Engineering topics

Geohegan, David B.

Publications and source records attributed to Geohegan, David B..

At least 19 records

DOE OSTI2024

Autonomous Synthesis of Thin Film Materials with Pulsed Laser Deposition Enabled by In Situ Spectroscopy and Automation

Autonomous systems that combine synthesis, characterization, and artificial intelligence can greatly accelerate the discovery and optimization of materials, however platforms for growth of macroscale thin films by physical vapor deposition techniques have lagged far behind others. Here this study demonstrates autonomous synthesis by pulsed laser deposition (PLD), a highly versatile synthesis technique, in the growth of ultrathin WSe 2 films. Further, by combing the automation of PLD synthesis and in situ diagnostic feedback with a high-throughput methodology, this study demonstrates a workflow and platform which uses Gaussian process regression and Bayesian optimization to autonomously identify growth regimes for WSe 2 films based on Raman spectral criteria by efficiently sampling 0.25% of the chosen 4D parameter space. With throughputs at least 10x faster than traditional PLD workflows, this platform and workflow enables the accelerated discovery and autonomous optimization of the vast number of materials that can be synthesized by PLD.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Anomalous isotope effect on the optical bandgap in a monolayer transition metal dichalcogenide semiconductor

Isotope effects have received increasing attention in materials science and engineering because altering isotopes directly affects phonons, which can affect both thermal properties and optoelectronic properties of conventional semiconductors. However, how isotopic mass affects the optoelectronic properties in 2D semiconductors remains unclear because of measurement uncertainties resulting from sample heterogeneities. Here, we report an anomalous optical bandgap energy red shift of 13 (±7) milli–electron volts as mass of Mo isotopes is increased in laterally structured 100 MoS 2 - 92 MoS 2 monolayers grown by a two-step chemical vapor deposition that mitigates the effects of heterogeneities. This trend, which is opposite to that observed in conventional semiconductors, is explained by many-body perturbation and time-dependent density functional theories that reveal unusually large exciton binding energy renormalizations exceeding the ground-state renormalization energy due to strong coupling between confined excitons and phonons. The isotope effect on the optical bandgap reported here provides perspective on the important role of exciton-phonon coupling in the physical properties of two-dimensional materials.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Role of Curvature in Stabilizing Boron-Doped Nanocorrugated Graphene

Boron-doped carbon nanostructures have attracted great interest recently because of their remarkable electrocatalytic performance comparable to or better than that of conventional metal catalysts. In a previous work (Carbon 123, 605 (2017)), we reported that along with significant performance improvement, B doping enhances the oxidation resistance of few-layer graphene (FLG) that provides increased structural stability for intermediate-temperature fuel-cell electrodes. In general, detailed characterization of the atomic and electronic structure transformations that occur in B-doped carbon nanostructures during fuel-cell operation is lacking. In this work, we use aberration-corrected scanning transmission electron microscopy, nanobeam electron diffraction, and electron energy-loss spectroscopy (EELS) to characterize the atomic and electronic structures of B-doped FLG before and after fuel-cell operation. These data point to the nanoscale corrugation of B-doped FLGs as the key factor responsible for increased stability and high corrosion resistance. In conclusion, the similarity of the 1s to π* and σ* transition features in the B K-edge EELS to those in B-doped carbon nanotubes provides an estimate for the curvature of nanocorrugation in B-FLG.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Armor for Steel: Facile Synthesis of Hexagonal Boron Nitride Films on Various Substrates

Abstract While hexagonal boron nitride (hBN) has been widely used as a buffer or encapsulation layer for emerging electronic devices, interest in utilizing it for large‐area chemical barrier coating has somewhat faded. A chemical vapor deposition process is reported here for the conformal growth of hBN on large surfaces of various alloys and steels, regardless of their complex shapes. In contrast to the previously reported very limited protection by hBN against corrosion and oxidation, protection of steels against 10% HCl and oxidation resistance at 850 °C in air is demonstrated. Furthermore, an order of magnitude reduction in the friction coefficient of the hBN coated steels is shown. The growth mechanism is revealed in experiments on thin metal films, where the tunable growth of single‐crystal hBN with a selected number of layers is demonstrated. The key distinction of the process is the use of N 2 gas, which gets activated exclusively on the catalyst's surface and eliminates adverse gas‐phase reactions. This rate‐limiting step allowed independent control of activated nitrogen along with boron coming from a solid source (like elemental boron). Using abundant and benign precursors, this approach can be readily adopted for large‐scale hBN synthesis in applications where cost, production volume, and process safety are essential.

