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DOE OSTI2024

Manipulating Photoconduction in Cu–Pyrene 1-D Coordination Nanosheets by Modulating Interlayer π–π Stacking

2D conductive metal organic frameworks (MOFs) have become promising candidates for applications in electronic and photoelectronic devices. However, the lack of a fundamental understanding of the charge transport mechanism and synthetic design to alter their conductivity limits their potential applications. In this work, we report the design and synthesis of two 1D Cu–pyrene coordination nanosheets, Cu–pyrene-4,5,9,10 tetrathiol (Cu-PTT) and Cu–2,7-di-tert-butylpyrene-4,5,9,10-tetrathiol (Cu– tBu PTT), as models of 2D conductive MOFs, where the introduction of two different functional groups (H and tert-butyl groups) at the 2 and 7 positions of the PTT ligands is used to tune the interlayer distance and π–π stacking of MOFs. Using optical pump terahertz probe spectroscopy, we show that both nanosheets exhibit appreciable photoconduction, but the photoconduction in Cu– tBu PTT is reduced with respect to that in Cu–PTT, which can be attributed to the larger interlayer distance in the former leading to the decoupling of the interlayer charge transport pathway. Furthermore, these results demonstrate a unique strategy to investigate the impact of out-of-plane extended conjugation on photoconduction in conductive conjugated polymers, MOFs, or coordination nanosheets through adjusting their interlayer spacing.

14 SOLAR ENERGY↗

DOE OSTI2017

Molecular Dynamics Study of CO 2 and H 2 O Intercalation in Smectite Clays: Effect of Temperature and Pressure on Interlayer Structure and Dynamics in Hectorite

Grand Canonical Molecular Dynamics (GCMD) simulations were performed to investigate the intercalation of CO 2 and H 2 O molecules in the interlayers of the smectite clay, Na-hectorite, at temperatures and pressures relevant to petroleum reservoir and geological carbon sequestration conditions and in equilibrium with H 2 O-saturated CO 2 . The computed adsorption isotherms indicate that CO 2 molecules enter the interlayer space of Na-hectorite only when it is hydrated with approximately three H 2 O molecules per unit cell. The computed immersion energies show that the bilayer hydrate structure (2WL) contains less CO 2 than the monolayer structure (1WL) but that the 2WL hydrate is the most thermodynamically stable state, consistent with experimental results for a similar Na-montmorillonite smectite. Under all T and P conditions examined (323–368 K and 90–150 bar), the CO 2 molecules are adsorbed at the midplane of clay interlayers for the 1WL structure and closer to one of the basal surfaces for the 2WL structure. Interlayer CO 2 molecules are dynamically less restricted in the 2WL structures. The CO 2 molecules are preferentially located near basal surface oxygen atoms and H 2 O molecules rather than in coordination with Na+ ions. Accounting for the orientation and flexibility of the structural -OH groups of the clay layer has a significant effect on the details of the computed structure and dynamics of H 2 O and CO 2 molecules but does not affect the overall trends with changing basal spacing or the principal structural and dynamical conclusions. Temperature and pressure in the ranges examined have little effect on the principal structural and energetic conclusions, but the rates of dynamical processes increase with increasing temperature, as expected.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Metastable Metallic Phase of a Bilayer Blue Phosphorene Induced by Interlayer Bonding and Intralayer Charge Redistributions

We have carried out diffusion Monte Carlo calculations for an A 1 B -1 -stacked bilayer blue phosphorene to find that it undergoes a semiconductor-metal transition as the interlayer distance decreases. While the most stable bilayer structure is a semiconducting one with two monolayers coupled through weak van der Waals interaction, the metallic bilayer at a shorter interlayer distance is found to be only metastable. This is in contrast to a recent theoretical prediction based on random phase approximation that the metallic phase would be the most stable bilayer configuration of blue phosphorene. Our analysis of charge density distributions reveals that the metastable metallic phase is induced by interlayer chemical bonding and intralayer charge redistributions. This study enriches our understanding of interlayer binding of a blue phosphorene and contributes to establishment of correct energetic order between its different phases, which will be essential in devising an experimental pathway for a metallic phosphorene.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

Enhanced Interlayer Coupling and Excitons in Twin-Stacked Two-Dimensional Magnetic CrSBr Bilayers

