Patrick J. Shamberger

Continuous ultra-thin MoS2 films grown by low-temperature physical vapor deposition

Uniform growth of pristine two dimensional (2D) materials over large areas at lower temperatures without sacrifice of their unique physical properties is a critical pre-requisite for seamless integration of next-generation van der Waals heterostructures into functional devices. This Letter describes a vapor phase growth technique for precisely controlled synthesis of continuous, uniform molecular layers of MoS2 on silicon dioxide and highly oriented pyrolitic graphite substrates of over several square centimeters at 350 °C. Synthesis of few-layer MoS2 in this ultra-high vacuum physical vapor deposition process yields materials with key optical and electronic properties identical to exfoliated layers. The films are composed of nano-scale domains with strong chemical binding between domain boundaries, allowing lift-off from the substrate and electronic transport measurements from contacts with separation on the order of centimeters.

Dielectric surface-controlled low-voltage organic transistors via n-alkyl phosphonic acid self-assembled monolayers on high-k metal oxide.

In this paper, we report on n-alkyl phosphonic acid (PA) self-assembled monolayer (SAM)/hafnium oxide (HfO(2)) hybrid dielectrics utilizing the advantages of SAMs for control over the dielectric/semiconductor interface with those of high-k metal oxides for low-voltage organic thin film transistors (OTFTs). By systematically varying the number of carbon atoms of the n-alkyl PA SAM from six to eighteen on HfO(2) with stable and low leakage current density, we observe how the structural nature of the SAM affects the thin-film crystal structure and morphology, and subsequent device performance of low-voltage pentacene based OTFTs. We find that two primary structural factors of the SAM play a critical role in optimizing the device electrical characteristics, namely, the order/disorder of the SAM and its physical thickness. High saturation-field-effect mobilities result at a balance between disordered SAMs to promote large pentacene grains and thick SAMs to aid in physically buffering the charge carriers in pentacene from the adverse effects of the underlying high-k oxide. Employing the appropriate n-alkyl PA SAM/HfO(2) hybrid dielectrics, pentacene-based OTFTs operate under -2.0 V with low hysteresis, on-off current ratios above 1 x 10(6), threshold voltages below -0.6 V, subthreshold slopes as low as 100 mV dec(-1), and field-effect mobilities as high as 1.8 cm(2) V(-1) s(-1).

Cross-plane thermal properties of transition metal dichalcogenides

In this work, we explore the thermal properties of hexagonal transition metal dichalcogenide compounds with different average atomic masses but equivalent microstructures. Thermal conductivity values of sputtered thin films were compared to bulk crystals. The comparison revealed a >10 fold reduction in thin film thermal conductivity. Structural analysis of the films revealed a turbostratic structure with domain sizes on the order of 5–10 nm. Estimates of phonon scattering lengths at domain boundaries based on computationally derived group velocities were consistent with the observed film microstructure, and accounted for the reduction in thermal conductivity compared to values for bulk crystals.

Cooling Capacity Figure of Merit for Phase Change Materials

In this paper, a figure of merit for the cooling capacity (FOMq) of phase change materials (PCMs) is defined from the analytical solution of the two-phase Neumann–Stefan problem of melting of a semi-infinite material with a fixed temperature boundary condition (BC). This figure of merit is a function of the thermophysical properties of a PCM and is proportional to the heat transfer across the interface with the surrounding medium in this general case. Thus, it has important implications for design and optimization of PCMs for high heat-flux thermal management applications. FOMq of example low melting point metals are presented which exceed those in common nonmetallic PCMs over the same temperature range by over an order of magnitude.

Plutonic xenoliths reveal the timing of magma evolution at Hualalai and Mauna Kea, Hawaii

238 U- 230 Th and U-Pb dating of zircons from leucocratic plutonic xenoliths indicating that lava stratigraphy is an incomplete monitor of magmatic evolution within subsurface res- ervoirs. Our results indicate that diorites from Mauna Kea record postshield evolution over tens of thousands of years when the depth of magma storage increased and highly evolved lavas began erupting. In contrast, diorites and syenogabbros from Hualalai record generation of evolved alkalic magma during the shield stage, and growth of a deep composite pluton ABSTRACT Hawaiian volcanoes evolve through stages that have been delimited by the compositions of their erupted lavas. New in situ 238 U- 230 Th and U-Pb dating of single zircons from leucocratic plutonic xenoliths erupted at Mauna Kea and Hualalai volcanoes, Hawaii, reveals that impor- tant episodes of magmatic evolution are not necessarily refl ected in the stratigraphy or com- positions of erupted lavas. Zircons from Mauna Kea diorites form a heterogeneous population with apparently bimodal ages of ca. 125 ka and ca. 65 ka, suggesting fractionation, intrusion, and crystal recycling about the time of transition of postshield volcanism from basaltic to hawaiitic compositions. Hualalai syenogabbros and diorites record extreme fractionation and generation of alkalic magma at 41 ± 9 ka and 261 ± 28 ka, indicating that alkalic magma was generated ~130,000 yr before the shield to postshield transition inferred from lava stra- tigraphy, and that coeval evolution of chemically distinct magma reservoirs at shallow and deep levels may have characterized the shield stage. These episodes at Hualalai did not cause eruption of evolved lavas, indicating that extreme differentiation in Hawaiian volcanoes is not necessarily followed by eruption of highly evolved magma.

