Individual Identification of DNA Nucleobases on Atomically Thin Black

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C: Surfaces, Interfaces, Porous Materials, and Catalysis

Individual Identification of DNA Nucleobases on Atomically Thin Black Phosphorene Nanoribbon: vdW Corrected DFT Calculations Rameshwar L Kumawat, and Biswarup Pathak J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/acs.jpcc.9b06239 • Publication Date (Web): 22 Aug 2019 Downloaded from pubs.acs.org on August 22, 2019

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The Journal of Physical Chemistry

Individual Identification of DNA Nucleobases on Atomically Thin Black Phosphorene Nanoribbon: vdW Corrected DFT Calculations Rameshwar L. Kumawat†,, Biswarup Pathak*,†,#, †Discipline

of Metallurgy Engineering and Materials Science, #Discipline of Chemistry,

School of Basic Sciences, Indian Institute of Technology (IIT) Indore, Indore, Madhya Pradesh, 453552, India *E-mail: [email protected] Abstract Monolayer-based nanodevices hold great promise for next-generation sequencing (biomolecular sensing/DNA sequencing) based applications. In this study, we have investigated the interaction of the nucleobases (adenine, thymine, guanine, and cytosine) on a phosphorene nanoribbon based device (APNR) for individual identification of DNA nucleobases. Using the van der Waals corrected (PBE+vdW) density functional theory (DFT) calculations, we have computed and analyzed the effect of interaction on the transmission properties of the APNR based nanodevice. The change in the electronic transport properties of APNR when nucleobases are physisorbed has been investigated by using the nonequilibrium Green’s function (NEGF) calculations. The coupling strength is different to some extent for different nucleobases, resulting in different transmission dips due to Fano resonance.

Keywords: DNA sequencing, black phosphorene, density functional theory, non-equilibrium Green’s function, Fano resonance

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1. Introduction Modern molecular biology explained the term genome as the genetic material of an organism, which consists of deoxyribonucleic acid (DNA), ribonucleic acid (RNA), and proteins. Such biomolecules contain genetic information at the molecular level. Therefore, understanding the interaction of biomolecules with inert surfaces (as inert surfaces do not favor a chemical reaction) of various low-dimensional materials has been a topic of research interest because of its significance for molecular recognition processes.1-11 Indeed, several theoretical and experimental works for the adsorption of DNA nucleobases (adenine [A], guanine [G], thymine [T], and cytosine [C]) on low-dimensional materials have been investigated for their recognition processes.11-20 Such studies have been done with DNA nucleobases to explore the adsorption/desorption

phenomenon,

relative

binding

strength,

and

their

binding

mechanism.18-21 For example, interactions of DNA bases with graphene have been widely studied and such studies allow scientists/researchers to understand the interactions, which in turn very helpful for molecular recognition processes .13,22-27 However, due to the complex binding nature of graphene-DNA nucleobases, numerous mechanisms have been examined such as π–π stacking, van der Waals, electrostatic, and hydrophobic interactions.28 These studies demonstrate that single-stranded DNA (ss-DNA) has a higher binding strength to graphene than the double-stranded DNA (ds-DNA).10,12 The strength of interactions of the different nucleobases with graphene varies as they depend on the polarizability of DNA nucleobases.12,25 Both theoretical and experimental studies have reported that guanine binds strongly to graphene compared to other three nucleobases.13,14,22 Furthermore, Heerema and Dekker have reported that adsorption of DNA bases on highly sensitive graphene nanoribbon can potentially usher to base-specific information. One significant advantage of the adsorption of DNA nucleobases is that the fluctuation (position and angles) of the nucleobases are minimized, which could lead to lower noise in the 2


