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At least 1,207 records · Page 67
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

In situ investigation of the formation and metastability of formamidinium lead tri-iodide perovskite solar cells

Organic–inorganic perovskites have emerged as an important class of next generation solar cells due to their remarkably low cost, band gap, and sub-900 nm absorption onset. Here, we show a series of in situ observations inside electron microscopes and X-ray diffractometers under device-relevant synthesis conditions focused on revealing the crystallization process of the formamidinium lead-triiodide perovskite at the optimum temperature of 175 °C. Direct in situ observations of the structure and chemistry over relevant spatial, temporal, and temperature scales enabled identification of key perovskite formation and degradation mechanisms related to grain evolution and interface chemistry. The lead composition was observed to fluctuate at grain boundaries, indicating a mobile lead-containing species, a process found to be partially reversible at a key temperature of 175 °C. Using low energy electron microscopy and valence electron energy loss spectroscopy, lead is found to be bonded in the grain interior with iodine in a tetrahedral configuration. At the grain boundaries, the binding energy associated with lead is consequently shifted by nearly 2 eV and a doublet peak is resolved due presumably to a greater degree of hybridization and the potential for several different bonding configurations. At the grain boundaries there is adsorption of hydrogen and OH¯ ions as a result of residual water vapor trapped as a non-crystalline material during formation. Lastly, insights into the relevant formation and decomposition reactions of formamidinium lead iodide at low to high temperatures, observed metastabilities, and relationship with the photovoltaic performance were obtained and used to optimize device processing resulting in conversion efficiencies of up to 17.09% within the stability period of the devices.

14 SOLAR ENERGY↗
DOE OSTI2016

Imaging ultrafast excited state pathways in transition metal complexes by X-ray transient absorption and scattering using X-ray free electron laser source

This report will describe our recent studies of transition metal complex structural dynamics on the fs and ps time scales using an X-ray free electron laser source, Linac Coherent Light Source (LCLS). Ultrafast XANES spectra at the Ni K-edge of nickel(II) tetramesitylporphyrin (NiTMP) were successfully measured for optically excited state at a timescale from 100 fs to 50 ps, providing insight into its sub-ps electronic and structural relaxation processes. Importantly, a transient reduced state Ni(I) (π, 3dx2-y2) electronic state is captured through the interpretation of a short-lived excited state absorption on the low-energy shoulder of the edge, which is aided by the computation of X-ray transitions for postulated excited electronic states. The observed and computed inner shell to valence orbital transition energies demonstrate and quantify the influence of electronic configuration on specific metal orbital energies. A strong influence of the valence orbital occupation on the inner shell orbital energies indicates that one should not use the transition energy from 1s to other orbitals to draw conclusions about the d-orbital energies. For photocatalysis, a transient electronic configuration could influence d-orbital energies up to a few eV and any attempt to steer the reaction pathway should account for this to ensure that external energies can be used optimally in driving desirable processes. NiTMP structural evolution and the influence of the porphyrin macrocycle conformation on relaxation kinetics can be likewise inferred from this study.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2018

Identifying the acceptor state in NiO hole collection layers: direct observation of exciton dissociation and interfacial hole transfer across a Fe 2 O 3 /NiO heterojunction

NiO is widely utilized as a hole transport layer in solar energy devices where light absorption in a photoactive layer is followed by charge separation and hole injection into a NiO collection layer. Due to the complex electronic structure of the hybridized valence band in NiO, the chemical nature of the hole acceptor state has remained an open question, despite the fact that hole localization in this material significantly influences device efficiency. To comment on this, we present results of ultrafast charge carrier dynamics in a NiO based model heterojunction (Fe 2 O 3 /NiO) using extreme ultraviolet reflection–absorption (XUV-RA) spectroscopy. Element specific XUV-RA spectroscopy demonstrates the formation of transient Ni 3+ within 10 ps following selective photoexcitation of the underlying Fe 2 O 3 substrate. This indicates that hole transfer in this system occurs to NiO valence band states composed of significant Ni 3d character. Additionally, we show that this hole injection process proceeds via a two-step sequential mechanism where fast, field-driven exciton dissociation occurs in Fe 2 O 3 in 680 ± 60 fs, followed by subsequent hole injection to NiO in 9.2 ± 2.9 ps. Furthermore, these results reveal the chemical nature of the hole acceptor state in widely used NiO hole transport layers and provides a direct observation of exciton dissociation and interfacial hole transfer in this model system.