2D materials↗

DOE OSTI2023

Molybdenum Disulfide Nanoribbons with Enhanced Edge Nonlinear Response and Photoresponsivity

MoS 2 nanoribbons have attracted increased interest due to their properties, which can be tailored by tuning their dimensions. Herein, the growth of MoS 2 nanoribbons and triangular crystals formed by the reaction between films of MoOx (2 2 nanoribbons arising from distinct contributions from the single–layer edges and multilayer core. Nanoscale imaging reveals a blue-shifted exciton emission of the monolayer edge compared to the isolated MoS 2 monolayers due to built-in local strain and disorder. We further report on an ultrasensitive photodetector made of a single MoS 2 nanoribbon with a responsivity of 8.72 × 10 2 A W –1 at 532 nm, among the highest reported up-to-date for single-nanoribbon photodetectors. These findings can inspire the design of MoS 2 semiconductors with tunable geometries for efficient optoelectronic devices.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Real-Time Diagnostics of 2D Crystal Transformations by Pulsed Laser Deposition: Controlled Synthesis of Janus WSSe Monolayers and Alloys

Energetic processing methods such as hyperthermal implantation hold special promise to achieve the precision synthesis of metastable two-dimensional (2D) materials such as Janus monolayers; however, they require precise control. Here, we report a feedback approach to reveal and control the transformation pathways in materials synthesis by pulsed laser deposition (PLD) and apply it to investigate the transformation kinetics of monolayer WS 2 crystals into Janus WSSe and WSe 2 by implantation of Se clusters with different maximum kinetic energies (<42 eV/Se-atom) generated by laser ablation of a Se target. Real-time Raman spectroscopy and photoluminescence are used to assess the structure, composition, and optoelectronic quality of the monolayer crystal as it is implanted with well-controlled fluxes of selenium for different kinetic energies that are regulated with in situ ICCD imaging, ion probe, and spectroscopy diagnostics. First-principles calculations, XPS, and atomic-resolution HAADF STEM imaging are used to understand the intermediate alloy compositions and their vibrational modes to identify transformation pathways. The real-time kinetics measurements reveal highly selective top-layer conversion as WS 2 transforms through WS 2(1–x) Se 2x alloys to WSe 2 and provide the means to adjust processing conditions to achieve fractional and complete Janus WSSe monolayers as metastable transition states. The general approach demonstrates a real-time feedback method to achieve Janus layers or other metastable alloys of the desired composition, and a general means to adjust the structure and quality of materials grown by PLD, addressing priority research directions for precision synthesis with real-time adaptive control.

2D materials↗

DOE OSTI2022

Stabilized Synthesis of 2D Verbeekite: Monoclinic PdSe 2 Crystals with High Mobility and In-Plane Optical and Electrical Anisotropy

PdSe 2 has a layered structure with an unusual, puckered Cairo pentagonal tiling. Its atomic bond configuration features planar 4-fold-coordinated Pd atoms and intralayer Se–Se bonds that enable polymorphic phases with distinct electronic and quantum properties, especially when atomically thin. PdSe 2 is conventionally orthorhombic, and direct synthesis of its metastable polymorphic phases is still a challenge. Here, we report an ambient-pressure chemical vapor deposition approach to synthesize metastable monoclinic PdSe 2 . Monoclinic PdSe 2 is shown to be synthesized selectively under Se-deficient conditions that induce Se vacancies. These defects are shown by first-principles density functional theory calculations to reduce the free energy of the metastable monoclinic phase, thereby stabilizing it during synthesis. Further, the structure and composition of the monoclinic PdSe 2 crystals are identified and characterized by scanning transmission electron microscopy imaging, convergent beam electron diffraction, and electron energy loss spectroscopy. Polarized Raman spectroscopy of the monoclinic PdSe 2 flakes reveals their strong in-plane optical anisotropy. Electrical transport measurements show that the monoclinic PdSe 2 exhibits n-type charge carrier conduction with electron mobilities up to ~298 cm 2 V –1 s –1 and a strong in-plane electron mobility anisotropy of ~1.9. The defect-mediated growth pathway identified in this work is promising for phase-selective direct synthesis of other 2D transition metal dichalcogenides.