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experimental measurements.29 In this respect, the interactions of DNA bases with various low-dimensional layered materials have received special attention.5,30 On the other hand, such studies demonstrate the adsorption phenomenon at the nano-biological interfaces, which can be very important for the molecular recognition processes for biomolecules. In 2011, Kwang S. Kim and co-workers have proposed a graphene nanochannel-based ultrafast DNA sequencing system that electrically distinguishes (conductance-based) all the four nucleobases.9 They have demonstrated that graphene nanoribbon (GNR) on which a DNA base is adsorbed unveils molecular Fano resonance.9,31-34 In addition, they have theoretically demonstrated that the transmission dips result from the Fano resonance between nucleobase and π-band of GNR states. This could be due to the interaction amongst different types of nucleobase and GNR, which diminishes the ballistic transport channel numbers, which in turn generates dips in the transmission spectra. The ballistic conductance of the GNR reduces at specific energies analogous to the specific π-molecular orbitals through the Fano resonance,31,32 which allows the four DNA bases to be distinguished.9,11,34 In a report, Thomas and co-workers have computationally proposed that DNA nucleobase based single molecular detection could be accomplished through conductance-based measurements. For this purpose, they have used progressive narrow and semiconducting nanoribbons, which can provide recognizably different dips in the transmission when arranged with DNA bases.11 In recent times, black phosphorene, a two-dimensional monolayer material has generated a lot of interest for various applications.35,36 Alike to graphene, phosphorene (P) has a puckered honeycomb-like configuration along the armchair direction. Phosphorene-based materials have attracted considerable heed due to their biocompatibility, unique optical, and electronic properties. Phosphorene has a finite tunable bandgap and high carrier mobility (~1000 cm2V-1s-1), which is special in the sense that these two properties are in general mutually exclusive in other 2D materials.35-39 The large-surface-to-volume ratio makes black P 3



principally sensitive to alter its immediate environment. Moreover, due to the strong hydrophilic character of phosphorene, it can be utilized for sensing biomolecules. Hence, such superior chemical and electronic properties of phosphorene can be utilized in molecular nanoscale sensing applications.39,40 Furthermore, it would be very interesting to find out whether the buckling nature of phosphorene can be promising for individual identification of DNA nucleobases. Inspired by these findings, using the density functional theory (DFT) based calculations, we have investigated the interaction of each nucleobase (A, G, T, and C) when stacked with armchair phosphorene nanoribbon (APNR) based device. The electronic transport properties of APNR and the conductance-caused by adsorption of each nucleobase on APNR have been investigated to examine its ability for individual identification of the four DNA nucleobases.

2. Model and Computational Methods In this work, we have proposed APNR-based nanodevice (Figure 1). Here APNR is used as the electrodes (left and right) as well as the central scattering region to avoid any contact resistance and to fulfill the condition of sub-nanometer of the membrane. We have taken Hfunctionalized phosphorene nanoribbon edges because H-terminated edges are easy to be produced experimentally.40-42 To investigate the adsorption phenomenon, we have studied the interactions of DNA nucleobases with phosphorene. To find the optimized electronic structures of each system, we have employed the state-of-the-art first-principles based density functional theory (DFT) approach, as implemented in SIESTA (Spanish Initiative for Electronic Simulations with Thousands of Atoms).43 We have employed van der Waals (vdW) energy-correction to the generalized gradient approximation (GGA) functional with Perdew-Burke-Ernzerhof (PBE)

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exchange-correlation functional in our calculations to employ the weak dispersion interaction,44,45 To model the atomic-core-electrons, the Troullier-Martins norm-conserving pseudopotentials, and Double-zeta-polarized (DZP) basis sets including polarization orbitals for all atoms have been employed.46,47 We have used a 32 Å of vacuum to avoid the interactions between the repeated images. The mesh cut off value is 300 Ry for the real space integration and k-space grid of 1 × 1 × 7 has been used, while a 1 × 1 × 25 grid is used for the electrodes. We have calculated the bandgap for all these systems with very high kpoints such as (1 × 1 × 100) for APNR and (1 × 100 × 100) for a monolayer of black phosphorene. The electrodes are periodic in the z-direction. The geometrical configurations are fully relaxed by the conjugate gradient (CG) algorithm. The tolerance in density matrix difference is 0.0001 and the atomic forces are lesser than 0.01 eVÅ-1.40,44 For the electronic transport calculations, we have employed the non-equilibrium Green’s functions (NEGFs) approach combined with DFT, as implemented in Tran-Siesta code.43-44 We have employed basis set and the real-space integration as same as used during the structure relaxation. For transport calculations, we have used gamma-centered k-points. The transmission coefficient, T(E), can be calculated using the following formula: 𝑇(𝐸) = Γ𝐿(𝐸,𝑉)𝒢(𝐸,𝑉)Γ𝑅(𝐸,𝑉)𝒢 † (𝐸,𝑉) † Where the coupling-matrices are given as 𝛤𝐿/𝑅 = 𝑖[𝛴𝐿/𝑅 ― 𝛴𝐿/𝑅 ] and the NEGFs for the

scattering region given as 𝒢(𝐸,𝑉) = [𝐸 × 𝑆𝑠 ― 𝐻𝑠[𝜌] ― 𝛴𝐿(𝐸,𝑉) ― 𝛴𝑅(𝐸,𝑉)] ―1, where 𝑆𝑠 is the overlap matrix and 𝐻𝑠 is the Hamiltonian matrix, Σ𝐿/𝑅 = 𝑉𝑆𝐿/𝑅𝑔𝐿/𝑅𝑉𝐿/𝑅𝑠 is the selfinteraction energy,

