Edge Doping Research Articles

Imaging Bulk and Edge Transport near the Dirac Point in Graphene Moiré Superlattices.

Van der Waals structures formed by aligning monolayer graphene with insulating layers of hexagonal boron nitride exhibit a moiré superlattice that is expected to break sublattice symmetry. Despite an energy gap of several tens of millielectronvolts opening in the Dirac spectrum, electrical resistivity remains lower than expected at low temperature and varies between devices. While subgap states are likely to play a role in this behavior, their precise nature is unclear. We present a scanning gate microscopy study of moiré superlattice devices with comparable activation energy but with different charge disorder levels. In the device with higher charge impurity (∼1010 cm-2) and lower resistivity (∼10 kΩ) at the Dirac point we observe current flow along the graphene edges. Combined with simulations, our measurements suggest that enhanced edge doping is responsible for this effect. In addition, a device with low charge impurity (∼109 cm-2) and higher resistivity (∼100 kΩ) shows subgap states in the bulk, consistent with the absence of shunting by edge currents.

Thermal transport characterization of carbon and silicon doped stanene nanoribbon: an equilibrium molecular dynamics study.

Equilibrium molecular dynamics simulation has been carried out for the thermal transport characterization of nanometer sized carbon and silicon doped stanene nanoribbon (STNR). The thermal conduction properties of doped stanene nanostructures are yet to be explored and hence in this study, we have investigated the impact of carbon and silicon doping concentrations as well as doping patterns namely single doping, double doping and edge doping on the thermal conductivity of nanometer sized zigzag STNR. The room temperature thermal conductivities of 15 nm × 4 nm doped zigzag STNR at 2% carbon and silicon doping concentration are computed to be 9.31 ± 0.33 W m−1 K−1 and 7.57 ± 0.48 W m−1 K−1, respectively whereas the thermal conductivity for the pristine STNR of the same dimension is calculated as 1.204 ± 0.21 W m−1 K−1. We find that the thermal conductivity of both carbon and silicon doped STNR increases with the increasing doping concentration for both carbon and silicon doping. The magnitude of increase in STNR thermal conductivity due to carbon doping has been found to be greater than that of silicon doping. Different doping patterns manifest different degrees of change in doped STNR thermal conductivity. Double doping pattern for both carbon and silicon doping induces the largest extent of enhancement in doped STNR thermal conductivity followed by single doping pattern and edge doping pattern respectively. The temperature and width dependence of doped STNR thermal conductivity has also been studied. For a particular doping concentration, the thermal conductivity of both carbon and silicon doped STNR shows a monotonic decaying trend at elevated temperatures while an opposite pattern is observed for width variation i.e. thermal conductivity increases with the increase in ribbon width. Such comprehensive study on doped stanene would encourage further investigation on the proper optimization of thermal transport characteristics of stanene nanostructures and provide deep insight in realizing the potential application of doped STNR in thermoelectric as well as thermal management of stanene based nanoelectronic devices.

Green preparation of Ag nanoparticles/graphite nanosheets composite

A simple chemical edge doping method to prepare the Ag nanoparticles/graphite nanosheets (Ag/GNS) composite is presented. The GNS were fabricated in water with the assistance of a high pressure homogenisation (HPH). Ag nanoparticles (Ag-NPs) were decorated on GNS by edge doping. HPH was proved to be an efficient way to fabricate GNS with active sites to anchor metal nanoparticles in the authors’ work. The Ag/GNS composite synthesised by edge doping barely had any defects. The average diameter of the Ag-NPs in this case was 52.6 nm. It was observed that the fabricated Ag-NPs distributed mainly on the edge of GNS where the active sites were. The Ag/GNS composite exhibited a distinct surface-enhanced Raman scattering effect with a low concentration of silver. The Ag-NPs on the composite had improved stability (up to a month). It is believed that this simple and green method of nanocomposite preparation will shed some lights on the large-scale production of metal-nanoparticles-decorated carbon matrices.

