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DOE OSTI2021

Ion specific, thin film confinement effects on conductivity in polymerized ionic liquids.

Acrylate-based polymerized ionic liquids (PILs) with ammonium (Am) or imidazolium (Im) cations and tetrafluoroborate (BF4) or bis(trifluoromethanesulfonyl)imide (TFSI) anions were synthesized and spin coated onto gold interdigitated electrodes on silica to investigate nanoconfinement effects on ion transport. The film thickness ranged from 23 to 313 nm. A significant reduction of the in-plane conductivity was observed in some PIL thin films with thickness below 100 nm. Specifically, Am BF4 PIL showed the largest conductivity drop (ca. 50% difference between a 22 nm and a 261 nm film) while Im TFSI PIL showed almost no change under confinement. The difference in conductivity drop is discussed in terms of (i) differences in interfacial layer thickness by fitting a two-layer conductivity model and (ii) potential changes in glass transition temperature (T-g) under confinement, which were estimated using the Vogel-Fulcher-Tammann fits of bulk conductivities. Decreasing film thickness also caused the dielectric loss peaks to shift to lower frequency, indicating that the ion diffusion process slowed under confinement.

Zhao, Qiujie↗

DOE OSTI2018

Mechanisms of Directed Self-Assembly in Cylindrical Hole Confinements

We report the directed self-assembly of block copolymers in cylindrical holes is a promising technology for lithographic patterning, particularly in the context of vertical interconnect accesses. While the hole-shrink process for single cylinders has been extensively explored, the proliferation of morphological defects remains a significant technological barrier. We use a coarse grained model to explore morphologies that form within cylindrical confinements for combinations of template surface energies. We identify metastable defect morphologies, in addition to the desired cylindrical morphology, in majority-wetting sidewall templates. We use our coarse-grained model and the string method to identify transition pathways between defective morphologies and the cylindrical morphology to elucidate the mechanism of defect annihilation within the confinements; the transition pathway from a disordered state is also identified. Lastly, this work demonstrates that the minimum free energy path for the formation of a cylinder goes through defective morphologies and that designing confinements can eliminate these undesirable transition states.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Impact of Arsenic- and Indium-Terminated InGaAs Stressors on Carrier Confinement, Strain, Defects, and Transport Properties of Tensile-Strained Ge

Device-quality tensile-strained Ge (ε-Ge) grown on a large bandgap semiconductor with superior electrical and optical carrier confinement is essential for group-IV-based optoelectronics. Properties of ε-Ge active layers synthesized on In 0.24 Ga 0.76 As buffers with two different surface terminations─arsenic-rich and indium-rich─were experimentally demonstrated, highlighting the factors not considered in theoretical calculations. High-resolution X-ray diffraction and Raman spectroscopy analyses of these ε-Ge/In 0.24 Ga 0.76 As heterostructures confirmed the fully strained (1.6%) and partially relaxed (0.82%) nature of the ε-Ge bonded with arsenic-terminated (Ge As-terminated ) and indium-terminated (Ge In-terminated ) In 0.24 Ga 0.76 As stressors, respectively. High-resolution cross-sectional transmission electron microscopy showed a coherent, sharp, and fully strained ε-Ge/In 0.24 Ga 0.76 As heterointerface in the Ge As-terminated heterostructure, whereas microtwin defects were present in the Ge In-terminated heterostructure. These heterostructures were further characterized by evaluating the minority carrier lifetimes, high for Ge As-terminated (525 ns) and low for Ge In-terminated (69 ns), using the photoconductive decay technique. Moreover, band alignment was constructed using X-ray photoelectron spectroscopy, where the Ge As-terminated heterostructure revealed that both holes and electrons were confined within the ε-Ge active layer as a type-I band alignment with ΔE V, As-terminated = 0.22 eV and ΔE C,As-terminated = 0.38 eV. On the other hand, the Ge In-terminated heterostructure exhibited a type-II band alignment with ΔE V,In-terminated = – 0.02 eV and ΔE C,In-terminated = 0.53 eV. Furthermore, the magnetotransport properties revealed high mobility (321 cm 2 /(V s)) with single-electron transport in Ge As-terminated heterostructure and low mobility (3.34 cm 2 /(V s)) with multihole transport in the Ge In-terminated heterostructure. Therefore, preferring the ε-Ge on the arsenic-rich surface of In 0.24 Ga 0.76 As stressor over the indium-rich surface during material synthesis offers device-quality materials with high carrier lifetime and superior carrier confinement, which can provide an opportunity to fabricate efficient group-IV-based optoelectronic devices.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Thickness-Independent Vibrational Thermal Conductance across Confined Solid-Solution Thin Films

