Interest in 2D materials and van der Waals solids is growing exponentially across various scientific and engineering disciplines owing to their fascinating electrical, optical, chemical, and thermal ...properties. Whereas the micromechanical exfoliation technique has been adopted for rapid material characterization and demonstration of innovative device ideas based on these 2D systems, significant advances have recently been made in large-scale homogeneous and heterogeneous growth of these materials. This review reflects recent progress and outlines future prospects of these novel 2D materials. We provide a holistic overview of the different synthesis and characterization techniques, electronic and photonic device characteristics, and catalytic properties of transition metal dichalcogenides and their heterostructures. We also comment on the challenges that need to be overcome for full-scale commercial implementation of this novel class of layered materials.
Since the isolation of graphene in 2004, there has been an exponentially growing number of reports on layered two-dimensional (2D) materials for applications ranging from protective coatings to ...biochemical sensing. Due to the exceptional, and often tunable, electrical, optical, electrochemical, and physical properties of these materials, they can serve as the active sensing element or a supporting substrate for diverse healthcare applications. In this review, we provide a survey of the recent reports on the applications of 2D materials in biosensing and other emerging healthcare areas, ranging from wearable technologies to optogenetics to neural interfacing. Specifically, this review provides (i) a holistic evaluation of relevant material properties across a wide range of 2D systems, (ii) a comparison of 2D material-based biosensors to the state-of-the-art, (iii) relevant material synthesis approaches specifically reported for healthcare applications, and (iv) the technological considerations to facilitate mass production and commercialization.
A multistep diffusion-mediated process was developed to control the nucleation density, size, and lateral growth rate of WSe2 domains on c-plane sapphire for the epitaxial growth of large area ...monolayer films by gas source chemical vapor deposition (CVD). The process consists of an initial nucleation step followed by an annealing period in H2Se to promote surface diffusion of tungsten-containing species to form oriented WSe2 islands with uniform size and controlled density. The growth conditions were then adjusted to suppress further nucleation and laterally grow the WSe2 islands to form a fully coalesced monolayer film in less than 1 h. Postgrowth structural characterization demonstrates that the WSe2 monolayers are single crystal and epitaxially oriented with respect to the sapphire and contain antiphase grain boundaries due to coalescence of 0° and 60° oriented WSe2 domains. The process also provides fundamental insights into the two-dimensional (2D) growth mechanism. For example, the evolution of domain size and cluster density with annealing time follows a 2D ripening process, enabling an estimate of the tungsten-species surface diffusivity. The lateral growth rate of domains was found to be relatively independent of substrate temperature over the range of 700–900 °C suggesting a mass transport limited process, however, the domain shape (triangular versus truncated triangular) varied with temperature over this same range due to local variations in the Se/W adatom ratio. The results provide an important step toward atomic level control of the epitaxial growth of WSe2 monolayers in a scalable process that is suitable for large area device fabrication.
A simple and inexpensive method to functionalize hexagonal boron nitride (hBN) was achieved by using an acid mixture of phosphoric and sulphuric acid. This functionalization induced the exfoliation ...of the layered structure of hBN into monolayer to few-layer sheets where the sizes of the sheets were dependent on the parent hBN powder used. Exfoliated hBN was shown to be stable in solvents such as ethanol, acetone, deionized water and isopropyl alcohol, and this stability was linked to sulfur functionalization that was induced during the exfoliation process. Further evidence of the functionalization was observed using transmission electron spectroscopy (TEM) and X-ray photoelectron spectroscopy (XPS). By deconvoluting the high resolution peaks for B 1s, the bonding of boron to oxygen and sulfur was confirmed. The exfoliated hBN nanosheets were crystalline as confirmed from X-ray diffraction and they also exhibited an optically active defect related to sulfur functionalization at 320 nm (3.9 ± 0.1 eV).