2D material↗

DOE OSTI2022

Photoluminescence Induced by Substitutional Nitrogen in Single-Layer Tungsten Disulfide

The electronic and optical properties of two-dimensional materials can be strongly influenced by defects, some of which can find significant implementations, such as controllable doping, prolonged valley lifetime, and single-photon emissions. Here, we demonstrate that defects created by remote N 2 plasma exposure in single-layer WS 2 can induce a distinct low-energy photoluminescence (PL) peak at 1.59 eV, which is in sharp contrast to that caused by remote Ar plasma. This PL peak has a critical requirement on the N 2 plasma exposure dose, which is strongest for WS 2 with about 2.0% sulfur deficiencies (including substitutions and vacancies) and vanishes at 5.6% or higher sulfur deficiencies. Both experiments and first-principles calculations suggest that this 1.59 eV PL peak is caused by defects related to the sulfur substitutions by nitrogen, even though low-temperature PL measurements also reveal that not all the sulfur vacancies are remedied by the substitutional nitrogen. The distinct low-energy PL peak suggests that the substitutional nitrogen defect in single-layer WS 2 can potentially serve as an isolated artificial atom for creating single-photon emitters, and its intensity can also be used to monitor the doping concentrations of substitutional nitrogen.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Janus Monolayers for Ultrafast and Directional Charge Transfer in Transition Metal Dichalcogenide Heterostructures

Charge transfer properties of van der Waals heterostructures formed by Janus and regular transition metal dichalcogenide monolayers are studied by time-resolved pump–probe measurements and photoluminescence spectroscopy. Measurements of electron and hole transfer in three heterostructures with atomic layer sequences of S–W–Se/S–W–S, Se–W–S/S–W–S, and S–W–Se/Se–W–Se reveal that charge transfer from regular to Janus monolayers is ultrafast regardless of the direction of the built-in electric field of the Janus monolayer (Janus field). However, the charge transfer from Janus to regular layers is directional and controlled by the Janus field. When the current direction is along the field, the charge transfer is ultrafast and efficient, while the field blocks the charge transfer with an opposite charge current direction. The transferred carriers form interlayer excitons with extended lifetimes compared to the intralayer excitons. The demonstrated ultrafast and directional charge transfer between Janus and regular TMD layers shows that the Janus structures can be used to make 2D heterostructures with efficient and directional charge transfer properties.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Selective Antisite Defect Formation in WS 2 Monolayers via Reactive Growth on Dilute W-Au Alloy Substrates

Defects are ubiquitous in 2D materials and can affect the structure and properties of the materials and also introduce new functionalities. Methods to adjust the structure and density of defects during bottom-up synthesis are required to control the growth of 2D materials with tailored optical and electronic properties. In this study, the authors present an Au-assisted chemical vapor deposition approach to selectively form S W and S2 W antisite defects, whereby one or two sulfur atoms substitute for a tungsten atom in WS 2 monolayers. Guided by first-principles calculations, they describe a new method that can maintain tungsten-poor growth conditions relative to sulfur via the low solubility of W atoms in a gold/W alloy, thereby significantly reducing the formation energy of the antisite defects during the growth of WS 2 . The atomic structure and composition of the antisite defects are unambiguously identified by Z-contrast scanning transmission electron microscopy and electron energy-loss spectroscopy, and their total concentration is statistically determined, with levels up to ≈5.0%. Furthermore, scanning tunneling microscopy/spectroscopy measurements and first-principles calculations also verified these antisite defects and revealed the localized defect states in the bandgap of WS 2 monolayers. This bottom-up synthesis method to form antisite defects should apply in the synthesis of other 2D materials.

2D materials↗

DOE OSTI2021

Signature of Many-Body Localization of Phonons in Strongly Disordered Superlattices

Many-body localization (MBL) has attracted significant research attention due to its immunity to thermalization, role in logarithmic entanglement entropy growth, and opportunities to reach exotic quantum orders. However, experimental realization of MBL in solid-state systems has remained challenging. Here we report evidence of a possible phonon MBL phase in disordered GaAs/AlAs superlattices. Through grazing-incidence inelastic X-ray scattering, we observe a strong deviation of the phonon population from equilibrium in disordered samples doped with ErAs nanodots at low temperature, signaling a departure from thermalization. This behavior occurs within finite phonon energy and wavevector windows, suggesting a localization-thermalization crossover. We support our observation by proposing a theoretical model for the effective phonon Hamiltonian in disordered superlattices, and showing that it can be mapped exactly to a disordered 1D Bose-Hubbard model with a known MBL phase. The large on-site repulsion qualitatively explains the experimental findings. Furthermore, our work provides mode-resolved experimental evidence of phonon localization, potentially extending the scope of MBL to disordered solid-state systems.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2021