𝛴𝐿/𝑅 is a molecule electrode that takes into account from the L/R

electrodes onto the central scattering region, 𝑔𝐿/𝑅 is the surface 𝐿/𝑅 Green’s function and 𝑉𝐿/𝑅𝑠 = 𝑉𝑆†𝐿/𝑅is the coupling-matrix between L/R electrodes and the scattering region.41-43

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Furthermore, the integration of transmission function provides the electric current as by given equation: 2𝑒 𝜇

𝐼(𝑉𝑏) = ℎ ∫𝜇𝐿 𝑇(𝐸,𝑉𝑏)[𝑓(𝐸 ― 𝜇𝐿) ― 𝑓(𝐸 ― 𝜇𝑅)]𝑑𝐸 𝑅

Where 𝑇(𝐸,𝑉𝑏) is to represent the transmission spectrum of the electrons entering at energy (E) from L to R electrode in presence of an applied finite bias voltage 𝑉𝑏, 𝑓(𝐸 ― μL, R) is showing the Fermi-Dirac distribution of electrons in the L and R electrodes and μL, R the chemical potential where μL/R = 𝐸𝐹 ± 𝑉𝑏 2 are moved correspondingly up and down according to the Fermi energy 𝐸𝐹.41-43,52,53

3. Results and Discussion 3.1 Phosphorene Nanoribbon (APNR) Figure 1 shows the proposed APNR based nanodevice with left and right electrodes and a central scattering region. We have considered armchair configuration for the nanoribbon along the transport-direction as the electrical conductance of phosphorene is higher in the armchair direction than in the zigzag direction.48 We have also passivated the armchair edges with hydrogen (H) atoms. At the equilibrium geometry, the lattice constants of the APNR (width =10) are |a|= 4.13, |b|= 3.12 Å and the calculated P-P bond lengths are 2.26 and 2.30 Å. The modeled electrodes and scattering region are in the nano-metric range, which is good enough for the interaction of nucleobases. The band structure and total density of state (TDOS) of the APNR device (Figure 1b) shows that it is a semiconductor with a bandgap of 0.96 eV, which further matches with the previously reported bandgap of ~1.0 eV of similar

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Figure 1. (a) Model of the APNR device illustrating the left (L) and right (R) electrodes, and a scattering region. Here red dotted lines represent the unit cell and red arrows represent the P-P bond lengths. (b) Electronic band structure and TDOS of the APNR device [width (n) = 10]. The Fermi level is set to zero and indicated by the black dashed line.

size.50 We have also calculated the bandgap of the monolayer of black phosphorene. We have found that it has a bandgap of around 0.89 eV (Figure S1, Supporting Information (SI)), which is quite in agreement with the previous report.38 In order to analyze the size effect of the nanoribbons corresponds to the width of the nanoribbons, we have studied ten armchair APNR-based devices at different widths (Figure S1, SI). The width of the APNR device can be identified by counting the number of atomic lines (n) of the phosphorus (P) atoms across the nanoribbon. We have considered width (n) from 4 to 22 (Figure S1). The edges are passivated with hydrogen (H) atoms. Our electronic structures (Figure S1/2) show that the bandgap decreases as we increase the width of the system (n ≤ 20), while the bandgap remains constant for n = 20 and 22.50,54 Therefore, there is a size effect on the APNR. We have also investigated the zero-bias transmission as function of width as shown in Figure S3. Figure S3 shows that the transmission function changes as we change the width of the system

