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Eric A. Stach

Publications and source records attributed to Eric A. Stach.

34 records · Page 2Linked to original sources
arXiv2023

Wafer-scale growth of two-dimensional, phase-pure InSe

Two-dimensional (2D) indium monoselenide (InSe) has attracted significant attention as a III-VI two-dimensional semiconductor (2D) with a combination of favorable attributes from III-V semiconductors as well as van der Waals 2D transition metal dichalcogenides. Nevertheless, the large-area synthesis of phase-pure 2D InSe remains unattained due to the complexity of the binary In-Se system and the difficulties in promoting lateral growth. Here, we report the first polymorph-selective synthesis of epitaxial 2D InSe by metal-organic chemical deposition (MOCVD) over 2 inch diameter sapphire wafers. We achieve thickness-controlled, layer-by-layer epitaxial growth of InSe on c-plane sapphire via dynamic pulse control of Se/In flux ratio. The layer-by-layer growth allows thickness control over wafer scale with tunable optical properties comparable to bulk crystals. Finally, the gate-tunable electrical transport suggests that MOCVD-grown InSe could be a potential channel material for back-end-of-line integration in logic transistors with field-effect mobility comparable to single-crystalline flakes.

cond-mat.mtrl-sci↗
arXiv2022

Surface Rearrangement and Evaporation Kinetics of Supported Gold Nanoparticle Catalysts

Heterogeneous catalysts consisting of supported metallic nanoparticles typically derive exceptional catalytic activity from their large proportion of under-coordinated surface sites which promote adsorption of reactant molecules. Simultaneously, these high energy surface configurations are unstable, leading to nanoparticle growth or degradation, and eventually a loss of catalytic activity. Surface morphology of catalytic nanoparticles is paramount to catalytic activity, selectivity, as well as degradation rates, however, it is well-known that harsh reaction conditions can cause the surface structure to change. Still, limited research has focused on understanding the link between nanoparticle surface facets and degradation rates or mechanisms. Here, we study a model Au supported catalyst system over a range of temperatures using a combination of \textit{in situ} Transmission Electron Microscopy, kinetic Monte Carlo simulations, and density functional theory calculations to establish an atomistic picture of how variations in surface structures and atomic coordination environments lead to shifting evolution mechanisms as a function of temperature. By combining experimental results, which yield direct observation of dynamic shape changes and particle evaporation rates, with computational techniques, which enable understanding the fundamental thermodynamics and kinetics of nanoparticle evolution, we illustrate a two-step evolution mechanism in which mobile adatoms form through desorption from low-coordination facets and subsequently evaporate off the particle surface. By understanding the role of temperature in the competition between surface diffusion and evaporation, we are able to show how individual atomic movements lead to particle-scale morphological changes, and rationalize why evaporation rates vary between particles in a system of nearly identical nanoparticles.

cond-mat.mtrl-sci↗
arXiv2022

High Density, Localized Quantum Emitters in Strained 2D Semiconductors

Two-dimensional chalcogenide semiconductors have recently emerged as a host material for quantum emitters of single photons. While several reports on defect and strain-induced single photon emission from 2D chalcogenides exist, a bottom-up, lithography-free approach to producing a high density of emitters remains elusive. Further, the physical properties of quantum emission in the case of strained 2D semiconductors are far from being understood. Here, we demonstrate a bottom-up, scalable, and lithography-free approach to creating large areas of localized emitters with high density (~150 emitters/um2) in a WSe2 monolayer. We induce strain inside the WSe2 monolayer with high spatial density by conformally placing the WSe2 monolayer over a uniform array of Pt nanoparticles with a size of 10 nm. Cryogenic, time-resolved, and gate-tunable luminescence measurements combined with near-field luminescence spectroscopy suggest the formation of localized states in strained regions that emit single photons with a high spatial density. Our approach of using a metal nanoparticle array to generate a high density of strained quantum emitters opens a new path towards scalable, tunable, and versatile quantum light sources.

cond-mat.mes-hall↗
arXiv2022

Scalable CMOS-BEOL compatible AlScN/2D Channel FE-FETs

Intimate integration of memory devices with logic transistors is a frontier challenge in computer hardware. This integration is essential for augmenting computational power concurrently with enhanced energy efficiency in big-data applications such as artificial intelligence. Despite decades of efforts, reliable, compact, energy efficient and scalable memory devices are elusive. Ferroelectric Field Effect Transistors (FE-FETs) are a promising candidate but their scalability and performance in a back-end-of-line (BEOL) process remain unattained. Here, we present scalable BEOL compatible FE-FETs using two-dimensional (2D) MoS2 channel and AlScN ferroelectric dielectric. We have fabricated a large array of FE-FETs with memory windows larger than 7.8 V, ON/OFF ratios of greater than 10^7, and ON current density greater than 250 uA/um, all at ~80 nm channel lengths. Our devices show stable retention up to 20000 secs and endurance up to 20000 cycles in addition to 4-bit pulse programmable memory features thereby opening a path towards scalable 3D hetero-integration of 2D semiconductor memory with Si CMOS logic.

