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At least 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Geminate exciton fusion fluorescence as a probe of triplet exciton transport after singlet fission

The geminate annihilation of two triplet excitons created by singlet exciton fission is affected by the dimensionality of transport as determined by typically anisotropic triplet exciton mobilities in organic molecular crystals. We analyze this process using a random-walk model where the time dynamics of the geminate annihilation probability is determined by the average exciton hopping times along the crystallographic directions. Here, the model is then applied to the geminate fluorescence dynamics in rubrene, where the main channel for triplet-triplet annihilation is via triplet fusion and subsequent photon emission, and we identify the transitions between transport in one, two, and three dimensions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Spin-Triplet Pairing State Evidenced by Half-Quantum Flux in a Noncentrosymmetric Superconductor

Building future fault-tolerant quantum computers may rely on a basic but so far elusive building-block-type of materials, superconductors with spin-triplet pairing, which were considered to be very rare. Now physicists demonstrate that they can be found in materials with low symmetry, different from most common crystalline materials. The new finding focuses on a particular type of crystals, the structure of which does not have inversion symmetry. For more than a decade, this material class (noncentrosymmetric superconductor) has been inferred to be a potential rich mine of spin-triplet superconductors. It is conceived that the spin-triplet pairing is promised by the broken inversion symmetry, however key experimental evidences remain lacking. Xu et al. applied a newly developed method to examine a prototype noncentrosymmetric superconductor, α-BiPd. Their experiment reveals the presence of the highly unusual half-integer quantization of magnetic flux in polycrystalline rings of α-BiPd, which is a smoking-gun evidence for spin-triplet pairing. This new finding ignites hopes that spin-triplet pairing may be a common presence among the dozens of known noncentrosymmetric superconductors as theoretically expected, which can now be unambiguously identified by the unique phenomenon of half-quantum magnetic flux.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

Long-lived, colour-triplet scalars from unnaturalness

We study that long-lived, colour-triplet scalars are a generic prediction of unnatural, or split, composite Higgs models where the spontaneous global-symmetry breaking scale f ≳ 10TeV and an unbroken SU(5) symmetry is preserved. Since the triplet scalars are pseudo Nambu- Goldstone bosons they are split from the much heavier composite-sector resonances and are the lightest exotic, coloured states. This makes them ideal to search for at colliders. Due to discrete symmetries the triplet scalar decays via a dimension-six term and given the large suppression scale f is often metastable. We show that existing searches for collider-stable R-hadrons from Run-I at the LHC forbid a triplet scalar mass below 845 GeV, whereas with 300 fb -1 at 13TeV triplet scalar masses up to 1.4TeV can be discovered. For shorter lifetimes displaced-vertex searches provide a discovery reach of up to 1.8TeV. Also, we present exclusion and discovery reaches of future hadron colliders as well as indirect limits that arise from modi cations of the Higgs couplings.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2019

Achieving Long-Lived Triplet States in Intramolecular SF Films through Molecular Engineering

Tuning singlet fission (SF) dynamics in the solid states in a controllable way is vitally important yet still a challenge due to the electronic coupling, which is highly sensitive to molecular packing. Here, we demonstrate a molecular engineering approach to independently optimize the triplet generation and decay process in intramolecular SF films by using terphenyl-bridged TIPS-pentacene tetramers. By controlling the degree of steric hindrance within individual tetramers, we can systematically tune the degree of intermolecular coupling in thin films. Taking advantage of both the intra- and intermolecular SF processes allows us to maintain a rapid triplet pair generation process, even in the case of weak intermolecular coupling. This approach allows us to maintain a picosecond triplet generation process while simultaneously varying the rate constants for triplet-triplet annihilation over three orders of magnitude.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2019