The degree of electronic coupling between individual layers in van der Waals heterostructures offers a route to engineer their magnetic, electronic, and optical functionalities. Using state-of-the-art first-principles calculations, in this work, we demonstrate that the electronic coupling between two monolayers of CrSBr─an anisotropic two-dimensional magnetic semiconductor─is highly nonlinear and nonmonotonic with respect to their relative twist angle, exhibiting a pronounced maximum at the twin-stacking configuration. The coupling strength scales with both the degree of overlap of Br orbitals adjacent to the van der Waals gap and the cosine of half of the interlayer spin angle. This enhanced interlayer electronic coupling leads to excitons delocalized across the two layers, with a polarization dependence that reflects the interlayer spin alignment. Our results reveal a sensitive interplay among twist angle, magnetism, and excitonic properties in twin-stacked CrSBr bilayers, suggesting twin stacking as an effective means for engineering interlayer coupling.

2D materials↗

DOE OSTI2024

Enhancing Interlayer Charge Transport of Two-Dimensional Perovskites by Structural Stabilization via Fluorine Substitution

Two-dimensional lead-halide perovskites provide a more robust alternative to three-dimensional perovskites in solar energy and optoelectronic applications due to increased chemical stability afforded by interlayer ligands. At the same time, the ligands create barriers for interlayer charge transport, reducing device performance. Using a recently developed ab initio simulation methodology, we demonstrate that ligand fluorination can enhance both hole and electron mobility by 1–2 orders of magnitude. The simulations show that the enhancement arises primarily from improved structural order and reduced thermal atomic fluctuations in the system rather than increased interlayer electronic coupling. Arising from stronger hydrogen bonding and dipolar interactions, the higher structural stability decreases the reorganization energy that enters the Marcus formula and increases the charge transfer rate. The detailed atomistic insights into the electron and hole transfer in layered perovskites indicate that the use of interlayer ligands that make the overall structure more robust is beneficial simultaneously for chemical stability and charge transport, providing an important guideline for the design of new, efficient materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Electro-chemo-mechanical evolution of sulfide solid electrolyte/Li metal interfaces: operando analysis and ALD interlayer effects

Sulfide solid electrolytes (SE) show promise for high-performance solid-state batteries because of their high ionic conductivity and ease of processing. However, sulfide electrolytes have suffered from chemical and electrochemical instability against Li metal anodes. In this paper, we use a suite of in situ/operando microscopy and spectroscopy techniques to demonstrate that Al 2 O 3 interlayers deposited using atomic layer deposition (ALD) delay degradation at the Li/LGPS interface by modifying the solid electrolyte interphase (SEI) chemistry and morphology. Optical and scanning electron microscopy are used to rationalize the electrochemical response of the system, which is attributed to a delayed onset of mechanical degradation at the interface when ALD interlayers are used. Operando X-ray photoelectron spectroscopy demonstrates that the dynamic evolution of SEI chemistry is impacted by the presence of the ALD interlayer. In situ Auger spectroscopy and operando optical microscopy provide visual evidence of spatial heterogeneity of Li plating, which is attributed to the chemo-mechanical degradation of the ALD interphase. The implications of these observations provide valuable insights toward the development of robust interlayers for solid-state batteries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Interlayer spacing in pillared and grafted MCM-22 type silicas: density functional theory analysis versus experiment

Pillaring of synthetic layered crystalline silicates and aluminosilicates provides a strategy to enhance their adsorption and separation performance, and can facilitate the understanding of such behavior in more complex natural clays. In this study, we perform the first-principles density functional theory calculations for the pillaring of the pure silica polymorph of an MCM-22 type molecular sieve. Starting with a precursor material MCM-22P with fully hydroxylated layers, a pillaring agent, (EtO) 3 SiR, can react with hydroxyl groups (–OH) on adjacent internal surfaces, 2(–OH) + (EtO) 3 SiR + H 2 O → (–O) 2 SiOHR + 3EtOH, to form a pillar bridging these surfaces, or with a single hydroxyl, –OH + (EtO) 3 SiR + 2H 2 O → (–O)Si(OH) 2 R + 3EtOH, grafting to one surface. For computational efficiency, we replace the experimental organic ligand, R, by a methyl group. We find that the interlayer spacing in MCM-22 is reduced by 2.66 Å relative to weakly bound layers in the precursor MCM-22P. Including (–O) 2 SiR bridges for 50% (100%) of the hydroxyl sites in MCM-22P increases the interlayer spacing relative to MCM-22 by 2.52 Å (2.46 Å). For comparison, we also analyze the system where all –OH groups in MCM-22P are replaced by non-bridging grafted (–O)Si(OH) 2 R which results in a smaller interlayer spacing expansion of 2.17 Å relative to MCM-22. Our results for the interlayer spacing in the pillared materials are compatible with experimental observations for a similar MCM-22 type material with low Al content (Si : Al = 51 : 1) of an expansion relative to MCM-22 of roughly 2.8 Å and 2.5 Å from our x-ray diffraction and scanning transmission electron microscopy analyses, respectively. The latter analysis reveals significant variation in individual layer spacings.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2018