Tuning a zigzag SiC nanoribbon as a thermal spin current generator

Quantum transport and spin current in a zigzag SiC nanoribbon device under a thermal gradient are investigated theoretically within the framework of the Landauer–Büttiker formalism using a first-principles technique. It is found that the edge state transport channels can be turned off or kept open by specific edge doping, and different spin channels can be controlled separately. Interestingly, by replacing an edge C atom with a B atom and an edge Si atom with a P atom in the scattering region, a Seebeck thermopower with different signs for different spins and a finite conductance for both spins can be obtained in the linear response regime. The subsequent thermoelectric field drives electrons of different spin channels in opposite directions, which leads unambiguously to a spin current. More importantly, by tuning the chemical potential and working temperature, pure spin current can be achieved. This provides a promising two-dimensional candidate system for producing pure spin current via the spin-dependent Seebeck effect.

Chemical functionalization and edge doping of zigzag graphene nanoribbon with l-(+)-leucine and group IB elements—A DFT study

First-principles based density functional theory (DFT) calculations have been carried out on the chemically functionalized pure and Cu, Ag and Au doped zigzag graphene nanoribbon (ZGNR(6,0)) with the use of the branched chain amino acid l-(+)-Leucine named as LLZGNR(6,0), LLCuZGNR(6,0), LLAgZGNR(6,0) and LLAuZGNR(6,0) respectively. The structural stability for minimum total energy was confirmed by perturbating the geometry of the relaxed structures. The physical and chemical properties, such as band gap, chemical potential, transmission spectrum, charge transfer, bonding character and Gibb’s free energy of solvation were analysed for all the four systems. It has been observed that the edge doping assisted functionalized systems (LLCuZGNR(6,0), LLAgZGNR(6,0) and LLAuZGNR(6,0)) without the inclusion of spin polarisation are semiconducting in nature. Whereas, barely functionalized system is found to be semi-metallic. An effective space charge polarisation in functionalized graphene nanoribbon has been revealed through charge transfer studies. Hence, it signifies the effective solubility of the nanoribbon in aqueous media. The results indicate the possibility of using such system as nanocarriers in targeted drug delivery applications.

High Resolution Sheet Resistance Mapping to Unveil Edge Effects in Industrial IBC Solar Cells

We present Terahertz (THz) transmission measurements with a spatial resolution of down to 10 μm as a new inspection technique for high-resolution sheet resistance (Rsh) measurements, that are well suited to quantify the local Rsh (n-type and p-type regions) of interdigitated back-contact (IBC) structures and to support further optimization of our IBC cells.Using this technique, we investigated the homogeneity of the emitter of our IBC cells. We have greatly improved the Rsh homogeneity of the boron diffusion. Moreover, we compared THz mapping with standard four point probe (4pp) technique. While the 4pp measurement showed a homogeneous mapping, the THz could unveil elevated Rsh near the very edge of the wafer. Higher Rsh of the surface doping can result in higher J0 at the metal contact regions (J0,contact). A local Voc mapping technique was used and it was found that the local Voc at the wafer edge was lowered by 17mV compared to the centre in the most extreme case. We estimate that an improved edge doping could result in a performance gain of at least 0.2% absolute, excluding FF and Jsc benefits.In summary we show that THz mapping is a powerful method in determining inhomogeneities and can aid in the development of diffused-junction IBC solar cells.

Electronic properties of Li-doped zigzag graphene nanoribbons

Zigzag graphene nanoribbons (ZGNRs) are known to exhibit metallic behavior. Depending on structural properties such as edge status, doping and width of nanoribbons, the electronic properties of these structures may vary. In this study, changes in electronic properties of crystal by doping Lithium (Li) atom to ZGNR structure are analyzed. In spin polarized calculations are made using Density Functional Theory (DFT) with generalized gradient approximation (GGA) as exchange correlation. As a result of calculations, it has been determined that Li atom affects electronic properties of ZGNR structure significantly. It is observed that ZGNR structure exhibiting metallic behavior in pure state shows half-metal and semiconductor behavior with Li atom.