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

Multiple pulse coherent dynamics and wave packet control of the N 2 a" 1 Σ$^+_g$ dark state by attosecond four-wave mixing

Nonlinear multidimensional spectroscopy is ubiquitous in the optical and radio frequency regions as a powerful tool to access structure and dynamics. The extension of this technique into the extreme ultraviolet (XUV) region with attosecond pulses holds promise for probing electronic dynamics and correlations with unprecedented time and spatial resolution. In this work, we use noncollinear four-wave mixing of a weak XUV attosecond pulse train (11–17 eV) and few-femtosecond NIR pulses (800 nm) to spectroscopically and dynamically probe the dipole-forbidden double-well potential of the a" 1 Σ + g electronic state of nitrogen. The results demonstrate optical coupling of the inner and outer limits of the initial XUV-prepared vibrational wave packet in the valence character b' 1 Σ + u state to the inner and outer wells, respectively, of the a" 1 Σ + g double well state by 800 nm light. Two four-wave mixing schemes with different pulse timing sequences and noncollinear beam geometries are used (one NIR pulse collinear and one NIR pulse noncollinear versus both NIR pulses noncollinear to the XUV beam) to measure the a" dark state energetic structure and to control the dynamical preparation and motion of a dark state wave packet by selective population of either the inner Rydberg or outer valence-character potential well. Finally, experimental measurements of the a" 1 Σ + g outer well vibrational spacing and anharmonicity closely match the values theoretically predicted for this previously unobserved state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Formation of resonances and anionic fragments upon electron attachment to benzaldehyde

Benzaldehyde is a simple aromatic aldehyde and has a wide range of applications in the food, pharmaceutical, and chemical industries. The positive electron affinity of this compound suggests that low-energy electrons can be easily trapped by neutral benzaldehyde. In the present study, we investigated the formation of negative ions following electron attachment to benzaldehyde in the gas-phase. Calculations on elastic electron scattering from benzaldehyde indicate a π* valence bound state of the anion at -0.48 eV and three π* shape resonances (0.78, 2.48 and 5.51 eV). The excited state spectrum of the neutral benzaldehyde is also reported to complement our findings. Using mass spectrometry, we observed the formation of the intact anionic benzaldehyde at ~0 eV. We ascribe the detection of the benzaldehyde anion to stabilization of the π* valence bound state upon dissociative electron attachment to a benzaldehyde dimer. In addition, we report the cross sections for nine fragment anions formed through electron attachment to benzaldehyde. Investigations carried out with partially deuterated benzaldehyde show that the hydrogen loss is site-selective with respect to the incident electron energy. In addition, we propose several dissociation pathways, backed up by quantum chemical calculations on their thermodynamic thresholds. The threshold calculations also support that the resonances formed at higher energies lead to fragment anions observable by mass spectrometry, whereas the resonances at low electron energies decay only by electron autodetachment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

The chemical and physical properties of tetravalent lanthanides: Pr, Nd, Tb, and Dy

The fundamental redox chemistry and valence electronic structure of the lanthanides in molecular complexes and extended solids continues to be a fertile area of research. The contemporary understanding of the accessible oxidation states of the lanthanide elements and the variability in their electronic structure is the result of several paradigm shifts. While the lanthanide elements have already found widespread use in technical and consumer applications, the continued reevaluation of basic redox properties is a central chemical concern to establish a more complete description of periodic properties. This fundamental understanding of valence electronic structure as it is derived from oxidation state and coordination environment is essential for the continued development of lanthanides in quantum information science and quantum materials research. This review presents the chemical and physical properties of tetravalent lanthanide ions in extended solids and molecules with a focus on the elements apart from cerium: praseodymium, neodymium, terbium, and dysprosium.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Band alignments and polarization properties of the Zn-IV-nitrides