Temperature dependence of interlayer coupling in perpendicular magnetic tunnel junctions with GdOx barriers

Perpendicular magnetic tunnel junctions with GdO X tunneling barriers have shown a unique voltage controllable interlayer magnetic coupling effect. Here we investigate the quality of the GdO X barrier and the coupling mechanism in these junctions by examining the temperature dependence of the tunneling magnetoresistance and the interlayer coupling from room temperature down to 11 K. The barrier is shown to be of good quality with the spin independent conductance only contributing a small portion, 14%, to the total room temperature conductance, similar to AlO X and MgO barriers. The interlayer coupling, however, shows an anomalously strong temperature dependence including sign changes below 80 K. This non-trivial temperature dependence is not described by previous models of interlayer coupling and may be due to the large induced magnetic moment of the Gd ions in the barrier.

36 MATERIALS SCIENCE↗

DOE OSTI2019

Interlayer correlated fractional quantum Hall state in the ν = 4 / 5 bilayer system

We perform exact diagonalization studies for fractional quantum Hall states at filling factor 4/5 in a bilayer system, on a torus with various aspect ratios and angles. In this work we find that in the absence of tunneling, two weakly coupled 2/5 layers undergo a phase transition into an interlayer-correlated regime, which is also Abelian with the fivefold degeneracy on the torus. In the limit of zero layer separation, this phase becomes a singlet in the pseudospin variable describing the layer degree of freedom. By studying the Chern-number matrix, we show that the K matrix describing the interlayer-correlated regime requires a matrix dimension larger than two and this regime is in particular not described by a Halperin state. A detailed analysis of possible 4 × 4 K matrices having the requisite symmetries and quantum numbers shows that there is only one equivalence class of such matrices. A model wave function representing this universality class is constructed. The role of separate particle number conservation in both layers is discussed, and it is argued that this additional symmetry allows for the further distinction of two different symmetry-protected Abelian phases in the interlayer correlated regime. Interlayer tunneling breaks this symmetry and can drive the system into a single-layer regime when strong enough. A qualitative phase diagram in the tunneling-layer separation parameter space is proposed based on our numerical results.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2020

Interlayer coupling induced quasiparticles

In this work, we present an exact treatment of layered many-body electronic systems in the presence of interlayer coupling within the Schwinger functional derivative approach on the Keldysh contour. Our transparent approach allows us to clarify the definition of interlayer coupling by showing the independent roles hybridization and interactions play in generating new electronic and magnetic excitations. We find interlayer coupling to induce a variety of plasmons, magnons, and excitons, residing within a layer, traversing between layers, or propagating along the interface. Moreover, we predict interfacial excitations, including an electron-hole pairing pathway, facilitated by previously ignored layer nonconserving interactions. Finally, we briefly explore the consequence of interlayer coupling on a bilayer square lattice system.

36 MATERIALS SCIENCE↗

DOE OSTI2017

Two-Dimensional J eff = 1 / 2 Antiferromagnetic Insulator Unraveled from Interlayer Exchange Coupling in Artificial Perovskite Iridate Superlattices