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and for higher width, the states are coming close to the Fermi level. Therefore, the required bias for transport will be lesser and lesser for the systems with higher width. 3.2 Physisorption of DNA Nucleobases: We have relaxed the stacking like configurations of the four DNA bases on APNR. Furthermore, we have systematically investigated the adsorption of the four DNA nucleobases at different adsorption sites (A1, A2, and A3) of the APNR surface as shown in Figure S4 (SI). The centre of the hexagonal ring of each nucleobase located on the hollow, top, and bridge sites of the APNR device for A1, A2, and A3 sites respectively. Figure S5 shows the initial and final geometries for all the cases and we find that all the nucleobases shift from their initial geometry. However, we have named A1, A2, and A3 sites as their preferred adsorptions sites based on our starting geometry. Table S1 shows that that A1 is the most favorable adsorption sites for all the cases though, in the case of T and C, they prefer to adsorb at the top site with a particular orientation. Furthermore, during the structural relaxation process, we have considered different adsorption heights (for example, 2.60, 2.80, 3.00, 3.20, and 3.40 Å) from the APNR surface as a starting geometry for each nucleobase parallel to with the APNR surface to ensure whether the resulting relaxed structure would be affected. Furthermore, the effect of the orientation of DNA nucleobases on APNR sheet has been investigated through the analysis of the energy of the fully relaxed APNR with nucleobase molecule on the surface as a function of the in-plane rotation of the nucleobase with respect to the nanoribbon plane. All the four DNA nucleobases have been adsorbed at different rotation angles between 0˚ and 90˚ in the steps of 30° (Figure S6, SI). The total energies of these rotated configurations with respect to original (0˚) orientation are given in Table S2 (SI). We have found that all the rotated configurations have similar energies. Therefore, the total energy of the system does not change much due to the rotation.

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Figure 2. The minimum energy structures (top and side views) of the APNR+nucleobase. Color code: (P: orange), (O: red), (N: blue), (C: grey), (H: white). Computed adsorption energies (Eads, in eV), and adsorption height (h, in Å) of the APNR+nucleobases are shown.

The most stable adsorption structures for the adsorbed DNA molecules on the APNR surface are presented in Figure 2. The adsorption height (h) is measured from P (phosphorus) atom of the APNR surface to the nearest atom of adsorbed nucleobase. Therefore, adoption height is the shortest distance between the APNR surface and nucleobases. For example, in the case of APNR+T (tilted structure), the adsorption height is the distance between P (of APNR) and O atom (of T) as shown in Figure 2. Similarly, the adsorption heights are 2.80 Å for APNR+G, 3.20 Å for APNR+A, and 2.91 Å for APNR+C. Figure 2, shows the computed adsorption energies and adsorption heights for all the APNR+nucleobase. As expected, our PBE+vdW adsorption energy values are significantly larger compared to the previous reports on such interactions using the PBE+GGA level of theory. However, we believe that the inclusion of vdW interaction is very important for such studies.27,44 We have observed that G

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base has the strongest adsorption energy ( ―2.32 eV) amongst all four nucleobases on the APNR surface,39 while T base has the smallest adsorption energy ( ―1.75 eV), followed closely by A and C base. Our calculated adsorption energies ( ―2.32 to ―1.75 eV) follow the order as 𝐺 > 𝐴 ≥ 𝐶 > 𝑇. The higher adsorption energy of G base indicates strong coupling, while lower adsorption energy of T base reveals weak coupling. Looking into the adsorption height and adsorption energies of different nucleobases on the APNR surface, it can be understood that the nature of the interaction is neither weak nor strong. Additionally, we have investigated the total density of states for the pristine APNR, nucleobases, and APNR+nucleobase devices to

Figure 3. The total density of states (TDOS) of the pristine APNR, and APNR+nucleobase, and the projected density of states (PDOS) for target nucleobases: (a) A, (b) G, (c) T, and (d) C. The Fermi level (E ― E𝑓) is set to zero.

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understand their nature of interactions (Figure 3). Figure 3 shows that G base has a maximum number of states in the -4 to 0 eV energy region, whereas T base has the least number of states in the same energy region. However, there are the significant number of states for all the four nucleobases in the -4 to 0 eV energy region, which suggest that all the four nucleobases are coupling with the APNR device, which is very important for their detection. 3.3 Transmission Furthermore, we have investigated the transport properties of APNR and APNR+nucleobase. Transmittance as a function of energy shows the possibility that an electron can be transmitted from one electrode to other through the scattering region. Such transmission

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Figure 4. (a) Transmission function of APNR and the APNR+nucleobase. The inset shows the zoomed visualizing of the transmission curve for all systems in the -0.9 to -1.3 eV energy range. (b-d) Molecular orbitals (top and side views) responsible for Fano resonance for APNR+G and APNR+T devices, respectively.

