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DOE OSTI2018

Applicability of the thin-film approximation in terahertz photoconductivity measurements

Thin mesoporous photoconductive layers are critically important for efficient water-spitting solar cells. A detailed understanding of photoconductivity in these materials can be achieved via terahertz transient absorption measurements. Such measurements are commonly interpreted using the thin-film approximation. We compare this approximation with a numerical solution of the transfer function without approximations using experimental results for thin-film mesoporous tin oxide (SnO 2 ) samples which range in thickness from 3.3 to 12.6 µm. These samples were sensitized with either a ruthenium polypyridyl complex or a porphyrin dye. The two sensitizers have markedly different absorption coefficients, resulting in penetration depths of 15 µm and 1 µm, respectively. The thin-film approximation results are in good agreement with the numerical work-up for the short penetration length dye. For the longer penetration length samples, the thin-film formula fails even for thicknesses of only 3 µm ≈ λ/100. The imaginary part of the conductivity calculated using the thin-film formula was significantly larger in magnitude than the value without approximations. This discrepancy between the commonly used thin-film approximation and the numerical solution demonstrates the need for a careful analysis of the thin-film formula.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2018

Strain tuning of excitons in monolayer WSe 2

Here, we investigate excitonic absorption and emission in monolayer (1L) WSe 2 under tensile strain. We observe a redshift of 100 meV in the A exciton energy and a decrease of 25 meV in its estimated binding energy under 2.1% strain. Surprisingly, the linewidth of the A exciton decreases by almost a factor of two under strain, from 42 to 24 meV at room temperature. We explain this effect as the result of suppression of phonon-mediated exciton scattering channels. We show that such a suppression results from the relative shift under strain of a secondary valley in the conduction band that is nearly degenerate with the K valley where the A exciton is formed.

2-dimensional systems↗

NASA NTRS1998

Study of the effects of MeV Ag, Cu, Au, and Sn implantation on the optical properties of LiNbO3

The authors present the results of characterization of linear absorption and nonlinear refractive index of Au, Ag, Cu and Sn ion implantation into LiNbO3. Ag was implanted at 1.5 MeV to fluences of 2 to 17 x 17(exp 16)/sq cm at room temperature. Au and Cu were implanted to fluences of 5 to 20 x 10(exp 16)/sq cm at an energy of 2.0 MeV. Sn was implanted to a fluence of 1.6 x 10(exp 17)/sq cm at 160 kV. Optical absorption spectrometry indicated an absorption peak for the Au implanted samples after heat treatment at 1,000 C at approx. 620 nm. The Ag implanted samples absorption peaks shifted from approx. 450 nm before heat treatment to 550 nm after 500 C for 1h. Heat treatment at 800 C returned the Ag implanted crystals to a clear state. Cu nanocluster absorption peaks disappears at 500 C. No Sn clusters were observed by optical absorption or XRD. The size of the Ag and Au clusters as a function of heat treatment were determined from the absorption peaks. The Ag clusters did not change appreciably in size with heat treatment. The Au clusters increased from 3 to 9 nm diameter upon heat treatment at 1000 C. TEM analysis performed on a Au implanted crystal indicated the formation of Au nanocrystals with facets normal to the c-axis. Measurements of the nonlinear refractive indices were carried out using the Z-scan method with a tunable dye laser pumped by a frequency doubled mode-locked Nd:YAG laser. The dye laser had a 4.5 ps pulse duration time and 76 MHz pulse repetition rate (575 nm).

Williams, E. K.↗

DOE OSTI2022

The Gaussian nature of the band-edge of ZnO microcrystalline thin films

A straightforward analytical approach based on the derivative of the absorption coefficient is presented, which enables probing the nature of the band edge (BE) of ZnO microcrystalline films. The study was conducted via transmission experiments at temperatures of 77–532 K and repeated for samples annealed up to 1073 K. It was found that the derivative of the natural log of the BE absorption coefficient resulted in a Gaussian function. The Gaussian linewidth is used in the electron–phonon (e–p) interaction model to characterize the defect-state of the films. The BE of the as-grown film was found to exhibit no thermal dependence and no e–p coupling, indicative of a disordered crystal. Upon annealing and improvement of the film quality, the thermal phonons became more activated, but only above room temperature with a phonon energy of ~75 meV, while up to room temperature, the impact of phonons on the BE is insignificant. A disorder–order transition was determined to take place at an annealing temperature of ~673 K. X-ray diffraction concurs with these results. The study indicates that the prevalent defects are of structural nature due to the inherent granular morphology of the films. This defect was found to dominate the behavior of the BE even at the elevated temperature regime rather than thermal phonons.

