Mechanistic Insight into the Limiting Factors of Graphene-Based Environmental Sensors

Rautela, Ranjana; Scarfe, Samantha; Guay, Jean‐Michel; Lazar, Petr; Pykal, Martin; Azimi, Saied; Grenapin, Cedric; Boddison-Chouinard, Justin; Halpin, Alexei; Wang, Weixiang; Andrzejewski, Lukasz; Plumadore, Ryan; Park, Jeongwon; Ménard, Jean‐Michel; Otyepka, Michal; Luican‐Mayer, Adina

doi:10.1021/acsami.0c09051

Cited by 17 publications

(27 citation statements)

References 52 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…PBE affords a reasonable trade‐off between the computational costs and the quality/accuracy of resulting geometries (Figure 5(a)). 74 Other typically used functionals include local spin‐density approximation (LSDA), 83 other GGAs (PW91), 89 and Klimeš vdW‐corrected functionals (optB86b‐vdW) 74,79,107 . Molecular mechanics (MM) force fields, such as the all‐atom optimized potentials for liquid simulations (OPLS‐AA) 79,107 and the universal force field (UFF), are also popular alternatives to DFT methods 99 .…”

Section: Adsorption Geometrymentioning

confidence: 99%

“… 74 Other typically used functionals include local spin‐density approximation (LSDA), 83 other GGAs (PW91), 89 and Klimeš vdW‐corrected functionals (optB86b‐vdW) 74,79,107 . Molecular mechanics (MM) force fields, such as the all‐atom optimized potentials for liquid simulations (OPLS‐AA) 79,107 and the universal force field (UFF), are also popular alternatives to DFT methods 99 . Periodic computations also imply that numerical integrations of the first Brillouin zone are performed and it is therefore necessary to define the k ‐point sampling scheme for a good performance/accuracy compromise 74,84 .…”

Section: Adsorption Geometrymentioning

confidence: 99%

“…Graphene is shown as gray sticks, ethanol as green/red/white sticks, and PMMA fragments as blue/red/white spheres. (Reprinted with permission from Reference 107. Copyright 2020 American Chemical Society)…”

Section: Adsorption Geometrymentioning

confidence: 99%

See 2 more Smart Citations

Sensing and sensitivity: Computational chemistry of graphene‐based sensors

Piras

Ehlert

Gryn’ova

2021

WIREs Comput Mol Sci

View full text Add to dashboard Cite

Highly efficient, tunable, biocompatible, and environmentally friendly electrochemical sensors featuring graphene‐based materials pose a formidable challenge for computational chemistry. In silico rationalization, optimization and, ultimately, prediction of their performance requires exploring a vast structural space of potential surface‐analyte complexes, further complicated by the presence of various defects and functionalities within the infinite graphene lattice. This immense number of systems and their periodic nature greatly limit the choice of computational tools applicable at a reasonable cost. An alternative approach using finite nanoflake models opens the doors to many more advanced and accurate electronic structure methods, while sacrificing the realism of representation. Locating the surface‐analyte complex is followed by an in‐depth in silico analysis of its energetic and electronic properties using, for example, energy decomposition schemes, as well as simulation of the signal, for example, a zero‐bias transmission spectra or a current–voltage curve, by means of the nonequilibrium Green's function method. These and other properties are examined in the context of a sensor's selectivity, sensitivity, and limit of detection with an aim to establish design principles for future devices. Herein, we analyze the advantages and limitations of diverse computational chemistry methods used at each of these steps in simulating graphene‐based electrochemical sensors. We present outstanding challenges toward predictive models and sketch possible solutions involving such contemporary techniques as multiscale simulations and high‐throughput screening. This article is categorized under: Structure and Mechanism > Computational Materials Science Electronic Structure Theory > Density Functional Theory Electronic Structure Theory > Ab Initio Electronic Structure Methods

show abstract

Section: Adsorption Geometrymentioning

confidence: 99%

Section: Adsorption Geometrymentioning

confidence: 99%

See 1 more Smart Citation

Sensing and sensitivity: Computational chemistry of graphene‐based sensors

Piras

Ehlert

Gryn’ova

2021

WIREs Comput Mol Sci

View full text Add to dashboard Cite

show abstract

“…For example, graphene has already been implemented into a broadband image sensor array for enhanced photodetection 4 as well as memristors based on layered two-dimensional materials 5 . Graphene was also demonstrated to be a sensitive chemical and biological sensor [6][7][8] . With the development of large-scale production techniques such as epitaxial growth or chemical vapor deposition (CVD), large area graphene shows increasing promise for implementation into macroscale modern devices 9 .…”