spectra are investigated to understand the changes in the transmittance of APNR device and for individual identification of each nucleobase. Figure 4 shows the transmission function for an energy window of ± 1.5 eV for all the devices. The transmission spectrum of pristine APNR shows that it has flat steps. However, in the presence of different DNA nucleobases (A/T/G/C), dip (sharp drop) appears in the electron transmission of the APNR with respect to energy (E ― Ef) at the characteristic molecular orbital (MO) energies of each nucleobase, which could be controlled through the gate voltage.32,51 The interaction between different types of nucleobases and APNR diminishes the ballistic transport channels number, which results in the formation of a dip in the electron transmission spectra. We find that there is a strong peak for G base (Figure S7, SI) in the TDOS of APNR+nucleobase, which indicates that there is a strong coupling, which is also the reason for the sharp dip for APNR+G. Furthermore, the characteristic transmission dip in the curve is proportional to the coupling strength of APNR+nucleobase. G base is known to be a strongly coupled system, so the dip is wider for G base, while other three nucleobases have weaker coupling so the dip is narrower. We have now shown a zoomed visualization of the transmission curve (Figure 4a) of the systems in the -0.9 to -1.3 eV energy range. Furthermore, at -1.24 eV energy, all the nucleobases show a dip though their corresponding DOS (Figure S7) is quite small. These observed transmission dips can help us in the individual identification of the G and T bases. However, A and C bases show overlap in the mentioned energy region. Therefore it may be difficult to distinguish all the four nucleobases though G and T can be distinguished from A

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and C. To understand this, we have further investigated the whole energy region and we find that at -1.06 eV, there is a strong Fano resonance (Figure S8a-b, SI) for APNR+G system. In order to confirm that transmission dips result from the Fano resonance, we have investigated the transmissions of the APNR+G system at increasing distances (Figure S8). The APNR+G system shows the most noticeable transmission dip around ―1.06 eV and the position of the dip changes as we change the adsorption height. Moreover, their DOS are also quite significant and the DOS peak shifts as we change the adsorption height. Hence, the characteristics dip of the DNA sequencing device consequence from the strong Fano resonance. The Fano resonance occurs between the localized MOs of the DNA base and the electron transport channels of the APNR, which can also be perceived from the noticeable peaks in the DOS (Figure S7) for the APNR+G device. The localized MOs of the G and T base and π-band of APNR is shown in Figure 4. The strong resonance between APNR and the G base MO at a specific energy (E ― Ef) of ―1.06 and weak resonance at 0.7 and -1.24 eV (Figure 4b, c), partially blocks the ballistic conduction-channels of the APNR device. Similarly, one can see for T base MO at the energy of -1.24 eV (Figure 4d), which reveals somewhat weaker coupling compared with G base system. Now based on our transmission spectra, DOS and molecular orbitals analysis we believe that at -1.06 eV, the G base exhibiting strong Fano resonance rather than that at -1.24 eV, whereas all these systems show weak Fano resonance at -1.24 eV. Additionally, we have computed the zero-bias transmission for all the configurations at different rotation angles between 0˚ and 90˚ in the steps of 30° and we do not see any significant change in the transmission function (Figure S9). Furthermore, the calculated sensitivity has the order of G > T > A ≥ C. This is different from the adsorption binding energy of nucleobases on APNR which has the order of G > A ≥ C > T, because Fano resonance arises from the orbital interactions which are not necessarily in the same order of adsorption energy. Interestingly, Kim and co-workers have shown that the

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orbital interaction order can match with their adsorption energies.33 However, in our case, we have four different nucleobases and the orbital interactions not necessarily be in the same order of their adsorption energies. In our case, the sharp Fano resonances arise at ~0.7 and ~1.06 eV for G and at 0.8 eV for T, while A, C, and G show a weak Fano dip at ~0.77 eV. At ~1.24 eV, G, T, and C/A show the different magnitude of dips. Thus, G and T can be well distinguished, while C/A are hardly distinguished. Therefore, the APNR device may be utilized for DNA nucleobase detection. We have further calculated the sensitivity of the device, although our zero-bias transmission spectra results are quite promising to distinguish the four nucleobases. However, sensing a molecule is basically dependent on the difference in their conductance. The sensitivity percentage (S%) can be calculated as; S (%) = |(G ― G0)/G0 |, where G is the conductance of APNR+nucleobase and G0 is the conductance of pristine APNR at zero bias. At ―1.24 eV, we have computed the resulting sensitivity for all the four nucleobases (Figure 5) for their detection and such quantum conductance of the device can be experimentally measured using

Figure 5. Sensitivity plot for the four DNA nucleobases (A, G, T, and C) at -1.24 V.