In this study, we experimentally show that the thermal conductance across confined solid-solution crystalline thin films between parent materials does not necessarily lead to an increase in thermal resistances across the thin-film geometries with increasing film thicknesses, which is counterintuitive to the notion that adding a material serves to increase the total thermal resistance. Confined thin epitaxial Ca 0.5 Sr 0.5 TiO 3 solid-solution films with systematically varying thicknesses in between two parent perovskite materials of calcium titanate and (001)-oriented strontium titanate are grown, and thermoreflectance techniques are used to accurately measure the thermal boundary conductance across the confined solid-solution films, showing that the thermal resistance does not substantially increase with the addition of solid-solution films with increasing thicknesses from ~1 to ~10 nm. Contrary to the macroscopic understanding of thermal transport where adding more material along the heat propagation direction leads to larger thermal resistances, our results potentially offer experimental support to the computationally predicted concept of vibrational matching across interfaces. This concept is based on the fact that a better match in the available heat-carrying vibrations due to an interfacial layer can lead to lower thermal boundary resistances, thus leading to an enhancement in thermal boundary conductance across interfaces driven by the addition of a thin “vibrational bridge” layer between two solids.

36 MATERIALS SCIENCE↗

DOE OSTI2026

Carrier Dynamics of Strongly Confined CsPbI 3 Nanowires

Here, we investigate the carrier dynamics of strongly confined cesium lead iodide (CsPbI 3 ) nanowires and compare them with weakly confined quantum dots (QDs) to understand how dimensionality affects recombination processes. Using time-resolved photoluminescence and ultrafast transient absorption spectroscopy, we find that nanowires exhibit a 5× faster recombination rate and more rapid carrier cooling than QDs. These differences are attributed to enhanced carrier interactions with trap states. Although nanowires exhibit slightly enhanced radiative rates as a result of confinement, their photoluminescence quantum yield remains relatively low, 23 ± 8%, due to competition from nonradiative recombination processes that occur at a faster rate. These findings highlight a dimensionality-dependent trade-off between radiative efficiency and nonradiative losses, providing insight into the limitations and opportunities for low-dimensional perovskite nanostructures. Our results establish design principles for tailoring CsPbI 3 nanocrystal dimensionality to optimize optical performance in optoelectronic applications such as LEDs and solar cells.

Oddo, Alexander M. [University of California, Berk↗

DOE OSTI2016

Effects of Zeolite Structural Confinement on Adsorption Thermodynamics and Reaction Kinetics for Monomolecular Cracking and Dehydrogenation of n -Butane