We report an experimental investigation of the two-dimensional J eff =1/2 antiferromagnetic Mott insulator by varying the interlayer exchange coupling in [(SrIrO 3 ) 1 , (SrTiO 3 ) m ] (m=1, 2 and 3) superlattices. Although all samples exhibited an insulating ground state with long-range magnetic order, temperature-dependent resistivity measurements showed a stronger insulating behavior in the m = 2 and m = 3 samples than the m = 1 sample which displayed a clear kink at the magnetic transition. This difference indicates that the blocking effect of the excessive SrTiO 3 layer enhances the effective electron-electron correlation and strengthens the Mott phase. The significant reduction of the Néel temperature from 150 K for m = 1 to 40 K for m = 2 demonstrates that the long-range order stability in the former is boosted by a substantial interlayer exchange coupling. Resonant x-ray magnetic scattering revealed that the interlayer exchange coupling has a switchable sign, depending on the SrTiO 3 layer number m, for maintaining canting-induced weak ferromagnetism. In conclusion, the nearly unaltered transition temperature between the m = 2 and the m = 3 demonstrated that we have realized a two-dimensional antiferromagnet at finite temperatures with diminishing interlayer exchange coupling.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2021

Twist Angle-Dependent Interlayer Exciton Lifetimes in van der Waals Heterostructures

In van der Waals (vdW) heterostructures formed by stacking two monolayers of transition metal dichalcogenides, multiple exciton resonances with highly tunable properties are formed and subject to both vertical and lateral confinement. We investigate how a unique control knob, the twist angle between the two monolayers, can be used to control the exciton dynamics. We observe that the interlayer exciton lifetimes in MoSe 2 /WSe 2 twisted bilayers (TBLs) change by one order of magnitude when the twist angle is varied from 1° to 3.5°. Additionally, using a low-energy continuum model, we theoretically separate two leading mechanisms that influence interlayer exciton radiative lifetimes. The shift to indirect transitions in the momentum space with an increasing twist angle and the energy modulation from the moiré potential both have a significant impact on interlayer exciton lifetimes. We further predict distinct temperature dependence of interlayer exciton lifetimes in TBLs with different twist angles, which is partially validated by experiments. While many recent studies have highlighted how the twist angle in a vdW TBL can be used to engineer the ground states and quantum phases due to many-body interaction, our studies explore its role in controlling the dynamics of optically excited states, thus, expanding the conceptual applications of “twistronics”.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Effect of relative humidity on the interlayer spacing of phosphate intercalated Mg, Al layered double hydroxide (hydrotalcite‐like) crystals

Abstract The availability of water and the type of interlayer anions present affect the arrangement and interlayer spacing of layered double hydroxide (LDH). A systematic study of the effect of relative humidity (RH) on the basal spacing of phosphate intercalated, magnesium aluminum LDHs (MgAl–PO 4 LDH) was conducted, confirming that MgAl‐PO 4 LDH exhibit distinct interlayer spacing corresponding to separate low‐ and high‐hydration states produced when exposed to low and high humidity conditions. The transition from the low‐ to high‐hydration form begins when RH exceeds 33% and is accompanied by the transition from one to two interlayers of water. An improved understanding of the effect of RH on MgAl–PO 4 LDHs will enable more accurate atomistic modeling and experimental characterization of MgAl–PO 4 LDHs and may lead to improvements in the tunability of MgAl‐PO 4 LDHs for commercial applications such as slow‐release fertilizer.

Reed, Titus↗

DOE OSTI2018

Photocarrier generation from interlayer charge-transfer transitions in WS 2 -graphene heterostructures

Efficient interfacial carrier generation in van der Waals heterostructures is critical for their electronic and optoelectronic applications. We demonstrate broadband photocarrier generation in WS 2 -graphene heterostructures by imaging interlayer coupling–dependent charge generation using ultrafast transient absorption microscopy. Interlayer charge-transfer (CT) transitions and hot carrier injection from graphene allow carrier generation by excitation as low as 0.8 eV below the WS 2 bandgap. The experimentally determined interlayer CT transition energies are consistent with those predicted from the first-principles band structure calculation. CT interactions also lead to additional carrier generation in the visible spectral range in the heterostructures compared to that in the single-layer WS 2 alone. The lifetime of the charge-separated states is measured to be ~1 ps. These results suggest that interlayer interactions make graphene–two-dimensional semiconductor heterostructures very attractive for photovoltaic and photodetector applications because of the combined benefits of high carrier mobility and enhanced broadband photocarrier generation.