36 MATERIALS SCIENCE↗

DOE OSTI2018

Study of the Structural, Electronic, Magnetic, and Optical Properties of Mn{sub 2}ZrGa Full-Heusler Alloy: First-Principles Calculations

In this work, the structural, electronic, magnetic, and optical properties of Mn{sub 2}ZrGa full-Heusler alloy were investigated by using density functional theory (DFT) calculations. It is found that the spin-up states have a metallic character, but the spin-down bands have a pseudo-gap at the Fermi level. The total spin magnetic moment of Mn{sub 2}ZrGa (per formula unit) is 3.00 µ{sub B} at an equilibrium lattice parameter of 6.15 Å. The calculations show that Mn{sub 2}ZrGa is a ferrimagnetic with 81% spin polarization at equilibrium lattice parameter. The effect of lattice parameter distortion on the magnetic properties and spin polarization is also studied. It is found that the total magnetic moment preserves its value for a lattice parameter range of 5.96–6.30 Å. The decreasing of the lattice parameter leads to improvement of spin polarization. The real and imaginary parts of dielectric function and hence the optical properties including energy absorption spectrum, reflectivity, and optical conductivity are also calculated. The value of plasma frequency for spin-up and down electrons is located at 1.78 and 0.74 eV, respectively.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2024

Epitaxial (Al x Ga 1-x-y In y ) 2 O 3 Alloys Lattice Matched to Monoclinic Ga 2 O 3 Substrates

We have epitaxially stabilized a series of monoclinic (Al x Ga 1-x-y In y ) 2 O 3 alloys by careful choice of molecular beam epitaxy growth conditions, which balance alloy growth with suboxide desorption. The films are pseudomorphic to (010) β-Ga 2 O 3 substrates at thicknesses up to 150 nm with compositions ranging from (Al 0.01 Ga 0.83 In 0.16 ) 2 O 3 to (Al 0.24 Ga 0.75 In 0.03 ) 2 O 3 . The absorption edge shifts from approximately 4.62-5.14 eV with coincidently increasing Al and decreasing In mole fractions. J-V measurements reveal an increase in resistivity over four orders of magnitude with a maximum value of 4.2 x 10 5 Ω-cm for (Al 0.17 Ga 0.76 In 0.07 ) 2 O 3 , which has nearly identical lattice parameters (both in-plane and out-of-plane) to the underlying β-Ga 2 O 3 . Scanning transmission electron microscopy of this sample reveals a mostly uniform and single crystalline film, though we identify areas of non-uniform In incorporation and some γ-phase inclusions. This work demonstrates the feasibility of thick layers lattice-matched to β-Ga 2 O 3 with increased bandgap compared to phase-separation limited (Al,Ga) 2 O 3 . These alloys can enable higher bandgap epitaxial dielectrics and high sheet charge density transistors by increasing the conduction band offset with respect to β-Ga 2 O 3 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Improved representation of black carbon mixing structures suggests stronger direct radiative heating

Black carbon significantly influences the Earth system because of its strong solar radiation absorption. However, its direct radiative effect remains poorly understood in current climate models, partly because current climate models oversimplify the diverse structures formed when black carbon mixes with other atmospheric components. Here we show that incorporating more realistic, multi-mixing-structure representations of black carbon increases the direct radiative effect. We find that aged black carbon particles, with thicker coatings and higher embedded fractions, enhance the direct radiative effect more efficiently. Using machine learning alongside the Community Earth System Model, we show that the direct radiative effect at the top of the atmosphere in regions with heavy black carbon pollution is 31.6% greater when multi-mixing structures are considered. These findings highlight the importance of modeling complex mixing structures of particle-resolved black carbon to accurately capture their warming impacts on global atmosphere, particularly in highly polluted regions.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2015