In the wake of the discovery of the remarkable electronic and physical properties of graphene, a vibrant research area on two-dimensional (2D) layered materials has emerged during the past decade. ...Transition metal dichalcogenides (TMDs) represent an alternative group of 2D layered materials that differ from the semimetallic character of graphene. They exhibit diverse properties that depend on their composition and can be semiconductors (e.g., MoS2, WS2), semimetals (e.g., WTe2, TiSe2), true metals (e.g., NbS2, VSe2), and superconductors (e.g., NbSe2, TaS2). The properties of TMDs can also be tailored according to the crystalline structure and the number and stacking sequence of layers in their crystals and thin films. For example, 2H-MoS2 is semiconducting, whereas 1T-MoS2 is metallic. Bulk 2H-MoS2 possesses an indirect band gap, but when 2H-MoS2 is exfoliated into monolayers, it exhibits direct electronic and optical band gaps, which leads to enhanced photoluminescence. Therefore, it is important to learn to control the growth of 2D TMD structures in order to exploit their properties in energy conversion and storage, catalysis, sensing, memory devices, and other applications. In this Account, we first introduce the history and structural basics of TMDs. We then briefly introduce the Raman fingerprints of TMDs of different layer numbers. Then, we summarize our progress on the controlled synthesis of 2D layered materials using wet chemical approaches, chemical exfoliation, and chemical vapor deposition (CVD). It is now possible to control the number of layers when synthesizing these materials, and novel van der Waals heterostructures (e.g., MoS2/graphene, WSe2/graphene, hBN/graphene) have recently been successfully assembled. Finally, the unique optical, electrical, photovoltaic, and catalytic properties of few-layered TMDs are summarized and discussed. In particular, their enhanced photoluminescence (PL), photosensing, photovoltaic conversion, and hydrogen evolution reaction (HER) catalysis are discussed in detail. Finally, challenges along each direction are described. For instance, how to grow perfect single crystalline monolayer TMDs without the presence of grain boundaries and dislocations is still an open question. Moreover, the morphology and crystal structure control of few-layered TMDs still requires further research. For wet chemical approaches and chemical exfoliation methods, it is still a significant challenge to control the lateral growth of TMDs without expansion in the c-axis direction. In fact, there is plenty of room in the 2D world beyond graphene. We envisage that with increasing progress in the controlled synthesis of these systems the unusual properties of mono- and few-layered TMDs and TMD heterostructures will be unveiled.
The world of two-dimensional (2D) heterostructures continues to expand at a rate much greater than anyone could have predicted 10 years ago, but if we are to make the leap from science to technology, ...many materials challenges must still be overcome. Recent advances, such as those by Liu et al. in this issue of ACS Nano, demonstrate that it is possible to grow rotationally commensurate 2D heterostructures, which could pave the way toward single crystal van der Waals solids. In this Perspective, I provide some insight into a few of the challenges associated with growth of heterostructures, and discuss some of the recent works that help us better understand synthetic realization of 2D heterostructures.
Monolayer transition metal dichalcogenide crystals, as direct-gap materials with strong light-matter interactions, have attracted much recent attention. Because of their spin-polarized valence bands ...and a predicted spin splitting at the conduction band edges, the lowest-lying excitons in WX2 (X = S, Se) are expected to be spin-forbidden and optically dark. To date, however, there has been no direct experimental probe of these dark excitons. Here, we show how an in-plane magnetic field can brighten the dark excitons in monolayer WSe2 and permit their properties to be observed experimentally. Precise energy levels for both the neutral and charged dark excitons are obtained and compared with ab initio calculations using the GW-BSE approach. As a result of their spin configuration, the brightened dark excitons exhibit much-increased emission and valley lifetimes. These studies directly probe the excitonic spin manifold and reveal the fine spin-splitting at the conduction band edges.
ACCOUNTABLE ALGORITHMS Kroll, Joshua A.; Huey, Joanna; Barocas, Solon ...