Triplet Tuning: A Novel Family of Non-Empirical Exchange–Correlation Functionals

In the framework of density functional theory (DFT), the lowest triplet excited state (T1) can be evaluated using multiple formulations, the most straightforward of which are unrestricted density functional theory (UDFT) and time-dependent density functional theory (TDDFT). Assuming the exact exchange-correlation (XC) functional is applied, UDFT and TDDFT provide identical energies for T1 ( ET), which is also a constraint that we require our XC functionals to obey. However, this condition is not satisfied by most of the popular XC functionals, leading to inaccurate predictions of low-lying, spectroscopically and photochemically important excited states, such as T1 and the lowest singlet excited state (S1). Inspired by the optimal tuning strategy for frontier orbital energies [T. Stein, L. Kronik, and R. Baer, J. Am. Chem. Soc. 2009, 131, 2818], we proposed a novel and nonempirical prescription of constructing an XC functional in which the agreement between UDFT and TDDFT in ET is strictly enforced. Referred to as "triplet tuning", our procedure allows us to formulate the XC functional on a case-by-case basis, using the molecular structure as the exclusive input, without fitting to any experimental data. The first triplet tuned XC functional, TT-ωPBEh, is formulated as a long-range-corrected (LRC) hybrid of Perdew-Burke-Ernzerhof (PBE) and Hartree-Fock (HF) functionals [M. A. Rohrdanz, K. M. Martins, and J. M. Herbert, J. Chem. Phys. 2009, 130, 054112] and tested on four sets of large organic molecules. Compared to existing functionals, TT-ωPBEh manages to provide more accurate predictions for key spectroscopic and photochemical observables, including but not limited to ET, the optical band gap ( ES), the singlet-triplet gap (Δ EST), and the vertical ionization potential ( I⊥), as it adjusts the effective electron-hole interactions to arrive at the correct excitation energies. This promising triplet tuning scheme can be applied to a broad range of systems that were notorious in DFT for being extremely challenging.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Resonance Raman Spectroscopy of the T 1 Triplet Excited State of Oligothiophenes

The characterization of triplet excited states is essential for research on organic photovoltaics and singlet fission. We report resonance Raman spectra of two triplet oligothiophenes with n-alkyl substituents, a tetramer and hexamer. The spectra of the triplets are more complex than the ground state, and we find that density functional theory calculations are a useful starting point for characterizing the bands. The spectra of triplet tetrathiophene and hexathiophene differ significantly from one another. This observation is consistent with a T 1 excitation that is delocalized over at least five rings in long oligomers. Bands in the 500–800 cm –1 region are greatly diminished for an aggregated sample of hexathiophene, likely caused by fast electronic dephasing. These experiments highlight the potential of resonance Raman spectroscopy to unequivocally detect and characterize triplets in thiophene materials. Furthermore, the vibrational spectra can also serve as rigorous standards for evaluating computational methods for excited-state molecules.

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

Triplet Photosensitized para -Hydrogen Induced Polarization

Despite its enormous utility in structural characterization, nuclear magnetic resonance (NMR) spectroscopy is inherently limited by low spin polarization. One method to address the low polarization is para-hydrogen (p-H 2 ) induced polarization (PHIP) which uses the singlet spin isomer of H 2 to generate disparate nuclear spin populations to amplify the associated NMR signals. PHIP often relies on thermal catalysis or, more infrequently, UV-activated catalytic hydrogenation. Light-activated hydrogenation enables direct and timed control over the hyperpolarization of target substrates, critical for identifying short-lived intermediates. Here, we use an established Ir(III) triplet photosensitizer (PS) to visible light sensitize the triplet ligand-field states in the d6-transition metal dihydride Ru(CO)(PPh 3 ) 3 (H) 2 (1). Excitation inside a 9.4 T NMR spectrometer with the PS and a 420 nm blue LED, under 3 atm of p-H 2 , successfully photosensitized hyperpolarization in 1 and in a range of unsaturated substrates at and below room temperature, up to 1630-fold. In otherwise identical experimental conditions without light activation, no polarization was realized in 1 or the substrates evaluated. We believe triplet-sensitized PHIP (Trip- PHIP) represents a facile experimental means for probing triplet sensitized light activation in transition metal catalysts possessing low-lying triplet ligand-field states, providing mechanistic insight of potentially tremendous value in chemical catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Triplet Management at Ligand-Perovskite Interface to Enhanced Photovoltaics Performance