Russian anthropogenic black carbon: Emission reconstruction and Arctic black carbon simulation

Development of reliable source emission inventories is needed to advance the understanding of the origin of Arctic haze using chemical transport modeling. This paper develops a regional anthropogenic black carbon (BC) emission inventory for the Russian Federation, the largest country by land area in the Arctic Council. Activity data from combination of local Russia information and international resources, emission factors based on either Russian documents or adjusted values for local conditions, and other emission source data are used to approximate the BC emissions. Emissions are gridded at a resolution of 0.1° × 0.1° and developed into a monthly temporal profile. Total anthropogenic BC emission of Russia in 2010 is estimated to be around 224 Gg. Gas flaring, a commonly ignored black carbon source, contributes a significant fraction of 36.2% to Russia's total anthropogenic BC emissions. Other sectors, i.e., residential, transportation, industry, and power plants, contribute 25.0%, 20.3%, 13.1%, and 5.4%, respectively. Three major BC hot spot regions are identified: the European part of Russia, the southern central part of Russia where human population densities are relatively high, and the Urals Federal District where Russia's major oil and gas fields are located but with sparse human population. BC simulations are conducted using the hemispheric version of Community Multi-scale Air Quality Model with emission inputs from a global emission database EDGAR (Emissions Database for Global Atmospheric Research)-HTAPv2 (Hemispheric Transport of Air Pollution) and EDGAR-HTAPv2 with its Russian part replaced by the newly developed Russian BC emissions, respectively. The simulation using the new Russian BC emission inventory could improve 30–65% of absorption aerosol optical depth measured at the AERONET sites in Russia throughout the whole year as compared to that using the default HTAPv2 emissions. At the four ground monitoring sites (Zeppelin, Barrow, Alert, and Tiksi) in the Arctic Circle, surface BC simulations are improved the most during the Arctic haze periods (October–March). The poor performance of Arctic BC simulations in previous studies may be partly ascribed to the Russian BC emissions built on out-of-date and/or missing information, which could result in biases to both emission rates and the spatial distribution of emissions. Finally, this study highlights that the impact of Russian emissions on the Arctic haze has likely been underestimated, and its role in the Arctic climate system needs to be reassessed. The Russian black carbon emission source data generated in this study can be obtained via http://abci.ornl.gov/download.shtml or http://acs.engr.utk.edu/Data.php.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2017

Single‐Junction Binary‐Blend Nonfullerene Polymer Solar Cells with 12.1% Efficiency

A new fluorinated nonfullerene acceptor, ITIC‐Th1, has been designed and synthesized by introducing fluorine (F) atoms onto the end‐capping group 1,1‐dicyanomethylene‐3‐indanone (IC). On the one hand, incorporation of F would improve intramolecular interaction, enhance the push–pull effect between the donor unit indacenodithieno[3,2‐b]thiophene and the acceptor unit IC due to electron‐withdrawing effect of F, and finally adjust energy levels and reduce bandgap, which is beneficial to light harvesting and enhancing short‐circuit current density ( J SC ). On the other hand, incorporation of F would improve intermolecular interactions through CF···S, CF···H, and CF···π noncovalent interactions and enhance electron mobility, which is beneficial to enhancing J SC and fill factor. Indeed, the results show that fluorinated ITIC‐Th1 exhibits redshifted absorption, smaller optical bandgap, and higher electron mobility than the nonfluorinated ITIC‐Th. Furthermore, nonfullerene organic solar cells (OSCs) based on fluorinated ITIC‐Th1 electron acceptor and a wide‐bandgap polymer donor FTAZ based on benzodithiophene and benzotriazole exhibit power conversion efficiency (PCE) as high as 12.1%, significantly higher than that of nonfluorinated ITIC‐Th (8.88%). The PCE of 12.1% is the highest in fullerene and nonfullerene‐based single‐junction binary‐blend OSCs. Moreover, the OSCs based on FTAZ:ITIC‐Th1 show much better efficiency and better stability than the control devices based on FTAZ:PC 71 BM (PCE = 5.22%).

