNT •+ ] nongeminate -(PDI –• ) CS states indicates a diminished H AB value (∼0.6 meV) and a larger λ T (∼1.1 eV), consistent with larger transfer distances. SWNT excitons that persist following photoinduced CS drive photooxidation of PDI –• components of [SWNT (•+)n ]-(PDI –• ) n CS states ( 1 SWNT* + PDI •– → PDI + SWNT •– ); this reaction manifests a significantly reduced λ T value (∼0.67 eV) as the initially prepared SWNT reduced state bears the character of a conduction band injected electron ([SWNT •– ] CB ). This reaction thus gives rise to relaxed, nongeminate SWNT electron and hole polarons on the same nanotube; these polarons react on a 10 2 ps time scale independent of the electronic structure of these SWNT-PDI superstructures.

anions↗
DOE OSTI2023

Auxiliary sequential deposition enables 19%-efficiency organic solar cells processed from halogen-free solvents

High-efficiency organic solar cells are often achieved using toxic halogenated solvents and additives that are constrained in organic solar cells industry. Therefore, it is important to develop materials or processing methods that enabled highly efficient organic solar cells processed by halogen free solvents. In this paper, we report an innovative processing method named auxiliary sequential deposition that enables 19%-efficiency organic solar cells processed by halogen free solvents. Our auxiliary sequential deposition method is different from the conventional blend casting or sequential deposition methods in that it involves an additional casting of dithieno[3,2-b:2’,3’-d]thiophene between the sequential depositions of the donor (D18-Cl) and acceptor (L8-BO) layers. The auxiliary sequential deposition method enables dramatic performance enhancement from 15% to over 18% compared to the blend casting and sequential deposition methods. Furthermore, by incorporating a branched-chain-engineered acceptor called L8-BO-X, device performance can be boosted to over 19% due to increased intermolecular packing, representing top-tier values for green-solvent processed organic solar cells. Comprehensive morphological and time-resolved characterizations reveal that the superior blend morphology achieved through the auxiliary sequential deposition method promotes charge generation while simultaneously suppressing charge recombination. This research underscores the potential of the auxiliary sequential deposition method for fabricating highly efficient organic solar cells using environmentally friendly solvents.

14 SOLAR ENERGY↗
DOE OSTI2024

Tuning polymer-backbone coplanarity and conformational order to achieve high-performance printed all-polymer solar cells

Abstract All-polymer solar cells (all-PSCs) offer improved morphological and mechanical stability compared with those containing small-molecule-acceptors (SMAs). They can be processed with a broader range of conditions, making them desirable for printing techniques. In this study, we report a high-performance polymer acceptor design based on bithiazole linker (PY-BTz) that are on par with SMAs. We demonstrate that bithiazole induces a more coplanar and ordered conformation compared to bithiophene due to the synergistic effect of non-covalent backbone planarization and reduced steric encumbrances. As a result, PY-BTz shows a significantly higher efficiency of 16.4% in comparison to the polymer acceptors based on commonly used thiophene-based linkers (i.e., PY-2T, 9.8%). Detailed analyses reveal that this improvement is associated with enhanced conjugation along the backbone and closer interchain π-stacking, resulting in higher charge mobilities, suppressed charge recombination, and reduced energetic disorder. Remarkably, an efficiency of 14.7% is realized for all-PSCs that are solution-sheared in ambient conditions, which is among the highest for devices prepared under conditions relevant to scalable printing techniques. This work uncovers a strategy for promoting backbone conjugation and planarization in emerging polymer acceptors that can lead to superior all-PSCs.

14 SOLAR ENERGY↗
DOE OSTI2022

Defect engineering in wide-bandgap perovskites for efficient perovskite–silicon tandem solar cells

Wide-bandgap (WBG) mixed-halide perovskites show promise of realizing efficient tandem solar cells but at present suffer from large open-circuit voltage loss and the mechanism is still unclear. Here we show that WBG perovskites with iodide–bromide compositions have an increased concentration of deep traps induced by iodide interstitials, which limits performance of WBG perovskite cells. We employ tribromide ions to suppress the iodide interstitial formation and thus reduce charge recombination in bladed WBG perovskite films of Cs 0.1 FA 0.2 MA 0.7 Pb(I 0.85 Br 0.15 )3. The 1-µm-thick opaque WBG perovskite solar cells have an efficiency of 21.9%, a small open-circuit voltage deficit of 0.40 V and a large fill factor of 83%. The efficiency of the best-performing monolithic perovskite–silicon tandem cell using this perovskite reaches 28.6%. Furthermore, the tribromide addition also suppresses light-induced phase segregation in WBG perovskites and thus enhance device stability. Encapsulated tandem cells maintain 93% of their initial efficiency after operation for 550 h.