Aromatic organic molecules are widely used as passivators in perovskite solar cells (PSCs). Efforts have been devoted to improving the energy alignments, band edge states, and defect passivation functionalities. However, potential energy loss through triplet states in such conjugated molecules has not been investigated in the past. Here, we report the observation of charge transfer from FAPbI 3 to the triplet state of a pyrene (Pyr)-based cationic ligand. Such a potential loss channel can be suppressed via delicate triplet management in polycyclic aromatic compounds. Interestingly, a subtle structural modification from Pyr to the triphenylene (TP) core gave rise to shallower triplets that prohibit electron transfer from perovskites. This strategy has led to TP-passivated PSCs achieving an enhanced power conversion efficiency (PCE) of 24.69% from 23.10% in Pyr-passivated counterparts. Moreover, the devices retained above 80% initial PCE after 4000 h of light soaking, which likely benefited from the reduced triplet electron trapping at the ligand-perovskite interface.

14 SOLAR ENERGY↗
DOE OSTI2020

Evolution from Tunneling to Hopping Mediated Triplet Energy Transfer from Quantum Dots to Molecules

Efficient energy transfer is particularly important for multiexcitonic processes like singlet fission and photon upconversion. Observation of the transition from short-range tunneling to long-range hopping during triplet exciton transfer from CdSe nanocrystals to anthracene is reported here. This is firmly supported by steady- state photon upconversion measurements, a direct proxy for the efficiency of triplet energy transfer (TET), as well as transient absorption measurements. When phenylene bridges are initially inserted between a CdSe nanocrystal donor and anthracene acceptor, the rate of TET decreases exponentially, commensurate with a decrease in the photon upconversion quantum efficiency from 11.6% to 4.51% to 0.284%, as expected from a tunneling mechanism. However, as the rigid bridge is increased in length to 4 and 5 phenylene units, photon upconversion quantum efficiencies increase again to 0.468% and 0.413%, 1.5–1.6 fold higher than that with 3 phenylene units (using the convention where the maximum upconversion quantum efficiency is 100%). This suggests a transition from exciton tunneling to hopping, resulting in relatively efficient and distance-independent TET beyond the traditional 1 nm Dexter distance. Transient absorption spectroscopy is used to confirm triplet energy transfer from CdSe to transmitter, and the formation of a bridge triplet state as an intermediate for the hopping mechanism. Lastly, this first observation of the tunneling-to-hopping transition for long-range triplet energy transfer between nanocrystal light absorbers and molecular acceptors suggests that these hybrid materials should further be explored in the context of artificial photosynthesis.

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

Electron Sextets as Optically Addressable Molecular Qubits: Triplet Carbenes

There is a growing demand in quantum information science and sensing for electron spin purification and readout via a spin-optical interface. This technique, known as optically detected magnetic resonance (ODMR), has been applied to diamond-NV centers and transition-metal complexes. Metal-free counterparts of these optically addressable spin qubits promise to be cheaper, more sustainable color centers with prolonged polarization lifetimes. However, progress has been hindered by the low ODMR signals of carbon-based π-diradicals, partly due to the lack of a ground singlet-to-triplet intersystem crossing (ISC). In this work, we propose exploring organic systems that are even more electron-deficient: electron sextets. Using triplet carbenes as an example, we illustrate how the ground singlet-triplet gap can be widened beyond thermal energy with the associated singlet-to-triplet ISC made available by vibronic effects. Through careful molecular engineering, this ISC can occur at a rate similar to and with an opposite spin selectivity from the excited-state ISC well-established in π-diradicals, unlocking a new ODMR pathway with potential signal gains. Persistent triplet carbenes are a renascent field, with multiple stable molecules being isolated in the past five years. To motivate further development of its emissive properties, we illustrate our design in three realistic carbene candidates that incorporate existing strategies for carbene stabilization. Furthermore, we believe that a new realm of quantum materials can be uncovered by expanding our scope toward stable electron sextets.