Zhao, Fuwen↗

DOE OSTI2023

Anisotropic Excitons Reveal Local Spin Chain Directions in a van der Waals Antiferromagnet

A long‐standing pursuit in materials science is to identify suitable magnetic semiconductors for integrated information storage, processing, and transfer. Van der Waals magnets have brought forth new material candidates for this purpose. Recently, sharp exciton resonances in antiferromagnet NiPS 3 have been reported to correlate with magnetic order, that is, the exciton photoluminescence intensity diminishes above the Néel temperature. Here, it is found that the polarization of maximal exciton emission rotates locally, revealing three possible spin chain directions. This discovery establishes a new understanding of the antiferromagnet order hidden in previous neutron scattering and optical experiments. Furthermore, defect‐bound states are suggested as an alternative exciton formation mechanism that has yet to be explored in NiPS 3 . The supporting evidence includes chemical analysis, excitation power, and thickness dependent photoluminescence and first‐principles calculations. This mechanism for exciton formation is also consistent with the presence of strong phonon side bands. This study shows that anisotropic exciton photoluminescence can be used to read out local spin chain directions in antiferromagnets and realize multi‐functional devices via spin‐photon transduction.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Revealing Excited‐State Trajectories on Potential Energy Surfaces with Atomic Resolution in Real Time

Abstract Photoexcited molecular trajectories on potential energy surfaces (PESs) prior to thermalization are intimately connected to the photochemical reaction outcome. The excited‐state trajectories of a diplatinum complex featuring photo‐activated metal–metal σ ‐bond formation and associated Pt−Pt stretching motions were detected in real time using femtosecond wide‐angle X‐ray solution scattering. The observed motions correspond well with coherent vibrational wavepacket motions detected by femtosecond optical transient absorption. Two key coordinates for intersystem crossing have been identified, the Pt−Pt bond length and the orientation of the ligands coordinated with the platinum centers, along which the excited‐state trajectories can be projected onto the calculated PESs of the excited states. This investigation has gleaned novel insight into electronic transitions occurring on the time scales of vibrational motions measured in real time, revealing ultrafast nonadiabatic or non‐equilibrium processes along excited‐state trajectories involving multiple excited‐state PESs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Dominant Role of Hole Transport Pathway in Achieving Record High Photoconductivity in Two‐Dimensional Metal–Organic Frameworks

Abstract Metal–organic frameworks (MOFs) with mobile charges have attracted significant attention due to their potential applications in photoelectric devices, chemical resistance sensors, and catalysis. However, fundamental understanding of the charge transport pathway within the framework and the key properties that determine the performance of conductive MOFs in photoelectric devices remain underexplored. Herein, we report the mechanisms of photoinduced charge transport and electron dynamics in the conductive 2D M−HHTP (M=Cu, Zn or Cu/Zn mixed; HHTP=2,3,6,7,10,11‐hexahydroxytriphenylene) MOFs and their correlation with photoconductivity using the combination of time‐resolved terahertz spectroscopy, optical transient absorption spectroscopy, X‐ray transient absorption spectroscopy, and density functional theory (DFT) calculations. We identify the through‐space hole transport mechanism through the interlayer sheet π–π interaction, where photoinduced hole state resides in HHTP ligand and electronic state is localized at the metal center. Moreover, the photoconductivity of the Cu−HHTP MOF is found to be 65.5 S m −1 , which represents the record high photoconductivity for porous MOF materials based on catecholate ligands.

Wang, Denan↗

DOE OSTI2023

Revealing Excited‐State Trajectories on Potential Energy Surfaces with Atomic Resolution in Real Time

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Dominant Role of Hole Transport Pathway in Achieving Record High Photoconductivity in Two‐Dimensional Metal–Organic Frameworks

14 SOLAR ENERGY↗

DOE OSTI2020

Spectroscopic Characterisation of a Bio-Inspired Ni-Based Proton Reduction Catalyst Bearing a Pentadentate N 2 S 3 Ligand with Improved Photocatalytic Activity