The results of zeolite structure on the kinetics of n -butane monomolecular cracking and dehydrogenation are investigated for eight zeolites differing in the topology of channels and cages. Monte Carlo simulations are used to calculate enthalpy and entropy changes for adsorption (Δ H ads-H+ and Δ S ads-H+ ) of gas-phase alkanes onto Brønsted protons. These parameters are used to extract intrinsic activation enthalpies (Δ H int ‡ ), entropies (Δ S int ‡ ), and rate coefficients ( k int ) from measured data. As Δ S ads-H+ decreases (i.e., as confinement increases), Δ H int ‡ and Δ S int ‡ for terminal cracking and dehydrogenation decrease for a given channel topology. These findings, together with positive values observed for Δ S int ‡ , indicate that the transition states for these reactions resemble products. For central cracking (an earlier transition state), Δ H int ‡ is relatively constant, while Δ S int ‡ increases as Δ S ads-H+ decreases because less entropy is lost upon protonation of the alkane. Concurrently, selectivities to terminal cracking and dehydrogenation decrease relative to central cracking because Δ S int ‡ decreases for the former reactions. Depending on channel topology, changes in the measured rate coefficients ( k app ) with confinement are driven by changes in k int or by changes in the adsorption equilibrium constant ( K ads-H+ ). Values of Δ S int ‡ and Δ H int ‡ are positively correlated, consistent with weaker interactions between the zeolite and transition state and with the greater freedom of movement of product fragments within more spacious pores. These results differ from earlier reports that Δ H int ‡ and Δ S int ‡ are structure-insensitive and that kappis dominated by K ads-H+ . They also indicate that Δ S ads-H+ is a meaningful descriptor of confinement for zeolites having similar channel topologies.

Janda, Amber↗

DOE OSTI2024

Unraveling the Luminescence Quenching Mechanism in Strong and Weak Quantum-Confined CsPbBr 3 Triggered by Triarylamine-Based Hole Transport Layers

Luminescence quenching by hole transport layers (HTLs) is one of the major issues in developing efficient perovskite light-emitting diodes (PeLEDs), particularly prominent in blue-emitting devices. While a variety of material systems have been used as interfacial layers, the origin of such quenching and the type of interactions between perovskites and HTLs are still ambiguous. Here, we present a systematic investigation of the luminescence quenching of CsPbBr 3 by a commonly employed hole transport polymer, Poly(9,9-dioctylfluorene-alt-N-(4-sec-butylphenyl)-diphenylamine) (TFB) in LEDs. Strong and weakly quantum-confined CsPbBr 3 (nanoplatelets (NPLs)/nanocrystals (NCs)) are rationally selected to study the quenching mechanism by considering the differences in their morphology, energy level alignments, and quantum confinement. The steady-state and time-resolved Stern-Volmer plots unravel the dominance of dynamic and static quenching at lower and higher concentrations of TFB, respectively, with maximum quenching efficiency of 98%. The quenching rate in NCs is faster than in NPLs owing to their longer PL lifetimes and weak quantum confinement. The ultrafast transient absorption results support these dynamics and rule out the involvement of Forster or Dexter energy transfer. Finally, the 1D 1 H and 2D NOESY NMR study confirms the exchange of native ligands at the NCs surface with TFB, leading to dark CsPbBr 3 -TFB ensemble formation accountable for luminescence quenching. This highlights the critical role of the triarylamine functional group on TFB (also the backbone of many HTLs) in the quenching process. These results shed light on the underlying reasons for the luminescence quenching in PeLEDs and will help to choose the interfacial layers rationally for developing efficient LEDs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2011

Aqueous NaCl and CsCl Solutions Confined in Crystalline Slit-Shaped Silica Nanopores of Varying Degree of Protonation

All-atom molecular dynamics simulations were conducted to study the dynamics of aqueous electrolyte solutions confined in slit-shaped silica nanopores of various degrees of protonation. Five degrees of protonation were prepared by randomly removing surface hydrogen atoms from fully protonated crystalline silica surfaces. Aqueous electrolyte solutions containing NaCl or CsCl salt were simulated at ambient conditions. In all cases, the ionic concentration was 1 M. The results were quantified in terms of atomic density distributions within the pores, and the self-diffusion coefficient along the direction parallel to the pore surface. We found evidence for ion-specific properties that depend on ion-surface, water-ion, and only in some cases ion-ion correlations. The degree of protonation strongly affects the structure, distribution, and the dynamic behavior of confined water and electrolytes. Cl - ions adsorb on the surface at large degrees of protonation, and their behavior does not depend significantly on the cation type (either Na + or Cs + ions are present in the systems considered). The cations show significant ion-specific behavior. Na + ions occupy different positions within the pore as the degree of protonation changes, while Cs + ions mainly remain near the pore center at all conditions considered. For a given degree of protonation, the planar self-diffusion coefficient of Cs + is always greater than that of Na + ions. The results are useful for better understanding transport under confinement, including brine behavior in the subsurface, with important applications such as environmental remediation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2014

