Temporally and Spatially Resolved Plasma Spectroscopy in Pulsed Laser Deposition of Ultra-Thin Boron Nitride Films

Physical vapor deposition (PVD) has recently been investigated as a viable, alternative growth technique for two-dimensional materials with multiple benefits over other vapor deposition synthesis methods. The high kinetic energies and chemical reactivities of the condensing species formed from PVD processes can facilitate growth over large areas and at reduced substrate temperatures. In this study, chemistry, kinetic energies, time of flight data, and spatial distributions within a PVD plasma plume ablated from aboron nitride (BN) target by a KrF laser at different pressures of nitrogen gas were investigated. Time resolved spectroscopy and wavelength specific imaging were used to identify and track atomic neutral and ionized species including B+, B*, N+, N*, and molecular species including N2*, N2 +, and BN. Formation and decay of these species formed both from ablation of the target and from interactions with the background gas were investigated and provided insights into fundamental growth mechanisms of continuous, amorphous boron nitride thin films. The correlation of the plasma diagnostic results with film chemical composition and thickness uniformity studies helped to identify that a predominant mechanism for BN film formation is condensation surface recombination of boron ions and neutral atomic nitrogen species. These species arrive nearly simultaneously to the substrate location, and BN formation occurs microseconds before arrival of majority of N+ ions generated by plume collisions with background molecular nitrogen. The energetic nature and extended dwelling time of incident N+ ions at the substrate location was found to negatively impact resulting BN film stoichiometry and thickness. Growth of stoichiometric films was optimized at enriched concentrations of ionized boron and neutral atomic nitrogen in plasma near the condensation surface, providing few nanometer thick films with 1:1 BN stoichiometry and good thicknesses uniformity over macroscopic areas

Large-area ultrathin Te films with substrate-tunable orientation.

Anisotropy in a crystal structure can lead to large orientation-dependent variations of mechanical, optical, and electronic properties. Material orientation control can thus provide a handle to manipulate properties. Here, a novel sputtering approach for 2D materials enables growth of ultrathin (2.5-10 nm) tellurium films with rational control of the crystalline orientation templated by the substrate. The anisotropic Te 〈0001〉 helical chains align in the plane of the substrate on highly oriented pyrolytic graphite (HOPG) and orthogonally to MgO(100) substrates, as shown by polarized Raman spectroscopy and high-resolution electron microscopy. Furthermore, the films are shown to grow in a textured fashion on HOPG, in contrast with previous reports. These ultrathin Te films cover exceptionally large areas (>1 cm2) and are grown at low temperature (25 °C) affording the ability to accommodate a variety of substrates including flexible electronics. They are robust toward oxidation over a period of days and exhibit the non-centrosymmetric P3121 Te structure. Raman signals are acutely dependent on film thickness, suggesting that optical anisotropy persists and is even enhanced at the ultrathin limit. Hall effect measurements indicate orientation-dependent carrier mobility up to 19 cm2 V-1 s-1. These large-area, ultrathin Te films grown by a truly scalable, physical vapor deposition technique with rational control of orientation/thickness open avenues for controlled orientation-dependent properties in semiconducting thin films for applications in electronic and optoelectronic devices.This research was supported by the Air Force Office of Scientific Research grant no. AFOSR-YIP FA9550-17-1-0202 and a 3M Non-Tenured Faculty Award. Elisabeth Bianco acknowledges the support of the National Science Foundation Graduate Research Fellowship under grant no. DGE-1450681. MS acknowledges support from Air Force Office of Scientific Research grant number FA9550-19RYCOR050. This research made use of instruments in the Shared Equipment Authority of Rice University. This research was supported by the Nanoelectronics Branch, Functional Materials Division, Materials and Manufacturing Directorate, Air Force Research Laboratory and made use of instruments in the Materials Characterization Facility in the Materials and Manufacturing Directorate, Air Force Research Laboratory. We thank Dr Dean Brown for performing the FEM modelling and his contributions to Figure S1. EB thanks Dr Krishnamurthy Mahalingam and Dr Brandon Howe for helpful discussions on TEM and growth

Domain Engineering of Physical Vapor Deposited Two-Dimensional Materials

Physical vapor deposited two-dimensional (2D) materials span larger areas compared to exfoliated flakes, but suffer from very small grain or domain sizes. In this letter, we fabricate freestanding molybdenum disulfide (MoS2) and amorphous boron nitride (BN) specimens to expose both surfaces. We performed in situ heating in a transmission electron microscope to observe the domain restructuring in real time. The freestanding MoS2 specimens showed up to 100× increase in domain size, while the amorphous BN transformed in to polycrystalline hexagonal BN (h-BN) at temperatures around 600 °C much lower than the 850–1000 °C range cited in the literature

Probing interlayer interactions and commensurate-incommensurate transition in twisted bilayer graphene through Raman spectroscopy

Twisted 2D layered materials have garnered a lot of attention recently as a class of 2D materials whose interlayer interactions and electronic properties are dictated by the relative rotation / twist angle between the adjacent layers. In this work, we explore a prototype of such a twisted 2D system, artificially stacked twisted bilayer graphene (TBLG), where we probe the changes in the interlayer interactions and electron-phonon scattering pathways as the twist angle is varied from 0{\deg} to 30{\deg}, using Raman spectroscopy. The long range Moir\'e potential of the superlattice gives rise to additional intravalley and intervalley scattering of the electrons in TBLG which have been investigated through their Raman signatures. The density functional theory (DFT) calculations of the electronic band structure of the TBLG superlattices was found to be in agreement with the resonant Raman excitations across the van Hove singularities in the valence and conduction bands predicted for TBLG due to hybridization of bands from the two layers. We also observe that the relative rotation between the graphene layers has a marked influence on the second order overtone and combination Raman modes signalling a commensurate-incommensurate transition in TBLG as the twist angle increases. This serves as a convenient and rapid characterization tool to determine the degree of commensurability in TBLG systems