Zn-IV-nitrides have a range of potential applications in electronic and optoelectronic devices and can be integrated with currently used III-nitride semiconductors and their alloys. Using hybrid density functional theory, we examine band gaps, band offsets, and polarization properties of the Zn-IV-nitrides and the ramifications of these properties on heterointerfaces formed between the Zn-IV-nitrides and III-nitrides. Here, we find a type-II band alignment between ZnGeN 2 and GaN, where the valence band of GaN is 0.28 eV above the valence band of ZnGeN 2 . Heterostructures between Zn-IV-nitrides and III-nitrides result in interface charges that allow for novel heterostructures and increased control over polarization fields. We find that an interface between In x Ga 1-x N and ZnGeN 2 can lead to zero interfacial polarization charge; however, the band alignments are unfavorable for carrier confinement in light-emitting devices. At the interface between AlN and ZnSiN 2 , we predict a large two-dimensional electron gas to form, confined to the ZnSiN 2 layer.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Electronically-coupled redox centers in trimetallic cobalt complexes

Synthesis and isolation of molecular building blocks of metal–organic frameworks (MOFs) can provide unique opportunities for characterization that would otherwise be inaccessible due to the heterogeneous nature of MOFs. Herein, we report a series of trinuclear cobalt complexes incorporating dithiolene ligands, triphenylene-2,3,6,7,10,11-hexathiolate (THT) (1 3+ ), and benzene hexathiolate (BHT) (2 3+ ), with 1,1,1,-tris(diphenylphosphinomethyl)ethane (triphos) employed as the capping ligand. Single crystal X-ray analyses of 1 3+ and 2 3+ display three five-coordinate cobalt centers bound to the triphos and dithiolene ligands in a distorted square pyramidal geometry. Cyclic voltammetry studies of 1 3+ and 2 3+ reveal three redox features associated with the formation of mixed valence states due to the sequential reduction of the redox-active metal centers (Co III/II ). Using this electrochemical data, the comproportionality values were determined for 1 and 2 (log K c = 1.4 and 1.5 for 1, and 4.7 and 5.8 for 2), suggesting strong resonance-stabilized coupling of the metal centers, with stronger electronic coupling observed for complex 2 compared to that for complex 1. Cyclic voltammetry studies were also performed in solvents of varying polarity, whereupon the difference in the standard potentials (ΔE 1/2 ) for 1 and 2 was found to shift as a function of the polarity of the solvent, indicating a negative correlation between the dielectric constant of the electrochemical medium and the stability of the mixed valence species. Spectroelectrochemical studies of in situ generated multi-valent (MV) states of complexes 1 and 2 display characteristic NIR intervalence charge transfer (IVCT) bands, and analysis of the IVCT transitions for complex 2 suggests a weakly coupled class II multi-valent species and relatively large electronic coupling factors (1700 cm –1 for the first multi-valent state of 2 2+ , and 1400 and 4000 cm –1 for the second multi-valent state of 2 + ). Here, density functional theory (DFT) calculations indicate a significant deviation in relative energies of the frontier orbitals of complexes 1 3+ , 2 3+ , and 3 + that contrasts those calculated for the analogous trinuclear cobalt dithiolene complexes employing pentamethylcyclopentadienyl (Cp*) as the capping ligand (Co 3 Cp* 3 THT and Co 3 Cp* 3 BHT, respectively), and may be a result of the cationic nature of complexes 1 3+ , 2 3+ , and 3 + .