14 SOLAR ENERGY↗
DOE OSTI2022

Photosynthetic modulation during the diurnal cycle in a unicellular diazotrophic cyanobacterium grown under nitrogen-replete and nitrogen-fixing conditions

Abstract Cyanobacteria are the only oxygenic photosynthetic organisms that can fix nitrogen. In diazotrophic cyanobacteria, the regulation of photosynthesis during the diurnal cycle is hypothesized to be linked with nitrogen fixation and involve the D1 protein isoform PsbA4. The amount of bioavailable nitrogen has a major impact on productivity in aqueous environments. In contrast to low- or nitrogen-fixing (−N) conditions, little data on photosynthetic regulation under nitrogen-replete (+ N) conditions are available. We compared the regulation of photosynthesis under −N and + N conditions during the diurnal cycle in wild type and a psbA4 deletion strain of the unicellular diazotrophic cyanobacterium Cyanothece sp. ATCC 51142. We observed common changes to light harvesting and photosynthetic electron transport during the dark in + N and −N conditions and found that these modifications occur in both diazotrophic and non-diazotrophic cyanobacteria. Nitrogen availability increased PSII titer when cells transitioned from dark to light and promoted growth. Under −N conditions, deletion of PsbA4 modified charge recombination in dark and regulation of PSII titer during dark to light transition. We conclude that darkness impacts the acceptor-side modifications to PSII and photosynthetic electron transport in cyanobacteria independently of the nitrogen-fixing status and the presence of PsbA4.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Mechanistic investigation of a visible light mediated dehalogenation/cyclisation reaction using iron( iii ), iridium( iii ) and ruthenium( ii ) photosensitizers

The mechanism of a visible light-driven dehalogenation/cyclization reaction was investigated using ruthenium(II), iridium(III) and iron(III) photosensitizers by means of steady-state photoluminescence, time-resolved infrared spectroscopy, and nanosecond/femtosecond transient absorption spectroscopy. The nature of the photosensitizer was found to influence the product distribution such that the dehalogenated, non-cyclized products were only detected for the iron photosensitizer. Strikingly, with the iron photosensitizer, large catalytic yields required a low dielectric solvent such as dichloromethane, consistent with a previous publication. This low dielectric solvent allowed ultrafast charge-separation to outcompete geminate charge recombination and improved cage escape efficiency. Finally, the identification of reaction mechanisms unique to the iron, ruthenium, and iridium photosensitizer represents progress towards the long-sought goal of utilizing earth-abundant, first-row transition metals for emerging energy and environmental applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Air-stable ternary organic solar cells achieved by using fullerene additives in non-fullerene acceptor-polymer donor blends

Organic solar cells (OSCs) based on donor–acceptor blends have shown a rapid improvement in power conversion efficiency (PCE) now approaching, for small cells, those of the state-of-the art commercial solar modules. However, performance degradation remains one of the most critical impediments for OSC technology commercialization. Ternary solar cells where a third component, for instance an acceptor, is added to a non-fullerene acceptor–polymer donor blend are an effective approach for improving both OSC efficiency and long-term stability. Here, in this work, we study the role of two fullerene acceptors, ET18 and PCBM, as the third component in P D :Y6 blends. These fullerene derivatives significantly enhance the cell stability, which retained >90% of their initial PCEs (13–14%) even after storage in air for 6 months, compared to only ~20% retention for the binary devices. GIWAXS, AFM, in situ impedance spectroscopy and femtosecond transient absorption spectroscopy measurements reveal that the enhanced stability of the ternary devices results from a more robust blend morphology reducing charge recombination in the ternary devices during aging.

14 SOLAR ENERGY↗
DOE OSTI2025

Unveiling the role of halide mixing in the crystallization kinetics and charge transfer mechanisms of wide-bandgap organic–inorganic halide perovskites

Understanding the crystallization kinetics of Br–I mixed-halide WBG perovskite films, and their correlation to the crystallographic structure and charge transfer dynamics, is critical for advancing WBG perovskite devices. Despite many efforts to increase the photovoltaic performances of wide-bandgap (WBG, with a Br content above 20%) perovskite solar cells based on bromine–iodine (Br–I) mixed-halide perovskites, understanding the crystallization kinetics of WBG perovskite films, as well as the role of Br mixing in the crystallization kinetics, is still lacking. Furthermore, an overlooked aspect is the correlation of the halide compositions, crystallization kinetics, crystallographic structure, and charge transfer dynamics. Here, we unveil that Br–I mixed-halide WBG perovskite films undergo two intrinsically different crystallization kinetic processes. One is the intermediate solvent-complex phase-assisted growth (I-rich), and the other is top-to-bottom downward growth (Br-rich). Such downward growth (including high Br concentrations) correlates with the formation of a highly vertically oriented perovskite film, which is accompanied by defect formation caused by a dissolving and recrystallization process coupled with halide homogenization. Consequently, Br-rich WBG perovskite films exhibit enhanced charge carrier transport, but are concurrently plagued by non-radiative charge recombination. Addressing this fundamental perspective is critical to precisely tailor Br-related crystallization, which significantly affects the structure and optoelectronic properties of WBG perovskite films and devices.