Impact of cycle-hysteresis interactions on the performance of giant magnetocaloric effect refrigerants

Magnetic refrigeration technology based on the giant magnetocaloric effect in solid-state refrigerants is known qualitatively to be limited by dissipative mechanisms accompanying hysteresis in the magneto-structural solid–solid phase transition. In this paper, we quantitatively explore the dependence of cycle performance metrics (cooling power, temperature span, work input, and fractional Carnot efficiency) on hysteresis properties (thermal hysteresis, one-way transition width) of the magneto-structural phase transition in a Ni45Co5Mn36.6In13.4 alloy system. We investigate a variety of Ericsson-type magnetic refrigeration cycles, using a Preisach-based non-equilibrium thermodynamic framework to model the evolution of the alloys magnetic and thermal properties. Performance metrics are found to depend strongly on hysteresis parameters, regardless of the cycle chosen. However, for a given hysteresis parameter set, the materials transformation temperatures determine a unique cycle that maximizes efficiency. For the model system used undergoing Ericsson cycles with and maximum field constraint, fractional Carnot efficiencies in excess of 0.9 require thermal hysteresis below and , respectively. We conclude briefly with some general materials considerations for mitigating these hysteresis inefficiencies through microstructure design and other materials processing strategies.

Mixing and electronic entropy contributions to thermal energy storage in low melting point alloys

Melting of crystalline solids is associated with an increase in entropy due to an increase in configurational, rotational, and other degrees of freedom of a system. However, the magnitude of chemical mixing and electronic degrees of freedom, two significant contributions to the entropy of fusion, remain poorly constrained, even in simple 2 and 3 component systems. Here, we present experimentally measured entropies of fusion in the Sn-Pb-Bi and In-Sn-Bi ternary systems, and decouple mixing and electronic contributions. We demonstrate that electronic effects remain the dominant contribution to the entropy of fusion in multi-component post-transition metal and metalloid systems, and that excess entropy of mixing terms can be equal in magnitude to ideal mixing terms, causing regular solution approximations to be inadequate in the general case. Finally, we explore binary eutectic systems using mature thermodynamic databases, identifying eutectics containing at least one semiconducting intermetallic phase as promising candidates to exceed the entropy of fusion of monatomic endmembers, while simultaneously maintaining low melting points. These results have significant implications for engineering high-thermal conductivity metallic phase change materials to store thermal energy.Melting of crystalline solids is associated with an increase in entropy due to an increase in configurational, rotational, and other degrees of freedom of a system. However, the magnitude of chemical mixing and electronic degrees of freedom, two significant contributions to the entropy of fusion, remain poorly constrained, even in simple 2 and 3 component systems. Here, we present experimentally measured entropies of fusion in the Sn-Pb-Bi and In-Sn-Bi ternary systems, and decouple mixing and electronic contributions. We demonstrate that electronic effects remain the dominant contribution to the entropy of fusion in multi-component post-transition metal and metalloid systems, and that excess entropy of mixing terms can be equal in magnitude to ideal mixing terms, causing regular solution approximations to be inadequate in the general case. Finally, we explore binary eutectic systems using mature thermodynamic databases, identifying eutectics containing at least one semiconducting intermetallic phase as pr...

Towards High Energy Density, High Conductivity Thermal Energy Storage Composites

Thermal energy storage (TES) materials absorb transient pulses of heat, allowing for rapid storage of low-quality thermal energy for later use, and effective temperature regulation as part of a thermal management system. This paper describes recent development of salt hydrate-based TES composites at the Air Force Research Laboratory. Salt hydrates are known to be susceptible to undercooling and chemical segregation, and their bulk thermal conductivities remain too low for rapid heat transfer. Here, we discuss recent progress towards solving these challenges in the composite system lithium nitrate trihydrate/graphitic foam. This system takes advantage of both the high volumetric thermal energy storage density of lithium nitrate trihydrate and the high thermal conductivity of graphitic foams. We demonstrate a new stable nucleation agent specific to lithium nitrate trihydrate which decreases undercooling by up to ∼70% relative to previously described nucleation agents. Furthermore, we demonstrate the compatibility of lithium nitrate trihydrate and graphitic foam with the addition of a commercial nonionic silicone polyether surfactant. Finally, we show that thermal conductivity across water-graphite interfaces is optimized by tuning the surfactant concentration. These advances demonstrate a promising route to synthesizing high energy density, high thermal conductivity TES composites.Copyright

Microstructure dependent filament forming kinetics in HfO2 programmable metallization cells

Variability remains the principal concern for commercialization of HfO2 based resistance switching devices. Here, we investigate the role of thermal processing conditions on internal structure of atomic layer deposited HfO2 thin films, and the impact of that structure on filament forming kinetics of p+ Si/HfO2/Cu and TiN/HfO2/Cu devices. Regardless of bias polarity or electrode metal, filament formation times are at least one order of magnitude shorter in polycrystalline than in amorphous films, which we attribute to the presence of fast ion migration along grain boundaries. Within polycrystalline films, filament formation times are correlated with degree of crystalline orientation. Inter-device variability in forming time is roughly equivalent across HfO2 film processing conditions. The kinetics of filament forming are shown to be highly dependent on HfO2 microstructure, with possible implications for the inter-device variability of subsequent switching cycles.

Effects of hysteresis and Brayton cycle constraints on magnetocaloric refrigerant performance

Despite promising proofs of concept, system-level implementation of magnetic refrigeration has been critically limited by history-dependent refrigerant losses that interact with governing thermodynamic cycles to adversely impact refrigeration performance. Future development demands a more detailed understanding of how hysteresis limits performance, and of how different types of cycles can mitigate these limitations, but without the extreme cost of experimental realization. Here, the utility of Brayton cycles for magnetic refrigeration is investigated via direct simulation, using a combined thermodynamic-hysteresis modeling framework to compute the path-dependent magnetization and entropy of a model alloy for a variety of feasible Brayton cycles between 0–1.5 T and 0–5 T. By simultaneously varying the model alloys hysteresis properties and applying extensions of the thermodynamic laws to non-equilibrium systems, heat transfers and efficiencies are quantified throughout the space of hystereses and Brayton ...