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

Intrinsic doping limitations in inorganic lead halide perovskites

Inorganic halide perovskites (HP's) of the CsPbX 3 (X = I, Br, Cl) type have reached prominence in photovoltaic solar cell efficiencies, leading to the expectation that they are a new class of semiconductors relative to the traditional ones. Peculiarly, they have shown an asymmetry in their ability to be doped by holes vs. electrons. Indeed, both structural defect-induced doping as well as extrinsic impurity-induced doping strangely often result in HP's in a unipolar doping (dominantly p-type) with low free carriers’ concentration. This raises the question whether such doping limitations presents just a temporary setback due to insufficient optimization of the doping process, or perhaps this represents an intrinsic, physically-mandated bottleneck. Here we study three fundamental Design Principles (DP's) for ideal doping, applying them via density functional doping theory to these HP's, thus identifying the violated DP that explains the doping limitations and asymmetry in these HP's. Here, the target DP are: (i) requires that the thermodynamic transition level between different charge states induced by the dopants must ideally be energetically shallow both for donors (n-type) or acceptors (p-type); DP-(ii) requires that the ‘Fermi level pinning energies’ for electrons E (n) pin and holes E (p) pin (being the limiting value of the Fermi level before a structural defect that compensate the doping forms spontaneously) should ideally be located inside the conduction band for n-type doping and inside the valence band for p-type doping. DP-(iii) requires that the doping-induced shift in equilibrium Fermi energy ΔE (n) F towards the conduction band for n-type doping (shift of ΔE (p) F towards the valence band, for p-type doping) to be sufficiently large. We find that, even though in HP's based on Br and Cl there are numerous shallow level dopants that satisfy DP-(i), in contrast DP-(ii) is satisfied only for holes and DP-(iii) fails for both holes and electrons, being the ultimate bottleneck for the n-type doping in Iodide HP's. This suggests an intrinsic mechanism for doping limitations in this class of semiconductors in terms of recognized physical mechanisms.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Synthesis and structural characterization of the new Zintl phases Eu 10 Mn 6 Bi 12 and Yb 10 Zn 6 Sb 12

Two new ternary compounds, Eu 10 Mn 6 Bi 12 and Yb 10 Zn 6 Sb 12 , were synthesized and structurally characterized. The synthesis was achieved either through reactions in sealed niobium tubes or in alumina crucibles by combining the elements in excess molten Sb. Their structures were elucidated using single-crystal X-ray diffraction, and they were determined to crystallize in the orthorhombic space group Cmmm (no. 65) with the Eu 10 Cd 6 Bi 12 structure type. Akin to the archetype phase, both Mn and Zn sites contain about 25% of vacancies. Furthermore, the anionic substructure of the title phases can be described as [M 6 Pn 12 ] (M = Zn, Mn; Pn = Sb, Bi) double layers composed of the corner and edge-sharing [MPn 4 ] tetrahedra, linked by [Pn 2 ] 4– dumbbells. Eu 2+ /Yb 2+ cations fill the space between the layers, with the valence electron counts adhering closely to the Zintl–Klemm rules, i.e., both Eu 10 Mn 6 Bi 12 and Yb 10 Zn 6 Sb 12 are expected to be valence-precise compounds. Analysis of the electronic structure and transport properties of Yb 10 Zn 6 Sb 12 indicate semimetallic behavior with relatively low Seebeck coefficient and resistivity that slightly decreases as a function of temperature.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Understanding the evolution of double perovskite band structure upon dimensional reduction