Inspired by the sulfur-rich environment found in active hydrogenase enzymes, a Ni-based proton reduction catalyst with pentadentate N 2 S 3 ligand was synthesised. When coupled with [Ru(bpy) 3 ] 2+ (bpy=2,2 '-bipyridine) as photosensitiser and ascorbate as electron donor in a 1:1 mixture of dimethylacetamide and aqueous ascorbic acid/ascorbate buffer, the catalyst showed improved photocatalytic activity compared with a homologous counterpart bearing a tetradentate N 2 S 2 ligand. The mechanistic pathway of photoinduced hydrogen evolution was comprehensively analysed through optical transient absorption and time-resolved X-ray absorption spectroscopy, which revealed important electronic and structural changes in the catalytic system during photoirradiation. Furthermore, the Ni-II catalyst undergoes a photoinduced metal-centred reduction to form a Ni-I intermediate with distorted square-bipyramidal geometry. Further kinetic analyses revealed differences in charge-separation dynamics between the pentadentate and tetradentate forms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Temperature-dependent structural transition following X-ray-induced metal center reduction in oxidized cytochrome c oxidase

Not Available

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2018

Electronic Structure of Manganese Corroles Revisited: X-ray Structures, Optical and X-ray Absorption Spectroscopies, and Electrochemistry as Probes of Ligand Noninnocence

Presented herein is a detailed multitechnique investigation of ligand noninnocence in S = 3/2 manganese corrole derivatives at the formal Mn IV oxidation state. The Soret maxima of Mn[T p XPC]Cl (T p XPC = meso -tris( p -X-phenyl)corrole, where X = CF 3 , H, Me, and OMe) were found to red-shift over a range of 37 nm with increasing electron-donating character of X. For Mn[T p XPC]Ph, in contrast, the complex Soret envelopes were found to be largely independent of X. These observations suggested a noninnocent corrole •2– -like ligand for the MnCl complexes and an innocent corrole 3– ligand for the MnPh complexes. Single-crystal X-ray structures of three Mn[T p XPC]Cl complexes revealed skeletal bond-length alternations indicative of a noninnocent corrole, while no such alternation was observed for Mn[T p OMePC]Ph. B3LYP density functional theory (DFT) calculations on Mn[TPC]Cl yielded strong spatial separation of the α and β spin densities, consistent with an antiferromagnetically coupled Mn III -corrole •2– description. By comparison, relatively little spatial separation of the α and β spin densities was found for Mn[TPC]Ph, consistent with an essentially Mn IV -corrole 3– description. X-ray absorption of near-edge spectroscopy (XANES) revealed a moderate blue shift of 0.6 eV for the Mn K-pre-edge of Mn[T p CF 3 PC]Ph and a striking enhancement of the pre-edge intensity, relative to Mn[T p CF 3 PC]Cl, consistent with a more oxidized, i.e., Mn IV , center in Mn[T p CF 3 PC]Ph. Time-dependent DFT calculations indicated that the enhanced intensity of the Mn K-pre-edge of Mn[T p CF 3 PC]Ph results from the extra 3d z 2 hole, which mixes strongly with the Mn 4p z orbital. Combined with similar results on Fe[TPC]Cl and Fe[TPC]Ph, the present study underscores the considerable potential of metal K-edge XANES in probing ligand noninnocence in first-row transition-metal corroles. As a result, cyclic voltammetry measurements revealed highly negative first reduction potentials for the Mn[T p XPC]Ph series (~–0.95 V) as well as large electrochemical HOMO-LUMO gaps of ~1.7 V. The first reductions, however, are irreversible, suggesting cleavage of the Mn–Ph bond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2018

Shedding Light on the Nature of Photoinduced States Formed in a Hydrogen-Generating Supramolecular RuPt Photocatalyst by Ultrafast Spectroscopy

Photoinduced electronic and structural changes of a hydrogen generating supramolecular RuPt photocatalyst are studied by a combination of time-resolved photoluminescence, optical transient absorption, and X-ray absorption spectroscopy. This work uses the element specificity of X-ray techniques to focus on the interplay between the photophysical and-chemical processes and the associated time scales at the catalytic Pt moiety. We observe very fast (<30 ps) photoreduction of the Pt catalytic site, followed by an similar to 600 ps step into a strongly oxidized Pt center. The latter process is likely induced by oxidative addition of reactive iodine species. The oxidized Pt species is long-lived and fully recovers to the original ground state complex on a >10 mu s time scale. However, the photosensitizing Ru moiety is fully restored on a much shorter similar to 300 ns time scale. In conclusion, this reaction scheme implies that we may withdraw two electrons from activated by a single photon.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