Carbene compounds↗
DOE OSTI2018

Long-Lived Correlated Triplet Pairs in a π-Stacked Crystalline Pentacene Derivative

Singlet fission is the spin-conserving process by which a singlet exciton splits into two triplet excitons. Singlet fission occurs via a correlated triplet pair intermediate, but direct evidence of this state has been scant, and in films of TIPS-pentacene, a small molecule organic semiconductor, even the rate of fission has been unclear. We use polarization-resolved transient absorption microscopy on individual crystalline domains of TIPS-pentacene to establish the fission rate and demonstrate that the initially created triplets remain bound for a surprisingly long time, hundreds of picoseconds, before separating. Furthermore, using a broadband probe, we show that it is possible to determine absorbance spectra of individual excited species in a crystalline solid. We find that triplet interactions perturb the absorbance, and provide evidence that triplet interaction and binding could be caused by the π-stacked geometry. Elucidating the relationship between the lattice structure and the electronic structure and dynamics has important implications for the creation of photovoltaic devices that aim to boost efficiency via singlet fission.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Cooperative Singlet and Triplet Exciton Transport in Tetracene Crystals Visualized by Ultrafast Microscopys

Singlet fission presents an attractive solution to overcome the Shockley–Queisser limit by generating two triplet excitons from one singlet exciton. Although triplet excitons are long-lived, their transport occurs through a Dexter transfer, making them slower than singlet excitons, which travel by means of a Förster mechanism. A thorough understanding of the interplay between singlet fission and exciton transport is therefore necessary to assess the potential and challenges of singlet-fission utilization. We report a direct visualization of exciton transport in single tetracene crystals using transient absorption microscopy with 200 fs time resolution and 50 nm spatial precision. Moreover, these measurements reveal a new singlet-mediated transport mechanism for triplets, which leads to an enhancement in effective triplet exciton diffusion of more than one order of magnitude on picosecond to nanosecond timescales. These results establish that there are optimal energetics of singlet and triplet excitons that benefit both singlet fission and exciton diffusion.

14 SOLAR ENERGY↗
DOE OSTI2021

Evidence for anisotropic spin-triplet Andreev reflection at the 2D van der Waals ferromagnet/superconductor interface

Fundamental symmetry breaking and relativistic spin–orbit coupling give rise to fascinating phenomena in quantum materials. Of particular interest are the interfaces between ferromagnets and common s-wave superconductors, where the emergent spin-orbit fields support elusive spin-triplet superconductivity, crucial for superconducting spintronics and topologically-protected Majorana bound states. Here, we report the observation of large magnetoresistances at the interface between a quasi-two-dimensional van der Waals ferromagnet Fe 0.29 TaS 2 and a conventional s-wave superconductor NbN, which provides the possible experimental evidence for the spin-triplet Andreev reflection and induced spin-triplet superconductivity at ferromagnet/superconductor interface arising from Rashba spin-orbit coupling. The temperature, voltage, and interfacial barrier dependences of the magnetoresistance further support the induced spin-triplet superconductivity and spin-triplet Andreev reflection. This discovery, together with the impressive advances in two-dimensional van der Waals ferromagnets, opens an important opportunity to design and probe superconducting interfaces with exotic properties.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Achieving spin-triplet exciton transfer between silicon and molecular acceptors for photon upconversion

Inorganic semiconductor nanocrystals interfaced with spin-triplet exciton-accepting organic molecules have emerged as promising materials for converting incoherent long-wavelength light into the visible range. However, these materials to date have made exclusive use of nanocrystals containing toxic elements, precluding their use in biological or environmentally sensitive applications. In this paper, we address this challenge by chemically functionalizing non-toxic silicon nanocrystals with triplet-accepting anthracene ligands. Photoexciting these structures drives spin-triplet exciton transfer from silicon to anthracene through a single 15 ns Dexter energy transfer step with a nearly 50% yield. When paired with 9,10-diphenylanthracene emitters, these particles readily upconvert 488–640 nm photons to 425 nm violet light with efficiencies as high as 7 ± 0.9% and can be readily incorporated into aqueous micelles for biological use. Our demonstration of spin-triplet exciton transfer from silicon to molecular triplet acceptors can critically enable new technologies for solar energy conversion, quantum information and near-infrared driven photocatalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Long-lived triplet excited state in a platinum(ii) perylene monoimide complex