Recent investigations into the effects of dimensional reduction on halide double perovskites have revealed an intriguing change in band structure when the three-dimensional (3D) perovskite is reduced to a two-dimensional (2D) perovskite with inorganic sheets of monolayer thickness (n = 1). The indirect bandgap of 3D Cs 2 AgBiBr 6 becomes direct in the n = 1 perovskite whereas the direct bandgap of 3D Cs 2 AgTlBr 6 becomes indirect at the n = 1 limit. Here, we apply a linear combination of atomic orbitals approach to uncover the orbital basis for this bandgap symmetry transition with dimensional reduction. We adapt our previously established method for predicting band structures of 3D double perovskites for application to their 2D congeners, emphasizing new considerations required for the 2D lattice. In particular, we consider the inequivalence of the terminal and bridging halides and the consequences of applying translational symmetry only along two dimensions. The valence and conduction bands of the layered perovskites can be derived from symmetry adapted linear combinations of halide p orbitals propagated across the 2D lattice. The dispersion of each band is then determined by the bonding and antibonding interactions of the metal and halide orbitals, thus affording predictions of the essential features of the band structure. We demonstrate this analysis for 2D Ag–Bi and Ag–Tl perovskites with sheets of mono- and bilayer thickness, establishing a detailed understanding of their band structures, which enables us to identify the key factors that drive the bandgap symmetry transitions observed at the n = 1 limit. Importantly, these insights also allow us to make the general prediction that direct → indirect or indirect → direct bandgap transitions in the monolayer limit are most likely in double perovskite compositions that involve participation of metal d orbitals at the band edges or that have no metal-orbital contributions to the valence band, laying the groundwork for the targeted realization of this phenomenon.

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

Water-coupled monovalent and divalent ion transport in polyviologen networks

Redox-active polymers (RAPs) are of interest as environmentally friendly and earth-abundant energy storage materials. Polyviologens are promising RAPs, but they tend to dissolve during operation. Further, the two-electron redox reaction for polyviologens in various electrolytes is not always reversible, highlighting the need for a deeper understanding of the redox mechanism. Here, the energy storage mechanism for a cross-linked viologen (PTPM) is demonstrated using electrochemical quartz crystal microbalance with dissipation monitoring (EQCM-D), comparing NaCl and Na2SO4 aqueous electrolytes. E-QCMD reveals that the ion-electron transport mechanism is strongly dependent on the valency of the anion. More sudden and dramatic changes in the electrode's mass were observed for the divalent sulfate ion as compared to the smooth mass transitions associated with the monovalent chloride ion. Meanwhile, there was marked hysteresis in the mass transfer profile for NaCl, but little hysteresis for Na2SO4. Our results demonstrate that electrolyte design, and specifically ion valency, will have a large impact on the nature of mass transport in polymer-based electrodes. This work enables electrolyte selection for the next generation polymer batteries with improved performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Energy band alignment of atomic layer deposited HfO{sub 2} oxide film on epitaxial (100)Ge, (110)Ge, and (111)Ge layers

Crystallographically oriented epitaxial Ge layers were grown on (100), (110), and (111)A GaAs substrates by in situ growth process using two separate molecular beam epitaxy chambers. The band alignment properties of atomic layer hafnium oxide (HfO{sub 2}) film deposited on crystallographically oriented epitaxial Ge were investigated using x-ray photoelectron spectroscopy (XPS). Valence band offset, {Delta}E{sub v} values of HfO{sub 2} relative to (100)Ge, (110)Ge, and (111)Ge orientations were 2.8 eV, 2.28 eV, and 2.5 eV, respectively. Using XPS data, variation in valence band offset, {Delta}E{sub V}(100)Ge>{Delta}E{sub V}(111)Ge>{Delta}E{sub V}(110)Ge, was obtained related to Ge orientation. Also, the conduction band offset, {Delta}E{sub c} relation, {Delta}E{sub c}(110)Ge>{Delta}E{sub c}(111)Ge>{Delta}E{sub c}(100)Ge related to Ge orientations was obtained using the measured bandgap of HfO{sub 2} on each orientation and with the Ge bandgap of 0.67 eV. These band offset parameters for carrier confinement would offer an important guidance to design Ge-based p- and n-channel metal-oxide field-effect transistor for low-power application.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Optical guided modes coupled with Cerenkov radiation excited in Si slab using angular-resolved electron energy-loss spectrum