Digital Transfer Growth of Patterned 2D Metal Chalcogenides by Confined Nanoparticle Evaporation

Developing methods for the facile synthesis of two-dimensional (2D) metal chalcogenides and other layered materials is crucial for emerging applications in functional devices. Controlling the stoichiometry, number of the layers, crystallite size, growth location, and areal uniformity is challenging in conventional vapor phase synthesis. Here, we demonstrate a new route to control these parameters in the growth of metal chalcogenide (GaSe) and dichalcogenide (MoSe 2 ) 2D crystals by precisely defining the mass and location of the source materials in a confined transfer growth system. A uniform and precise amount of stoichiometric nanoparticles are first synthesized and deposited onto a substrate by pulsed laser deposition (PLD) at room temperature. This source substrate is then covered with a receiver substrate to form a confined vapor transport growth (VTG) system. By simply heating the source substrate in an inert background gas, a natural temperature gradient is formed that evaporates the confined nanoparticles to grow large, crystalline 2D nanosheets on the cooler receiver substrate, the temperature of which is controlled by the background gas pressure. Large monolayer crystalline domains (~ 100 m lateral sizes) of GaSe and MoSe 2 are demonstrated, as well as continuous monolayer films through the deposition of additional precursor materials. This novel PLD-VTG synthesis and processing method offers a unique approach for the controlled growth of large-area, metal chalcogenides with a controlled number of layers in patterned growth locations for optoelectronics and energy related applications.

2D layered materials↗

DOE OSTI2016

Direct observation of confined acoustic phonon polarization branches in free-standing semiconductor nanowires

Similar to electron waves, the phonon states in semiconductors can undergo changes induced by external boundaries. However, despite strong scientific and practical importance, conclusive experimental evidence of confined acoustic phonon polarization branches in individual free-standing nanostructures is lacking. Here we report results of Brillouin-Mandelstam light scattering spectroscopy, which reveal multiple (up to ten) confined acoustic phonon polarization branches in GaAs nanowires with a diameter as large as 128 nm, at a length scale that exceeds the grey phonon mean-free path in this material by almost an order-of-magnitude. The dispersion modification and energy scaling with diameter in individual nanowires are in excellent agreement with theory. The phonon confinement effects result in a decrease in the phonon group velocity along the nanowire axis and changes in the phonon density of states. Furthermore, the obtained results can lead to more efficient nanoscale control of acoustic phonons, with benefits for nanoelectronic, thermoelectric and spintronic devices.

36 MATERIALS SCIENCE↗

DOE OSTI2016

Imaging electrostatically confined Dirac fermions in graphene quantum dots

Electrostatic confinement of charge carriers in graphene is governed by Klein tunnelling, a relativistic quantum process in which particle-hole transmutation leads to unusual anisotropic transmission at p-n junction boundaries. Reflection and transmission at these boundaries affect the quantum interference of electronic waves, enabling the formation of novel quasi-bound states. Here we report the use of scanning tunnelling microscopy to map the electronic structure of Dirac fermions confined in quantum dots defined by circular graphene p-n junctions. The quantum dots were fabricated using a technique involving local manipulation of defect charge within the insulating substrate beneath a graphene monolayer. Inside such graphene quantum dots we observe resonances due to quasi-bound states and directly visualize the quantum interference patterns arising from these states. Outside the quantum dots Dirac fermions exhibit Friedel oscillation-like behaviour. Bolstered by a theoretical model describing relativistic particles in a harmonic oscillator potential, our findings yield insights into the spatial behaviour of electrostatically confined Dirac fermions.