Li, Nian↗
DOE OSTI2020

Probing the surface oxidation process in hexagonal boron nitride epilayers

Thermal neutron detectors based on hexagonal boron nitride ( h -BN) epilayers have demonstrated a record high efficiency among solid-state detectors at 58%. It was found that the performance of h -BN detectors is profoundly influenced by charge recombination at the surfaces. The dynamic process of surface oxidation in h -BN epilayers has been probed by x-ray photoelectron spectroscopy. The spectra of high-resolution (0.1 eV) scans indicated that the linewidth of the B 1s peak at 190.6 eV increased and the peak intensity decreased with an increase in exposure time in-air (t air ). The main B 1s peak at 190.6 eV evolved into multiple peaks at a higher binding energy position due to oxygen impurities tending to occupy nitrogen sites and form the B–O bond. Time constants of the oxidation process have been determined, revealing that the formation process of the B–O bond is very fast and within minutes in h -BN. The results suggest that reducing nitrogen vacancy generation during growth and employing surface treatment techniques would further improve the performance of h -BN devices.

2D materials↗
DOE OSTI2020

15.9% organic tandem solar cell with extended near-infrared absorption

Stacking single-junction organic solar cells is effective in increasing the power conversion efficiency (PCE) by reducing the thermalization loss and increasing the open circuit voltage. Current developments of non-fullerene acceptors (NFAs) offer a range of materials whose energy gaps are suited for absorbing relatively narrow slices of the solar spectrum, thus easing requirements for current balance between sub-elements in the multijunction stacks. In this report, we demonstrate a solution-processed tandem organic solar cell comprising a binary, visible-absorbing sub-cell and a ternary near-infrared (NIR) absorbing sub-cell. The ternary NIR sub-cell utilizes a narrow energy gap NFA acceptor that enables a broadened and increased absorption compared to a binary NIR sub-cell. An isopropanol surface treatment is developed to connect the hydrophilichydrophobic surfaces in the charge recombination zone (CRZ) located between the sub-cells. The nearly optically and electrically lossless CRZ combined with an anti-reflection coating results in a tandem OPV with PCE = 15.9 ± 0.2 % under AM 1.5G simulated illumination.

14 SOLAR ENERGY↗
DOE OSTI2024

Interface-modulated kinetic differentials in electron and hole transfer rates as a key design principle for redox photocatalysis by Sb2VO5/QD heterostructures

The efficient conversion of solar energy to chemical energy represents a critical bottleneck to the energy transition. Photocatalytic splitting of water to generate solar fuels is a promising solution. Semiconductor quantum dots (QDs) are prime candidates for light-harvesting components of photocatalytic heterostructures, given their size-dependent photophysical properties and band-edge energies. A promising series of heterostructured photocatalysts interface QDs with transition-metal oxides which embed midgap electronic states derived from the stereochemically active electron lone pairs of p-block cations. Here, we examine the thermodynamic driving forces and dynamics of charge separation in Sb2VO5/CdSe QD heterostructures, wherein a high density of Sb 5s2-derived midgap states are prospective acceptors for photogenerated holes. Hard-x-ray valence band photoemission spectroscopy measurements of Sb2VO5/CdSe QD heterostructures were used to deduce thermodynamic driving forces for charge separation. Interfacial charge transfer dynamics in the heterostructures were examined as a function of the mode of interfacial connectivity, contrasting heterostructures with direct interfaces assembled by successive ion layer adsorption and reaction (SILAR) and interfaces comprising molecular bridges assembled by linker-assisted assembly (LAA). Transient absorption spectroscopy measurements indicate ultrafast (<2 ps) electron and hole transfer in SILAR-derived heterostructures, whereas LAA-derived heterostructures show orders of magnitude differentials in the kinetics of hole (<100 ps) and electron (∼1 ns) transfer. The interface-modulated kinetic differentials in electron and hole transfer rates underpin the more effective charge separation, reduced charge recombination, and greater photocatalytic efficiency observed for the LAA-derived Sb2VO5/CdSe QD heterostructures.