We report here the synthesis and solution based photophysical properties of a new Pt(II)-terpyridine complex coupled to a perylene monoimide (PMI) chromophoric unit through an acetylene linkage. This structural arrangement resulted in quantitative quenching of the highly fluorescent PMI chromophore by introducing metal character into the lowest energy singlet state, thereby leading to the formation of a long-lived PMI-ligand localized triplet excited state (τ = 8.4 μs). Even though the phosphorescence from this triplet state was not observed, highly efficient quenching of this excited state by dissolved oxygen and the observation of singlet oxygen photoluminescence in the near-IR at 1270 nm initially pointed towards triplet excited state character. Furthermore, the coincidence of the excited state absorbance difference spectra from the sensitized PMI ligand using a triplet donor and the Pt-PMI complex provided strong evidence for this triplet state assignment, which was further supported by TD-DFT calculations.

14 SOLAR ENERGY↗
DOE OSTI2021

Adsorption of a single Pt atom on graphene: spin crossing between physisorbed triplet and chemisorbed singlet states

Diffusion Monte Carlo (DMC) calculations have been performed to study the adsorption of a single Pt atom on pristine graphene. In this work, we obtain the adsorption energy curves of a single Pt atom adsorbed at three different adsorption sites (bridge, on-top, hollow) as functions of the vertical distance from a graphene surface for both spin singlet and triplet states. The bridge-site adsorption in a singlet spin state is found to be energetically most stable, which is consistent with previous theoretical predictions. As the Pt atom moves away from a graphene surface, spin triplet states are favored over spin singlet states for all three adsorption sites, reflecting that the ground state of an isolated Pt atom is in a spin triplet state. Furthermore, our DMC calculations reveal local-minimum features in the triplet region which is understood to be due to van der Waals interaction between the Pt atom and graphene. This provides a comprehensive understanding for a spin crossing from a physisorbed triplet state to a chemisorbed singlet state in the adsorption process of a single Pt atom on graphene.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Singlet fission and triplet pair recombination in bipentacenes with a twist

We investigate triplet pair dynamics in pentacene dimers that have varying degrees of coplanarity (pentacene–pentacene twist angle). The fine-tuning of the twist angle was achieved by alternating connectivity at the 1-position or 2-positions of pentacene. This mix-and-match connectivity leads to tunable twist angles between the two covalently linked pentacenes. These twisted dimers allow us to investigate the subtle effects that the dihedral angle between the covalently linked pentacenes imparts on singlet fission and triplet pair recombination dynamics. We observe that as the dihedral angle between the two bonded pentacenes is increased, the rates of singlet fission decrease, while the accompanying decrease in triplet recombination rates is stark. Temperature-dependent transient optical studies combined with theoretical calculations show that the triplet pair recombination proceeds primarily through a direct multiexciton internal conversion process. Calculations further show that the significant decrease in recombination rates can be directly attributed to a corresponding decrease in the magnitude of the nonadiabatic coupling between the singlet multiexcitonic state and the ground state. Furthermore, these results highlight the importance of the twist angle in designing systems that exhibit rapid singlet fission, while maintaining long triplet pair lifetimes in pentacene dimers.

14 SOLAR ENERGY↗
DOE OSTI2021

Bulk halide perovskites as triplet sensitizers: progress and prospects in photon upconversion

Triplet–triplet annihilation-based photon upconversion (TTA-UC) is a promising mechanism for harvesting lower energy photons by converting them to a higher energy. Photons generated from this process can be used for numerous applications, including photovoltaics, infrared sensing and imaging, biomedicine and photochemical reactions. Recently, bulk metal halide perovskite semiconductors have been introduced as triplet sensitizers for the TTA-UC process. While relatively efficient upconversion has been achieved at low fluences, the full potential of these materials as triplet sensitizers has not been unlocked. In this study, we examine four pathways for device optimization and improvements, while discussing relevant works and potential further improvements. Finally, we discuss the outlook and bright future of such perovskite materials as triplet sensitizers and their important role in solid-state upconversion applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