Section: Introductionmentioning

confidence: 99%

“…To date, graphene-substrate interactions have been studied in devices by measuring the unpumped/non-excited carrier dynamics with both optical techniques and electrical transport techniques. For example, far-infrared spectroscopy (3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16) was used to characterize graphene on different polar dielectric and organic polymer films. Graphene on hexamethyldisilazane (HMDS) notably exhibits a mobility four times higher than on SiO2 29,30 .…”

Section: Introductionmentioning

confidence: 99%

Systematic THz Study of the Substrate Effect in Limiting the Mobility of Graphene

Scarfe

Cui

Luican‐Mayer

et al. 2021

Preprint

Self Cite

View full text Add to dashboard Cite

We explore the substrate-dependent charge carrier dynamics of large area graphene films using contact-free non-invasive terahertz spectroscopy. The graphene samples are deposited on seven distinct substrates relevant to semiconductor technologies and flexible/photodetection devices. Using a Drude model for Dirac fermions in graphene and a fitting method based on statistical signal analysis, we extract transport properties such as the charge carrier density and carrier mobility. We find that graphene films supported by substrates with minimal charged impurities exhibit an enhanced carrier mobility, while substrates with a high surface roughness generally lead to a lower transport performance. The smallest amount of doping is observed for graphene placed on the polymer Zeonor, which also has the highest carrier mobility. This work provides valuable guidance in choosing an optimal substrate for graphene to enable applications where high mobility is required.

show abstract

Aqueous Microlenses for Localized Collection and Enhanced Raman Spectroscopy of Gaseous Molecules

Kim

Park

et al. 2021

Advanced Optical Materials

View full text Add to dashboard Cite

light extraction in organic light-emitting diodes, [4,5] miniaturized imaging systems, [6][7][8] optical manipulation, [9] and spectral amplification. [10,11] Microlenses are generally solid-state objects [1][2][3][4][5][6][7][8]10] with fixed shapes whose interactions with chemical environments have been considered both insignificant and undesirable. In contrast, liquid lenses have tunable shapes that enable focal length control and operation in flexible systems. [12][13][14] Liquid lenses are usually made of non-volatile organic compounds [15][16][17][18] and encapsulated to ensure minimal exposure to the environment. [12][13][14]19] An aqueous microlens in the open air is expected to absorb gaseous molecules that are water-soluble and locally concentrate them within the lens. Therefore, aqueous microlenses can be unique optical tools for the collection and analysis of gaseous molecules in the open air. The application of aqueous lenses to gas analysis, however, has not been demonstrated because of poor long-term lens stability resulting from the evaporation of water [3,20,21] and the lack of methods for fabricating them in a well-controlled manner.Raman spectroscopy enables the label-free and reliable identification of various molecular species based on unique molecular fingerprints. Identifying gas-phase molecules by Raman spectroscopy, however, is challenging compared to identifying them in condensed phases because low-density gases at atmospheric pressure provide weak signals. [22,23] As a result, there exist very few studies that report the Raman spectroscopy of volatile organic compounds (VOCs) in the gas phase, [24][25][26][27][28] especially ones that are lethal at low concentrations, such as chemical warfare agents (CWAs). [29][30][31] Spectroscopy of gaseous molecules based on localized collection has been reported using different approaches, such as electrodynamic precipitation, [32][33][34][35] and the use of graphene plasmon [36] and microfluidic [37,38] devices; however, these approaches require complicated experimental procedures and peripheral devices. Electronic sensors based on nanomaterials [39][40][41] are highly sensitive to VOCs including CWAs, but identifying such gaseous analytes has been challenging, even after surface treatment with receptors. [36,42,43] Therefore, developing a technology that enables the Raman spectroscopy of gaseous molecular species is critical for identifying chemicals in the environment.Raman spectroscopy of gaseous molecules has been challenging, requiring complicated experimental procedures and peripheral devices for concentrating the analytes. Here, Raman spectroscopy of gaseous molecules at parts-per-billion (ppb) levels is demonstrated using aqueous microlenses of LiCl solution that spontaneously absorb water-soluble gas molecules from the environment. The lenses are easily formed by filling the microwells of an elastomeric stamp with an aqueous solution of LiCl and stamping onto a substrate. Because LiCl is hygroscopic, the aqueous lenses maintain their liqu...

show abstract

Mechanistic Insight into the Limiting Factors of Graphene-Based Environmental Sensors

Cited by 17 publications

References 52 publications

Sensing and sensitivity: Computational chemistry of graphene‐based sensors

Sensing and sensitivity: Computational chemistry of graphene‐based sensors

Systematic THz Study of the Substrate Effect in Limiting the Mobility of Graphene

Aqueous Microlenses for Localized Collection and Enhanced Raman Spectroscopy of Gaseous Molecules

Contact Info

Product

Resources

About