Retardation effects in the valence electron energy-loss spectrum (EELS) of a Si slab are analyzed by angular-resolved EELS. The dispersion curves of the valence spectra excited in a slab are directly observed from a specimen area with several different thicknesses and are interpreted by performing a calculation of the dispersion relation using Kroeger's formula. The dispersion curves observed below about 3 eV are attributed to guided modes coupled with Cerenkov radiation (CR). The coupling between guided modes and CR is found to be dependent on the sample thickness (t). For the sample with t > 150 nm, the intensity of the guided modes increased linearly with thickness, revealing the coupling with CR. For t < 150 nm, however, the intensity of the guided modes rapidly decreased due to a diminished coupling with CR, resulting from the thickness-dependent dispersion curves of the guided modes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2013

Interfacial chemical bonding state and band alignment of CaF{sub 2}/hydrogen-terminated diamond heterojunction

CaF{sub 2} films are deposited on hydrogen-terminated diamond (H-diamond) by a radio-frequency sputter-deposition technique at room temperature. Interfacial chemical bonding state and band alignment of CaF{sub 2}/H-diamond heterojunction are investigated by X-ray photoelectron spectroscopy. It is confirmed that there are only C-Ca bonds at the CaF{sub 2}/H-diamond heterointerface. Valence and conductance band offsets of the CaF{sub 2}/H-diamond heterojunciton are determined to be 3.7 {+-} 0.2 and 0.3 {+-} 0.2 eV, respectively. It shows a type I straddling band configuration. The large valence band offset suggests advantage of the CaF{sub 2}/H-diamond heterojunciton for the development of high power and high frequency field effect transistors.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Band offsets of La{sub 2}O{sub 3} on (0001) GaN grown by reactive molecular-beam epitaxy

La{sub 2}O{sub 3} films were prepared on (0001)-oriented GaN substrates via reactive molecular-beam epitaxy. Film orientation and phase were assessed using reflection high-energy electron and X-ray diffraction. Films were observed to grow as predominantly hexagonal La{sub 2}O{sub 3} for thicknesses less than 10 nm while film thickness greater than 10 nm favored mixed cubic and hexagonal symmetries. Band offsets were characterized by X-ray photoelectron spectroscopy on hexagonally symmetric films and valence band offsets of 0.63 {+-} 0.04 eV at the La{sub 2}O{sub 3}/GaN interface were measured. A conduction band offset of approximately 1.5 eV could be inferred from the measured valence band offset.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Investigation of band offsets and direct current leakage properties of nitrogen doped epitaxial Gd{sub 2}O{sub 3} thin films on Si

Dielectric properties of epitaxial Gd{sub 2}O{sub 3} thin films grown on Si have been found to improve significantly by incorporation of suitable dopants. However, in order to achieve optimum electrical properties from such doped oxides, it is important to understand the correlation between doping and the electronic structure of the material. In the present article, we report about the effect of nitrogen doping on the electronic structure and room temperature dc leakage properties of epitaxial Gd{sub 2}O{sub 3} thin films. Epitaxial Gd{sub 2}O{sub 3}:N thin films were grown on p-type Si (111) substrates by solid source molecular beam epitaxy technique using molecular N{sub 2}O as the nitridation agent. First investigations confirmed the presence of substitutional N in the Gd{sub 2}O{sub 3}:N layers. Incorporation of nitrogen did not affect the structural quality of the oxide layers. X ray photoelectron spectroscopy investigations revealed band gap narrowing in epitaxial Gd{sub 2}O{sub 3} due to nitrogen doping, which leads to reduction in the valence band offset of the Gd{sub 2}O{sub 3}:N layers with Si. DC leakage current measured at room temperature revealed that despite reduction in the band gap and valence band offsets due to N doping, the Gd{sub 2}O{sub 3}:N layers remain sufficiently insulating. A significant reduction of the leakage current densities in the Gd{sub 2}O{sub 3}:N layers with increasing nitrogen content suggests that doping of epitaxial Gd{sub 2}O{sub 3} thin films with nitrogen can be an effective route to eliminate the adverse effects of the oxygen vacancy induced defects in the oxide layers.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