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.Comment: 45 pages, 20 figures (5 main figures, 15 supporting figures

Exciton Confinement in Two-Dimensional, In-Plane, Quantum Heterostructures

Two-dimensional (2D) semiconductors are promising candidates for optoelectronic application and quantum information processes due to their inherent out-of-plane 2D confinement. In addition, they offer the possibility of achieving low-dimensional in-plane exciton confinement, similar to zero-dimensional quantum dots, with intriguing optical and electronic properties via strain or composition engineering. However, realizing such laterally confined 2D monolayers and systematically controlling size-dependent optical properties remain significant challenges. Here, we report the observation of lateral confinement of excitons in epitaxially grown in-plane MoSe2 quantum dots (~15-60 nm wide) inside a continuous matrix of WSe2 monolayer film via a sequential epitaxial growth process. Various optical spectroscopy techniques reveal the size-dependent exciton confinement in the MoSe2 monolayer quantum dots with exciton blue shift (12-40 meV) at a low temperature as compared to continuous monolayer MoSe2. Finally, single-photon emission was also observed from the smallest dots at 1.6 K. Our study opens the door to compositionally engineered, tunable, in-plane quantum light sources in 2D semiconductors.Comment: Main Manuscript: 29 pages, 4 figures Supplementary Information: 14 pages, 12 figure

Scalable and Stable Ferroelectric Non-Volatile Memory at > 500 ∘^\circC

Non-volatile memory (NVM) devices that reliably operate at temperatures above 300 $^\circ$C are currently non-existent and remains a critically unmet challenge in the development of high-temperature (T) resilient electronics, necessary for many emerging, complex computing and sensing in harsh environments. Ferroelectric Al$_x$Sc$_{1-x}$N exhibits strong potential for utilization in NVM devices operating at very high temperatures (> 500 $^\circ$C) given its stable and high remnant polarization (PR) above 100 $\mu$C/cm$^2$ with demonstrated ferroelectric transition temperature (TC) > 1000 $^\circ$C. Here, we demonstrate an Al$_{0.68}$Sc$_{0.32}$N ferroelectric diode based NVM device that can reliably operate with clear ferroelectric switching up to 600 $^\circ$C with distinguishable On and Off states. The coercive field (EC) from the Pulsed I-V measurements is found to be -5.84 (EC-) and +5.98 (EC+) (+/- 0.1) MV/cm at room temperature (RT) and found to decrease with increasing temperature up to 600 $^\circ$C. The devices exhibit high remnant polarizations (> 100 $\mu$C/cm$^2$) which are stable at high temperatures. At 500 $^\circ$C, our devices show 1 million read cycles and stable On-Off ratio above 1 for > 6 hours. Finally, the operating voltages of our AlScN ferrodiodes are < 15 V at 600 $^\circ$C which is well matched and compatible with Silicon Carbide (SiC) based high temperature logic technology, thereby making our demonstration a major step towards commercialization of NVM integrated high-T computers.Comment: MS and S

Graphene and Beyond: Recent Advances in Two-Dimensional Materials Synthesis, Properties, and Devices

Since the isolation of graphene in 2004, two-dimensional (2D) materials research has rapidly evolved into an entire subdiscipline in the physical sciences with a wide range of emergent applications. The unique 2D structure offers an open canvas to tailor and functionalize 2D materials through layer number, defects, morphology, moir\ue9 pattern, strain, and other control knobs. Through this review, we aim to highlight the most recent discoveries in the following topics: theory-guided synthesis for enhanced control of 2D morphologies, quality, yield, as well as insights toward novel 2D materials; defect engineering to control and understand the role of various defects, including in situ and ex situ methods; and properties and applications that are related to moir\ue9 engineering, strain engineering, and artificial intelligence. Finally, we also provide our perspective on the challenges and opportunities in this fascinating field

Laser writing of electronic circuitry in thin film molybdenum disulfide: A transformative manufacturing approach

Electronic circuits, the backbone of modern electronic devices, require precise integration of conducting, insulating, and semiconducting materials in two- and three-dimensional space to control the flow of electric current. Alternative strategies to pattern these materials outside of a cleanroom environment, such as additive manufacturing, have enabled rapid prototyping and eliminated design constraints imposed by traditional fabrication. In this work, a transformative manufacturing approach using laser processing is implemented to directly realize conducting, insulating, and semiconducting phases within an amorphous molybdenum disulfide thin film precursor. This is achieved by varying the incident visible (514 nm) laser intensity and raster-scanning the thin film a-MoS2 sample (900 nm thick) at different speeds for micro-scale control of the crystallization and reaction kinetics. The overall result is the transformation of select regions of the a-MoS2 film into MoO2, MoO3, and 2H-MoS2 phases, exhibiting conducting, insulating, and semiconducting properties, respectively. A mechanism for this precursor transformation based on crystallization and oxidation is developed using a thermal model paired with a description of the reaction kinetics. Finally, by engineering the architecture of the three crystalline phases, electrical devices such as a resistor, capacitor, and chemical sensor were laser-written directly within the precursor film, representing an entirely transformative manufacturing approach for the fabrication of electronic circuitry