Controllable Thin‐Film Approaches for Doping and Alloying Transition Metal Dichalcogenides Monolayers

Abstract Two‐dimensional (2D) transition metal dichalcogenides (TMDs) exhibit exciting properties and versatile material chemistry that are promising for device miniaturization, energy, quantum information science, and optoelectronics. Their outstanding structural stability permits the introduction of various foreign dopants that can modulate their optical and electronic properties and induce phase transitions, thereby adding new functionalities such as magnetism, ferroelectricity, and quantum states. To accelerate their technological readiness, it is essential to develop controllable synthesis and processing techniques to precisely engineer the compositions and phases of 2D TMDs. While most reviews emphasize properties and applications of doped TMDs, here, recent progress on thin‐film synthesis and processing techniques that show excellent controllability for substitutional doping of 2D TMDs are reported. These techniques are categorized into bottom–up methods that grow doped samples on substrates directly and top–down methods that use energetic sources to implant dopants into existing 2D crystals. The doped and alloyed variants from Group VI TMDs will be at the center of technical discussions, as they are expected to play essential roles in next‐generation optoelectronic applications. Theoretical backgrounds based on first principles calculations will precede the technical discussions to help the reader understand each element's likelihood of substitutional doping and the expected impact on the material properties.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Intrinsic Defects in MoS 2 Grown by Pulsed Laser Deposition: From Monolayers to Bilayers

Pulsed laser deposition (PLD) can be considered a powerful method for the growth of two-dimensional (2D) transition-metal dichalcogenides (TMDs) into van der Waals heterostructures. However, despite significant progress, the defects in 2D TMDs grown by PLD remain largely unknown and yet to be explored. In this work, we combine atomic resolution images and first-principles calculations to reveal the atomic structure of defects, grains, and grain boundaries in mono- and bilayer MoS 2 grown by PLD. We find that sulfur vacancies and MoS antisites are the predominant point defects in 2D MoS 2 . We predict that the aforementioned point defects are thermodynamically favorable under a Mo-rich/S-poor environment. The MoS 2 monolayers are polycrystalline and feature nanometer size grains connected by a high density of grain boundaries. In particular, the coalescence of nanometer grains results in the formation of 180° mirror twin boundaries consisting of distinct 4- and 8-membered rings. We show that PLD synthesis of bilayer MoS 2 results in various structural symmetries, including AA' and AB, but also turbostratic with characteristic moiré patterns. Moreover, we report on the experimental demonstration of an electron beam-driven transition between the AB and AA' stacking orientations in bilayer MoS 2 . These results provide a detailed insight into the atomic structure of monolayer MoS 2 and the role of the grain boundaries on the growth of bilayer MoS 2 , which has importance for future applications in optoelectronics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Excitonic Dynamics in Janus MoSSe and WSSe Monolayers

We report here details of steady-state and time-resolved spectroscopy of excitonic dynamics for Janus transition metal dichalcogenide monolayers, including MoSSe and WSSe, which were synthesized by low-energy implantation of Se into transition metal disulfides. Absorbance and photoluminescence spectroscopic measurements determined the room-temperature exciton resonances for MoSSe and WSSe monolayers. Transient absorption measurements revealed that the excitons in Janus structures form faster than those in pristine transition metal dichalcogenides by about 30% due to their enhanced electron–phonon interaction by the built-in dipole moment. Here, by combining steady-state photoluminescence quantum yield and time-resolved transient absorption measurements, we find that the exciton radiative recombination lifetime in Janus structures is significantly longer than in their pristine samples, supporting the predicted spatial separation of the electron and hole wave functions due to the built-in dipole moment. These results provide fundamental insight in the optical properties of Janus transition metal dichalcogenides.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Giant enhancement of exciton diffusivity in two-dimensional semiconductors