Chemistry↗
DOE OSTI2024

Angular correlations of cosmic microwave background spectrum distortions from photon diffusion

ABSTRACT During cosmic recombination, charged particles bind into neutral atoms and the mean free path of photons rapidly increases, resulting in the familiar diffusion damping of primordial radiation temperature variations. An additional effect is a small photon spectrum distortion, because photons arriving from a particular sky direction were originally in thermal equilibrium at various spatial locations with different temperatures; the combination of these different blackbody temperature distributions results in a spectrum with a Compton y-distortion. Using the approximation that photons had zero mean free path prior to their second-to-last scattering, we derive an expression for the resulting y-distortion, and compute the angular correlation function of the diffusion y-distortion and its cross-correlation with the square of the photon temperature fluctuation. Detection of the cross-correlation is within reach of existing arcminute-resolution microwave background experiments such as the Atacama Cosmology Telescope and the South Pole Telescope.

Astronomy & Astrophysics↗
DOE OSTI2024

Inkjet-printed SnO x as an effective electron transport layer for planar perovskite solar cells and the effect of Cu doping

Inkjet printing is a more sustainable and scalable fabrication method than spin coating for producing perovskite solar cells (PSCs). Although spin-coated SnO 2 has been intensively studied as an effective electron transport layer (ETL) for PSCs, inkjet-printed SnO 2 ETLs have not been widely reported. Here, we fabricated inkjet-printed, solution-processed SnO x ETLs for planar PSCs. A champion efficiency of 17.55% was achieved for the cell using a low-temperature processed SnO x ETL. The low-temperature SnO x exhibited an amorphous structure and outperformed high-temperature crystalline SnO 2 . The improved performance was attributed to enhanced charge extraction and transport and suppressed charge recombination at ETL/perovskite interfaces, which originated from enhanced electrical and optical properties of SnO x , improved perovskite film quality, and well-matched energy level alignment between the SnO x ETL and the perovskite layer. Furthermore, SnO x was doped with Cu. Cu doping increased surface oxygen defects and upshifted energy levels of SnO x , leading to reduced device performance. A tunable hysteresis was observed for PSCs with Cu-doped SnO x ETLs, decreasing at first and turning into inverted hysteresis afterwards with increasing Cu doping level. This tunable hysteresis was related to the interplay between charge/ion accumulation and recombination at ETL/perovskite interfaces in the case of electron extraction barriers.

14 SOLAR ENERGY↗
DOE OSTI2022

Charge carrier coupling to the soft phonon mode in a ferroelectric semiconductor

Many crystalline solids possess strongly anharmonic “soft” phonon modes characterized by diminishing frequency as temperature approaches a critical point associated with a symmetry breaking phase transition. While electron–soft phonon coupling can introduce unique scattering channels for charge carriers in ferroelectrics, recent studies on the nonferroelectric lead halide perovskites have also suggested the central role of anharmonic phonons bearing resemblance to soft modes in charge carrier screening. Here we apply coherent phonon spectroscopy to directly study electron coupling to the soft transverse optical phonon mode in a ferroelectric semiconductor SbSI. Photogenerated charge carriers in SbSI are found to be exceptionally long lived and are associated with a transient electro-optical effect that can be explained by interactions between charge carriers and thermally stimulated soft phonon excitations. Furthermore, these results provide strong evidence for the role of electron–soft phonon coupling in the efficient screening of charge carriers and in reducing charge recombination rates, both desirable properties for optoelectronics.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Surface-modified, dye-sensitized niobate nanosheets enabling an efficient solar-driven Z-scheme for overall water splitting

While dye-sensitized metal oxides are good candidates as H 2 evolution photocatalysts for solar-driven Z-scheme water splitting, their solar-to-hydrogen (STH) energy conversion efficiencies remain low because of uncontrolled charge recombination reactions. Here, we show that modification of Ru dye–sensitized, Pt-intercalated HCa 2 Nb 3 O 10 nanosheets ( Ru /Pt/HCa 2 Nb 3 O 10 ) with both amorphous Al 2 O 3 and poly(styrenesulfonate) (PSS) improves the STH efficiency of Z-scheme overall water splitting by a factor of ~100, when the nanosheets are used in combination with a WO 3 -based O 2 evolution photocatalyst and an I 3 - /I - redox mediator, relative to an analogous system that uses unmodified Ru /Pt/HCa 2 Nb 3 O 10 . By using the optimized photocatalyst, PSS/ Ru /Al 2 O 3 /Pt/HCa 2 Nb 3 O 10 , a maximum STH of 0.12% and an apparent quantum yield of 4.1% at 420 nm were obtained, by far the highest among dye-sensitized water splitting systems and comparable to conventional semiconductor-based suspended particulate photocatalyst systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