University of Pennsylvania law review,
02/2017, Letnik:
165, Številka:
3
Journal Article
Recenzirano
Many important decisions historically made by people are now made by computers. Algorithms count votes, approve loan and credit card applications, target citizens or neighborhoods for police ...scrutiny, select taxpayers for IRS audit, grant or deny immigration visas, and more. The accountability mechanisms and legal standards that govern such decision processes have not kept pace with technology. The tools currently available to policymakers, legislators, and courts were developed to oversee human decisionmakers and often fail when applied to computers instead. For example, how do you judge the intent of a piece of software? Because automated decision systems can return potentially incorrect, unjustified, or unfair results, additional approaches are needed to make such systems accountable and governable. This Article reveals a new technological toolkit to verify that automated decisions comply with key standards of legal fairness. We challenge the dominant position in the legal literature that transparency will solve these problems. Disclosure of source code is often neither necessary (because of alternative techniques from computer science) nor sufficient (because of the issues analyzing code) to demonstrate the fairness of a process. Furthermore, transparency may be undesirable, such as when it discloses private information or permits tax cheats or terrorists to game the systems determining audits or security screening. The central issue is how to assure the interests of citizens, and society as a whole, in making these processes more accountable. This Article argues that technology is creating new opportunities—subtler and more flexible than total transparency—to design decisionmaking algorithms so that they better align with legal and policy objectives. Doing so will improve not only the current governance of automated decisions, but also—in certain cases—the governance of decisionmaking in general. The implicit (or explicit) biases of human decisionmakers can be difficult to find and root out, but we can peer into the "brain" of an algorithm: computational processes and purpose specifications can be declared prior to use and verified afterward. The technological tools introduced in this Article apply widely. They can be used in designing decisionmaking processes from both the private and public sectors, and they can be tailored to verify different characteristics as desired by decisionmakers, regulators, or the public. By forcing a more careful consideration of the effects of decision rules, they also engender policy discussions and closer looks at legal standards. As such, these tools have far-reaching implications throughout law and society. Part I of this Article provides an accessible and concise introduction to foundational computer science techniques that can be used to verify and demonstrate compliance with key standards of legal fairness for automated decisions without revealing key attributes of the decisions or the processes by which the decisions were reached. Part II then describes how these techniques can assure that decisions are made with the key governance attribute of procedural regularity, meaning that decisions are made under an announced set of rules consistently applied in each case. We demonstrate how this approach could be used to redesign and resolve issues with the State Department's diversity visa lottery. In Part III, we go further and explore how other computational techniques can assure that automated decisions preserve fidelity to substantive legal and policy choices. We show how these tools may be used to assure that certain kinds of unjust discrimination are avoided and that automated decision processes behave in ways that comport with the social or legal standards that govern the decision. We also show how automated decisionmaking may even complicate existing doctrines of disparate treatment and disparate impact, and we discuss some recent computer science work on detecting and removing discrimination in algorithms, especially in the context of big data and machine learning. And lastly, in Part IV, we propose an agenda to further synergistic collaboration between computer science, law, and policy to advance the design of automated decision processes for accountability.
Celotno besedilo
Dostopno za:
BFBNIB, DOBA, IZUM, KILJ, NMLJ, NUK, PILJ, PNG, PRFLJ, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
The isolation of graphene in 2004 from graphite was a defining moment for the “birth” of a field: two-dimensional (2D) materials. In recent years, there has been a rapidly increasing number of papers ...focusing on non-graphene layered materials, including transition-metal dichalcogenides (TMDs), because of the new properties and applications that emerge upon 2D confinement. Here, we review significant recent advances and important new developments in 2D materials “beyond graphene”. We provide insight into the theoretical modeling and understanding of the van der Waals (vdW) forces that hold together the 2D layers in bulk solids, as well as their excitonic properties and growth morphologies. Additionally, we highlight recent breakthroughs in TMD synthesis and characterization and discuss the newest families of 2D materials, including monoelement 2D materials (i.e., silicene, phosphorene, etc.) and transition metal carbide- and carbon nitride-based MXenes. We then discuss the doping and functionalization of 2D materials beyond graphene that enable device applications, followed by advances in electronic, optoelectronic, and magnetic devices and theory. Finally, we provide perspectives on the future of 2D materials beyond graphene.
A two-dimensional (2D) heterobilayer system consisting of MoS2 on WSe2, deposited on epitaxial graphene, is studied by scanning tunneling microscopy and spectroscopy at temperatures of 5 and 80 K. A ...moiré pattern is observed, arising from lattice mismatch of 3.7% between the MoS2 and WSe2. Significant energy shifts are observed in tunneling spectra observed at the maxima of the moiré corrugation, as compared with spectra obtained at corrugation minima, consistent with prior work. Furthermore, at the minima of the moiré corrugation, sharp peaks in the spectra at energies near the band edges are observed for spectra acquired at 5 K. The peaks correspond to discrete states that are confined within the moiré unit cells. Conductance mapping is employed to reveal the detailed structure of the wave functions of the states. For measurements at 80 K, the sharp peaks in the spectra are absent, and conductance maps of the band edges reveal little structure.
PDF