Two-dimensional (2D) semiconductors bear great promise for application in optoelectronic devices, but the low diffusivity of excitons stands as a notable challenge for device development. Here, we demonstrate that the diffusivity of excitons in monolayer MoS 2 can be improved from 1.5 ± 0.5 to 22.5 ± 2.5 square centimeters per second with the presence of trapped charges. This is manifested by a spatial expansion of photoluminescence when the incident power reaches a threshold value to enable the onset of exciton Mott transition. The trapped charges are estimated to be in a scale of 10 10 per square centimeter and do not affect the emission features and recombination dynamics of the excitons. The result indicates that trapped charges provide an attractive strategy to screen exciton scattering with phonons and impurities/defects. Pointing towards a new pathway to control exciton transport and many-body interactions in 2D semiconductors.

42 ENGINEERING↗

DOE OSTI2020

Non-Equilibrium Synthesis of Highly Active Nanostructured, Oxygen-Incorporated Amorphous Molybdenum Sulfide HER Electrocatalyst

Molybdenum sulfide emerged as promising hydrogen evolution reaction (HER) electrocatalyst thanks to its high intrinsic activity, however its limited active sites exposure and low conductivity hamper its performance. To address these drawbacks, the non-equilibrium nature of pulsed laser deposition (PLD) is exploited to synthesize self-supported hierarchical nanoarchitectures by gas phase nucleation and sequential attachment of defective molybdenum sulfide clusters. Furthermore, the physics of the process are studied by in situ diagnostics and correlated to the properties of the resulting electrocatalyst. The as-synthesized architectures have a disordered nanocrystalline structure, with nanodomains of bent, defective S-Mo-S layers embedded in an amorphous matrix, with excess sulfur and segregated molybdenum particles. Oxygen incorporation in this structure fosters the creation of amorphous oxide/oxysulfide nanophases with high electrical conductivity, enabling fast electron transfer to the active sites. The combined effect of the nanocrystalline pristine structure and the surface oxidation enhances the performance leading to small overpotentials, very fast kinetics (35.1 mV dec -1 Tafel slope) and remarkable long-term stability for continuous operation up to -1 A cm -2 . This work shows possible new avenues in catalytic design arising from a non-equilibrium technique as PLD and the importance of structural and chemical control to improve the HER performance of MoS-based catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Enhancement of van der Waals Interlayer Coupling through Polar Janus MoSSe

Interlayer coupling plays essential roles in the quantum transport, polaritonic, and electrochemical properties of stacked van der Waals (vdW) materials. In this work, we report the unconventional interlayer coupling in vdW heterostructures (HSs) by utilizing an emerging 2D material, Janus transition metal dichalcogenides (TMDs). In contrast to conventional TMDs, monolayer Janus TMDs have two different chalcogen layers sandwiching the transition metal and thus exhibit broken mirror symmetry and an intrinsic vertical dipole moment. Such a broken symmetry is found to strongly enhance the vdW interlayer coupling by as much as 13.2% when forming MoSSe/MoS 2 HS as compared to the pristine MoS 2 counterparts. Our noncontact ultralow-frequency Raman probe, linear chain model, and density functional theory calculations confirm the enhancement and reveal the origins as charge redistribution in Janus MoSSe and reduced interlayer distance. Furthermore, our results uncover the potential of tuning interlayer coupling strength through Janus heterostacking.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Heterogeneities at multiple length scales in 2D layered materials: From localized defects and dopants to mesoscopic heterostructures

Two-dimensional (2D) materials hold great promise for applications in optoelectronics, quantum information science, and energy conversion due to their remarkable properties imbued by their physical characteristics. Although heterogeneities in their intrinsic structure are the major challenges limiting their synthesis and predictable properties, they also provide a pathway to controllably tune the properties and broaden the potential of 2D materials. Heterogeneities that can be tailored, including defects, dopants, strain, edges, and layer stackings offer transformative opportunities in heterogeneous 2D materials through the introduction of novel properties for technological applications. This article provides a review of recent progress in studying heterogeneities in 2D materials. The review uses examples from our work to develop a strategy to understand the heterogeneities across multiple length scales to link the effect of heterogeneity at the nanoscale with the macroscale properties of 2D materials. We describe specific types of heterogeneities and explore novel synthesis and processing methods for their controlled production with example of the potential impact and applications enabled by their intriguing properties. Finally, we provide a perspective on how to extend the range of tunable properties through further engineering the heterogeneities in 2D materials.

2D materials↗