74 ATOMIC AND MOLECULAR PHYSICS↗

DOE OSTI2019

Hydrogen bonding structure of confined water templated by a metal-organic framework with open metal sites

Abstract Water in confinement exhibits properties significantly different from bulk water due to frustration in the hydrogen-bond network induced by interactions with the substrate. Here, we combine infrared spectroscopy and many-body molecular dynamics simulations to probe the structure and dynamics of confined water as a function of relative humidity within a metal-organic framework containing cylindrical pores lined with ordered cobalt open coordination sites. Building upon the agreement between experimental and theoretical spectra, we demonstrate that water at low relative humidity binds initially to open metal sites and subsequently forms disconnected one-dimensional chains of hydrogen-bonded water molecules bridging between cobalt atoms. With increasing relative humidity, these water chains nucleate pore filling, and water molecules occupy the entire pore interior before the relative humidity reaches 30%. Systematic analysis of rotational and translational dynamics indicates heterogeneity in this pore-confined water, with water molecules displaying variable mobility as a function of distance from the interface.

Science & Technology - Other Topics↗

DOE OSTI2023

Vibrational signature of hydrated protons confined in MXene interlayers

Here, the hydration structure of protons has been studied for decades in bulk water and protonated clusters due to its importance but has remained elusive in planar confined environments. Two-dimensional (2D) transition metal carbides known as MXenes show extreme capacitance in protic electrolytes, which has attracted attention in the energy storage field. We report here that discrete vibrational modes related to protons intercalated in the 2D slits between Ti 3 C 2 T x MXene layers can be detected using operando infrared spectroscopy. The origin of these modes, not observed for protons in bulk water, is attributed to protons with reduced coordination number in confinement based on Density Functional Theory calculations. This study therefore demonstrates a useful tool for the characterization of chemical species under 2D confinement.

36 MATERIALS SCIENCE↗

DOE OSTI2017

Size-tunable Lateral Confinement in Monolayer Semiconductors

Three-dimensional confinement allows semiconductor quantum dots to exhibit size-tunable electronic and optical properties that enable a wide range of opto-electronic applications from displays, solar cells and bio-medical imaging to single-electron devices. Additional modalities such as spin and valley properties in monolayer transition metal dichalcogenides provide further degrees of freedom requisite for information processing and spintronics. In nanostructures, however, spatial confinement can cause hybridization that inhibits the robustness of these emergent properties. Here in this paper, we show that laterally-confined excitons in monolayer MoS 2 nanodots can be created through top-down nanopatterning with controlled size tunability. Unlike chemically-exfoliated monolayer nanoparticles, the lithographically patterned monolayer semiconductor nanodots down to a radius of 15 nm exhibit the same valley polarization as in a continuous monolayer sheet. The inherited bulk spin and valley properties, the size dependence of excitonic energies, and the ability to fabricate MoS 2 nanostructures using semiconductor-compatible processing suggest that monolayer semiconductor nanodots have potential to be multimodal building blocks of integrated optoelectronics and spintronics systems

77 NANOSCIENCE AND NANOTECHNOLOGY↗

DOE OSTI2017

Confinement Effects on Carbon Dioxide Methanation: A Novel Mechanism for Abiotic Methane Formation

An important scientific debate focuses on the possibility of abiotic synthesis of hydrocarbons during oceanic crust-seawater interactions. While on-site measurements near hydrothermal vents support this possibility, laboratory studies have provided data that are in some cases contradictory. At conditions relevant for sub-surface environments it has been shown that classic thermodynamics favour the production of CO 2 from CH 4 , while abiotic methane synthesis would require the opposite. However, confinement effects are known to alter reaction equilibria. This report shows that indeed thermodynamic equilibrium can be shifted towards methane production, suggesting that thermal hydrocarbon synthesis near hydrothermal vents and deeper in the magma-hydrothermal system is possible. We report reactive ensemble Monte Carlo simulations for the CO 2 methanation reaction. We compare the predicted equilibrium composition in the bulk gaseous phase to that expected in the presence of confinement. In the bulk phase we obtain excellent agreement with classic thermodynamic expectations. When the reactants can exchange between bulk and a confined phase our results show strong dependency of the reaction equilibrium conversions, X CO 2 , on nanopore size, nanopore chemistry, and nanopore morphology. Some physical conditions that could shift significantly the equilibrium composition of the reactive system with respect to bulk observations are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2017