physics.app-ph↗
arXiv2021

Scalable synthesis of 2D van der Waals superlattices

Heterostructure materials form the basis of much of modern electronics, from transistors to lasers and light-emitting diodes. Recent years have seen a renewed focus on creating heterostructures through the vertical integration of two-dimensional materials, including graphene, hexagonal boron nitride, and transition metal dichalcogenides (TMDCs). However, fundamental challenges associated with materials processing have limited material quality and impeded scalability. We demonstrate a method to convert sub-nanometer metal films deposited on silicon and sapphire into TMDC heterostructures through vapor-phase processing. The resulting heterostructures and superlattices exhibit novel properties compared with stand-alone TMDCs, including reduced bandgap, enhanced light-matter coupling, and improved catalytic performance. This robust and scalable synthetic method provides new opportunities to generate a wide range of artificially stacked 2D superlattices with controlled morphology and composition.

cond-mat.mtrl-sci↗
arXiv2021

Light-Matter Coupling in Scalable Van der Waals Superlattices

Two-dimensional (2D) crystals have renewed opportunities in design and assembly of artificial lattices without the constraints of epitaxy. However, the lack of thickness control in exfoliated van der Waals (vdW) layers prevents realization of repeat units with high fidelity. Recent availability of uniform, wafer-scale samples permits engineering of both electronic and optical dispersions in stacks of disparate 2D layers with multiple repeating units. We present optical dispersion engineering in a superlattice structure comprised of alternating layers of 2D excitonic chalcogenides and dielectric insulators. By carefully designing the unit cell parameters, we demonstrate > 90 % narrowband absorption in < 4 nm active layer excitonic absorber medium at room temperature, concurrently with enhanced photoluminescence in cm2 samples. These superlattices show evidence of strong light-matter coupling and exciton-polariton formation with geometry-tunable coupling constants. Our results demonstrate proof of concept structures with engineered optical properties and pave the way for a broad class of scalable, designer optical metamaterials from atomically-thin layers.

cond-mat.mtrl-sci↗
arXiv2020

Efficacy of Boron Nitride Encapsulation against Plasma-Processing in van der Waals Heterostructures

Two-dimensional (2D) transition metal dichalcogenides (TMDCs) are the subject of intense investigation for applications in optics, electronics, catalysis, and energy storage. Their optical and electronic properties can be significantly enhanced when encapsulated in an environment that is free of charge disorder. Because hexagonal boron nitride (h-BN) is atomically thin, highly-crystalline, and is a strong insulator, it is one of the most commonly used 2D materials to encapsulate and passivate TMDCs. In this report, we examine how ultrathin h-BN shields an underlying MoS2 TMDC layer from the energetic argon plasmas that are routinely used during semiconductor device fabrication and post-processing. Aberration-corrected Scanning Transmission Electron Microscopy is used to analyze defect formation in both the h-BN and MoS2 layers, and these observations are correlated with Raman and photoluminescence spectroscopy. Our results highlight that h-BN is an effective barrier for short plasma exposures (< 30 secs) but is ineffective for longer exposures, which result in extensive knock-on damage and amorphization in the underlying MoS2.

cond-mat.mtrl-sci↗
arXiv2020

Post-CMOS Compatible Aluminum Scandium Nitride/2D Channel Ferroelectric Field-Effect-Transistor