36 MATERIALS SCIENCE↗

DOE OSTI2017

Spin-filter tunneling in superconducting mesa structures with a ferromagnetic manganite interlayer

We have studied the current transport and magnetism in epitaxial hybrid superconducting mesa structures consisting of a cuprate superconductor and superconducting niobium with a manganite LaMnO{sub 3} (LMO) interlayer. We have shown experimentally using magnetic resonance that the magnetization, magnetic anisotropy parameters, and transition temperature to the ferromagnetic state of the interlayer of the structures are analogous to those of an autonomous LMO film grown on a neodymium gallate substrate. The estimate of the barrier height obtained from the dependence of the characteristic resistance of mesa structures on the interlayer thickness has shown the barrier height variation with the thickness in the range of 5–30 mV. The temperature dependences of the conductivity of the mesa structure in the range between superconducting transition temperatures of the superconductors can be described in the theory taking into account the d-wave nature of the superconductivity for one of the electrodes and the spin-filtering of carriers passing through the tunnel interlayer. Spin-filtering is confirmed by the tunnel magnetoresistance and the high sensitivity of mesa structures to a weak external magnetic field in a voltage interval smaller than the gap of niobium.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2016

Molecular Dynamics Simulations of Anion Exclusion in Clay Interlayer Nanopores

© 2016, Clays and Clay Minerals. All rights reserved. The aqueous chemistry of water films confined between clay mineral surfaces remains an important unknown in predictions of radioelement migration from radioactive waste repositories. This issue is particularly important in the case of long-lived anionic radioisotopes ( 129 I - , 99 TcO - 4 , 36 Cl - ) which interact with clay minerals primarily by anion exclusion. For example, models of ion migration in clayey media do not agree as to whether anions are completely or partially excluded from clay interlayer nanopores. In the present study, this key issue was addressed for Cl - using MD simulations for a range of nanopore widths (6 to 15 Å) overlapping the range of average pore widths that exists in engineered clay barriers. The MD simulation results were compared with the predictions of a thermodynamic model (Donnan Equilibrium model) and two pore-scale models based on the Poisson-Boltzmann equation under the assumption that interlayer water behaves as bulk liquid water. The simulations confirmed that anion exclusion from clay interlayers is greater than predicted by the pore-scale models, particularly at the smallest pore size examined. This greater anion exclusion stems from Cl - being more weakly solvated in nano-confined water than it is in bulk liquid water. Anion exclusion predictions based on the Poisson-Boltzmann equation were consistent with the MD simulation results, however, if the predictions included an ion closest approach distance to the clay mineral surface on the order of 2.0 ± 0.8 Å. These findings suggest that clay interlayers approach a state of complete anion exclusion (hence, ideal semi-permeable membrane properties) at a pore width of 4.2 ± 1.5 Å.

Tournassat, Christophe↗

DOE OSTI2023

Optical reflectance imaging reveals interlayer coupling in mechanically stacked MoS 2 and WS 2 bilayers

Optical reflectance imaging is a popular technique for characterizing 2D materials, thanks to its simplicity and speed of data acquisition. The use of this method for studying interlayer phenomena in stacked 2D layers has, however, remained limited. Here we demonstrate that optical imaging can reveal the nature of interlayer coupling in stacked MoS 2 and WS 2 bilayers through their observed reflectance contrast versus the substrate. Successful determination of interlayer coupling requires co-optimization of the illumination wavelength and the thickness of an underlying SiO 2 film. Our observations are supported by multilayer optical calculations together with an analysis of the effect of any interlayer gap. This approach promises quick characterization of constructed 2D material systems.

Nguyen, Vu↗

NASA NTRS2003

Antiferromagnetic Interlayer Exchange Coupling in All-Semiconducting EuS/PbS/EuS Trilayers

A comprehensive experimental study on the antiferromagnetic interlayer exchange coupling in high quality epitaxial all-semiconducting EuSPbSEuS trilayers is reported. The influence of substrates, the thickness of the non-magnetic PbS spacer layer, and of temperature, was investigated by means of SQUID magnetometry. In trilayers with a PbS thickness between 4 and 12 deg A the low temperature hysteresis loops showed the signature of antiferromagnetic coupling. The value of the interlayer exchange coupling energy was determined by simulating the data with a modified Stoner model, including Zeeman, anisotropy, and exchange coupling energies. An important observation was of a strong dependence of the interlayer exchange coupling energy on temperature, consistent with a power law dependence of the exchange coupling constant on the saturation magnetization of the EuS layers. While no theoretical description is readily available, we conjecture that the observed behavior is due to a dependence of the interlayer exchange coupling energy on the exchange splitting of the EuS conduction band.

Smits, C. J. P.↗