Kerogen Swelling and Confinement: Its implication on Fluid Thermodynamic Properties in Shales

Type I kerogen was isolated from Green River Shale and characterized using SEM, TGA, DSC, and nitrogen adsorption. The swelling behavior of this kerogen with decane was analyzed using traditional test-tube swelling experiment and Dynamic Light Scattering. The TGA and DSC were used to analyze the thermodynamic behavior of decane that was sorbed in the kerogen and show that kerogen suppresses the boiling point of decane due to the effect of confinement. However, the suppression is larger when oil (a multicomponent mixture) was used, possibly due to the combined effect of differential uptake of components by kerogen (kerogen prefers and sorbs polars and aromatics more than saturates, leading to splitting of oil into a sorbed and a free phase) and confinement in nano pores. Test-tube swelling, TGA, and DSC experiments were also performed on pyridine(polar-aromatic)-swelled kerogen. The combined and individual contributions from the two effects (the effect of confinement and differential uptake of hydrocarbon components) on properties of liquid in contact with kerogen, are studied in this work. Molecular Dynamics (MD) simulations revealed the variation in the swelling of type II kerogen in the presence of same amount of different liquids (differential swelling of kerogen).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Enhanced thermoelectric performance via quantum confinement in a metal oxide semiconductor field effect transistor for thermal management

Abstract The performance of thermoelectric devices is gauged by the dimensionless figure of merit $${{{{{\boldsymbol{ZT}}}}}}$$ ZT . Improving $${{{{{\boldsymbol{ZT}}}}}}$$ ZT has proven to be a formidable challenge given the interdependence of its constitutive quantities, namely Seebeck coefficient, electrical conductivity, thermal conductivity, and temperature. Here, we use quantum confinement to decouple Seebeck coefficient and electrical conductivity to demonstrate an order of magnitude quantum-based enhancement to the thermoelectric figure of merit $${{{{{\boldsymbol{ZT}}}}}}$$ ZT in complimentary metal-oxide-semiconductor field-effect transistors. While most quantum-based enhancement is done through physical confinement using two-dimensional materials, our approach uses electrical confinement. Because of this, our device is more robust than the two-dimensional materials currently used. We further articulate that improvement by as much as a factor of 50 could be achieved in a practical setting. Our approach further provides a path for monolithic integration of on-chip coolers and energy scavengers with virtually no deviation from the fabrication flow of standard electronics.

Oxandale, Samuel W. (ORCID:0000000207484066)↗

DOE OSTI2014

Thickness-dependent structural arrangement in nano-confined imidazolium-based ionic liquid films

Here we report that a fundamental understanding of interfacial processes in nano-confined ionic liquids is crucial to increase the performance of modern energy storage devices. It is well-known that interfaces between electrodes and ionic liquids exhibit structures distinct from that of the bulk liquid. Following the recent interest in these systems, we studied the structure of thin ionic liquid films confined in flexible uncharged carbon nano-pores by using fully-atomistic molecular dynamics simulations. We show that the interfacial ions self-assemble into a closely-packed chequerboard-like pattern, formed by both cations and anions in direct contact with the pore wall, and that within this structure we find changes dependent on the thickness of the confined films. At low coverages a dense layer is formed in which both the imidazolium-ring and its alkyl-tail lie parallel to the pore wall. With increasing coverage the alkyl-chains reorient perpendicular to the surface, making space for additional ions until a densified highly ordered layer is formed. This wall-induced self-patterning into interfacial layers with significantly higher than bulk density is consistent with recent experimental and theoretical studies of similar systems. Lastly, this work reveals additional molecular-level details on the effect of the film-thickness on the structure and density of the ionic liquid.

25 ENERGY STORAGE↗