In 1963, Moll and Tarui suggested that the field-effect conductance of a semiconductor could be controlled by the remanent polarization of a ferroelectric (FE) material to create a ferroelectric field-effect transistor (FE-FET). However, subsequent efforts to produce a practical, compact FE-FET have been plagued by low retention and incompatibility with Complementary Metal Oxide Semiconductor (CMOS) process integration. These difficulties led to the development of trapped-charge based memory devices (also called floating gate or flash memory), and these are now the mainstream non-volatile memory (NVM) technology. Over the past two decades, advances in oxide FE materials have rejuvenated the field of ferroelectrics and made FE random access memories (FE-RAM) a commercial reality. Despite these advances, commercial FE-RAM based on lead zirconium titanate (PZT) has stalled at the 130 nm due to process challenges.The recent discovery of scandium doped aluminum nitride (AlScN) as a CMOS compatible ferroelectric presents new opportunities for direct memory integration with logic transistors due to the low temperature of AlScN deposition (approx. 350 C). This temperature is compatible with CMOS back end of line processes. Here, we present a FE-FET device composed of an AlScN FE dielectric layer integrated with a channel layer of a van der Waals two-dimensional (2D) semiconductor, MoS2. Our devices show an ON/OFF ratio ~ 10^6, concurrent with a normalized memory window of 0.3 V/nm. The devices also demonstrate stable, two-state memory retention for up to 10^4 seconds. Our simulations and experimental results suggest that the combination of AlScN and 2D semiconductors is nearly ideal for low power FE-FET memory. These results demonstrate a new approach in embedded memory and in-memory computing, and could even lead to effective neuromorphic computing architectures.

physics.app-ph↗
arXiv2020

Giant gate-tunability of complex refractive index in semiconducting carbon nanotubes

Electrically-tunable optical properties in materials are desirable for many applications ranging from displays to lasing and optical communication. In most two-dimensional thin-films and other quantum confined materials, these constants have been measured accurately. However, the optical constants of single wall nanotubes (SWCNT) as a function of electrostatic tuning are yet to be measured due to lack of electronic purity and spatial homogeneity over large areas. Here, we measure the basic optical constants of ultrathin high-purity (>99%) semiconducting single wall carbon nanotube (s-SWCNT) films with spectroscopic ellipsometry. We extract the gate-tunable complex refractive index of s-SWCNT films and observe giant modulation of the real refractive index (~11.2% or an absolute value of >0.2) and extinction coefficient (~11.6%) in the near-infrared (IR) region (1.3-1.55 μm) induced by the applied electric field significantly higher than all existing electro-optic semiconductors in this wavelength range. We further design a multilayer IR reflection phase modulator stack by combining s-SWCNT and monolayer MoS2 heterostructures that can attain >45° reflection phase modulation at 1600 nm wavelength for < 200 nm total stack thickness. Our results highlight s-SWCNT as a promising material system for infrared photonics and electro-optics in telecommunication applications.

physics.optics↗
arXiv2020

Direct Visualisation of Out-of-Equilibrium Structural Transformations in Atomically-Thin Chalcogenides

Two-dimensional (2D) transition metal dichalcogenides (TMDCs) have been the subject of sustained research interest due to their extraordinary electronic and optical properties. They also exhibit a wide range of structural phases because of the different orientations that the atoms can have within a single layer, or due to the ways that different layers can stack. Here we report the first study of direct-visualization of structural transformations in atomically-thin layers under highly non-equilibrium thermodynamic conditions. We probe these transformations at the atomic scale using real-time, aberration corrected scanning transmission electron microscopy and observe strong dependence of the resulting structures and phases on both heating rate and temperature. A fast heating rate (25 C/sec) yields highly ordered crystalline hexagonal islands of sizes of less than 20 nm which are composed of a mixture of 2H and 3R phases. However, a slow heating rate (25 C/min) yields nanocrystalline and sub-stoichiometric amorphous regions. These differences are explained by different rates of sulfur evaporation and redeposition. The use of non-equilibrium heating rates to achieve highly crystalline and quantum-confined features from 2D atomic layers present a new route to synthesize atomically-thin, laterally confined nanostrucutres and opens new avenues for investigating fundamental electronic phenomena in confined dimensions.

cond-mat.mtrl-sci↗
arXiv2019

Understanding Important Features of Deep Learning Models for Transmission Electron Microscopy Image Segmentation

Cutting edge deep learning techniques allow for image segmentation with great speed and accuracy. However, application to problems in materials science is often difficult since these complex models may have difficultly learning physical parameters. In situ electron microscopy provides a clear platform for utilizing automated image analysis. In this work we consider the case of studying coarsening dynamics in supported nanoparticles, which is important for understanding e.g. the degradation of industrial catalysts. By systematically studying dataset preparation, neural network architecture, and accuracy evaluation, we describe important considerations in applying deep learning to physical applications, where generalizable and convincing models are required.

eess.IV↗
arXiv2017

Cathodoluminescence as an Effective Probe of Carrier Transport and Deep Level Defects in Droop-Mitigating InGaN/GaN Quantum Well Heterostructures