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a gate voltage of ―1.24 V. The observed sensitivity values are 2.01%, 19.06%, 9.04%, and 1.63% for A, G, T, and C, respectively. The sensitivity is in the following order: G > T > A ≥ C. Hence, the APNR device exhibits larger selectivity toward G and T base, while smaller sensitivity for A and C base. These sensitivity values suggest that individual identification of DNA nucleobases can be possible using APNR based device. 3.4 Current-Voltage (𝑰 ― 𝑽) Characteristics Furthermore, we have performed the current-voltage (𝐼 ― 𝑉) characteristics for individual identifications of the four target nucleobases on the APNR surface. The calculated 𝐼 ― 𝑉 curves for APNR+A, APNR+G, APNR+T, and APNR+C are shown in Figure 6. Figure 6a shows that A and T base can be clearly distinguished from the C and G base. We have further illustrated the 𝐼 ― 𝑉 sensitivity of detection of four target nucleobases at the higher bias regime (V= 1.8 to 2.0 V). In Figure 6b, we have shown the current responses of individual nucleobases for the bias voltage between 1.8 and 2.0 V. This figure principally summarizes the read-outs of current traces for the four DNA nucleobases within a given bias window of 1.8 ― 2.0 V.

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Figure 6. (a) Current-voltage (𝐼 ― 𝑉) characteristics of all four target nucleobases (A, G, T, and C) on the APNR surface. The inset shows the zoomed visualizing of the 𝐼 ― 𝑉 plot within the bias range of 1.8-2.0 V. (b) Current responses (read-outs of current traces from 𝐼 ― 𝑉 plots for all four target nucleobases within the bias range of 1.8-2.0 V.

The observed sensitivity values of four target nucleobases are as follows: 1.97 µA, 1.41 µA, 2.11 µA, and 1.46 µA for A, G, T, and C, respectively. Hence, we find that A and T base can be clearly distinguished from G and C.

4. Conclusions In conclusion, we have demonstrated that the adsorption of four DNA nucleobases (A, T, G, and C) on a phosphorene nanoribbon and explored the possibility of its emerging application in DNA sequencing. Using the van der Waals corrected DFT calculations, we have demonstrated that the four nucleobases are physisorbed on phosphorene in the stable-stacking like configurations, with adsorption strength is in the following order: G > A ≥ C > T. The higher adsorption energies of G and A indicate strong coupling, while lower adsorption energies of C and T reveal weak coupling. Furthermore, we show that the identification of DNA nucleobases is possible through transmission measurements. As transmission dips occur in the APNR in the presence of DNA nucleobases due to the Fano resonance, such Fano resonance occurs due to the coupling between nucleobases and APNR. The calculated molecular orbitals of the nucleobases in those specific energies show that there is a strong orbital mixing between APNR and G base, whereas weak mixing between APNR and T base. Such features of the DNA base appear with molecular orbitals characteristic coupling dips.

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Thus, our results show that phosphorene-based nanodevice can be a promising material for individual identification of DNA nucleobases.

5. Supporting Information: Details regarding the width effect of the phosphorene nanoribbons, adsorption energies calculations, adsorption sites/energies, structural rotation, relative energies, zero-bias DOS of pristine APNR and APNR+nucleobases, transmission function and density of states of the APNR+G system at various distances, zero-bias transmission function of all the APNR+nucleobase systems while nucleobases are adsorbed at four different angles, are given.

6. Conflicts of interest There are no conflicts of interest to declare. 7. Acknowledgments We thank IIT Indore for the lab and computing facilities. This work is supported by DSTSERB, (Project Number: EMR/2015/002057) New Delhi and CSIR [Grant number: 01(2886)/17/EMR (II)]. R.L.K. thanks MHRD for research fellowships. We would like to thank Dr. Vivekanand Shukla for fruitful discussion throughout this work. 8. ORCID Rameshwar L. Kumawat: 0000-0002-2210-3428 Biswarup Pathak: 0000-0002-9972-9947

9. References 1

Siwy, Z. S.; Davenport, M. Graphene opens up to DNA. Nat. Nanotechnol. 2010, 5,

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Individual Identification of DNA Nucleobases on Atomically Thin Black

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