Commercial InGaN/GaN light emitting diode heterostructures continue to suffer from efficiency droop at high current densities. Droop mitigation strategies target Auger recombination and typically require structural and/or compositional changes within the multi-quantum well active region. However, these modifications are often accompanied by a corresponding degradation in material quality that decreases the expected gains in high-current external quantum efficiency. We study origins of these efficiency losses by correlating chip-level quantum efficiency measurements with structural and optical properties obtained using a combination of electron microscopy tools. The drop in quantum efficiency is not found to be correlated with quantum well (QW) width fluctuations. Rather, we show direct correlation between active region design, deep level defects, and delayed electron beam induced cathodoluminescence (CL) with characteristic rise time constants on the order of tens of seconds. We propose a model in which the electron beam fills deep level defect states and simultaneously drives reduction of the built-in field within the multi-quantum well active region, resulting in a delay in accumulation of carrier populations within the QWs. The CL measurements yield fundamental insights into carrier transport phenomena, efficiency-reducing defects, and quantum well band structure that are important in guiding future heterostructure process development.

cond-mat.mes-hall↗
arXiv2012

Revealing Correlation of Valence State with Nanoporous Structure in Cobalt Catalyst Nanoparticles by in Situ Environmental TEM

Simultaneously probing the electronic structure and morphology of materials at the nanometer or atomic scale while a chemical reaction proceeds is significant for understanding the underlying reaction mechanisms and optimizing a materials design. This is especially important in the study of nanoparticle catalysts, yet such experiments have rarely been achieved. Utilizing an environmental transmission electron microscope (ETEM) equipped with a differentially pumped gas cell, we are able to conduct nanoscopic imaging and electron energy loss spectroscopy (EELS) in situ for cobalt catalysts under reaction conditions. Analysis revealed quantitative correlation of the cobalt valence states to the particles' nanoporous structures. The in situ experiments were performed on nanoporous cobalt particles coated with silica while a 15 mTorr hydrogen environment was maintained at various temperatures (300-600\degreeC). When the nanoporous particles were reduced, the valence state changed from cobalt oxide to metallic cobalt and concurrent structural coarsening was observed. In situ mapping of the valence state and the corresponding nanoporous structures allows quantitatively analysis necessary for understanding and improving the mass activity and lifetime of cobalt-based catalysts, i.e., for Fischer-Tropsch synthesis that converts carbon monoxide and hydrogen into fuels, and uncovering the catalyst optimization mechanisms.

cond-mat.mtrl-sci↗
arXiv2011

Control and Characterization of Individual Grains and Grain Boundaries in Graphene Grown by Chemical Vapor Deposition

The strong interest in graphene has motivated the scalable production of high quality graphene and graphene devices. Since large-scale graphene films synthesized to date are typically polycrystalline, it is important to characterize and control grain boundaries, generally believed to degrade graphene quality. Here we study single-crystal graphene grains synthesized by ambient CVD on polycrystalline Cu, and show how individual boundaries between coalescing grains affect graphene's electronic properties. The graphene grains show no definite epitaxial relationship with the Cu substrate, and can cross Cu grain boundaries. The edges of these grains are found to be predominantly parallel to zigzag directions. We show that grain boundaries give a significant Raman "D" peak, impede electrical transport, and induce prominent weak localization indicative of intervalley scattering in graphene. Finally, we demonstrate an approach using pre-patterned growth seeds to control graphene nucleation, opening a route towards scalable fabrication of single-crystal graphene devices without grain boundaries.

cond-mat.mes-hall↗
arXiv2010

Large-scale Graphitic Thin Films Synthesized on Ni and Transferred to Insulators: Structural and Electronic Properties

We present a comprehensive study of the structural and electronic properties of ultrathin films containing graphene layers synthesized by chemical vapor deposition (CVD) based surface segregation on polycrystalline Ni foils then transferred onto insulating SiO2/Si substrates. Films of size up to several mm's have been synthesized. Structural characterizations by atomic force microscopy (AFM), scanning tunneling microscopy (STM), cross-sectional transmission electron microscopy (XTEM) and Raman spectroscopy confirm that such large scale graphitic thin films (GTF) contain both thick graphite regions and thin regions of few layer graphene. The films also contain many wrinkles, with sharply-bent tips and dislocations revealed by XTEM, yielding insights on the growth and buckling processes of the GTF. Measurements on mm-scale back-gated transistor devices fabricated from the transferred GTF show ambipolar field effect with resistance modulation ~50% and carrier mobilities reaching ~2000 cm^2/Vs. We also demonstrate quantum transport of carriers with phase coherence length over 0.2 $μ$m from the observation of 2D weak localization in low temperature magneto-transport measurements. Our results show that despite the non-uniformity and surface roughness, such large-scale, flexible thin films can have electronic properties promising for device applications.

cond-mat.mtrl-sci↗