Strain-induced programmable half-metal and spin-gapless semiconductor in an edge-doped boron nitride nanoribbon

The search for half-metals and spin-gapless semiconductors has attracted extensive attention in material design for spintronics. Existing progress in such a search often requires peculiar atomistic lattice configuration and also lacks active control of the resulting electronic properties. Here we reveal that a boron-nitride nanoribbon with a carbon-doped edge can be made a half-metal or a spin-gapless semiconductor in a programmable fashion. The mechanical strain serves as the on/off switches for functions of half-metal and spin-gapless semiconductor to occur. Our findings shed light on how the edge doping combined with strain engineering can affect electronic properties of two-dimensional materials

Edge functionalization and doping effects on the stability, electronic and magnetic properties of silicene nanoribbons

A spectacular SGS character with 100% spin polarized currents around the Fermi level is found in z2–1 functionalized with Cl.

On intersubband absorption of radiation in delta-doped QWs

The results of calculation of intersubband absorption coefficients for either center-, or edge-delta-doped with Phosphorus 10nm and 20nm-wide Si0.8Ge0.2/Si/Si0.8Ge0.2 quantum wells are presented. It is shown, that the absorption for delta-doped structures differs substantially from that of a pure rectangular or uniformly doped ones. There are two main features for delta-doped quantum wells. The first one is the blue-shift for optical transitions between first and others (more pronounced), and second and others (less pronounced) space quantized energy levels. The second one is that edge doping changes the symmetry of the quantum well and forbidden optical transitions for the rectangular structure become now allowed. The influences of temperature, quantum well width, and impurity concentration on the optical absorption are studied. It is shown that the most dramatic changes in comparison with rectangular quantum wells are for wider investigated edge-doped structures with bigger number of ionized impurities.

About possible THz modulator on the base of delta-doped QWs

The idea about a new type of THz modulator, based on the dependence of separation between space quantized energy levels in a quantum well (QW) on the degree of ionization of shallow impurity delta doped layer situated within the QW is supported with theoretical calculations of absorption coefficients for intersubband optical transitions of n-type Si0.8Ge0.2/Si/Si0.8Ge0.2 QW structure. Both center and edge doping of two QWs widths of – 10 and 20nm – were considered at lattice temperatures 4 and 77K for low and high degrees of impurity ionization. The obtained results are explained and they point to out the ranges of THz tuning of the structures under study. It is also emphasized that besides the electric field the changing temperature can control the efficiency of THz modulation.

Effect of edge chemistry doping on the transport and optical properties for asymmetric armchair-edge graphene nanoribbons under a uniaxial strain

The effect of edge n-type nitrogen (N) and p-type oxygen (O) doping on the transport and optical properties for asymmetric 6- and 8-armchair-edge graphene nanoribbons (AGNRs) under a uniaxial strain has been demonstrated in the method of the first-principles density functional theory combined with nonequilibrium Green’s function. The transmission spectra and current–voltage (I–V) curves of the semiconducting 6- and metallic 8-AGNRs have been found to be qualitatively unchanged as the uniaxial strain along the armchair edge (Ac-strain), while the quantitative variations come from the mutual actions of the strain and edge doping. However, the observed semiconductor–metal transition and metal–semiconductor transition in the transport properties for 6- and 8-AGNRs should be mainly from the resonance scattering of the doping edges when the external strain is applied along the zigzag edge (Zz-strain). The distinct variation trends of the system transport properties are well confirmed from the optical absorption spectra. It is believed that the obtained results are of importance in exploiting chemistry at the reactive edges of the asymmetric AGNRs and strain engineering of the nanoelectronic/optoelectronic devices based on AGNRs.

Self-consistent model of edge doping in graphene

Dopants positioned near edges in nanostructured graphene behave differently from bulk dopants. Most notable, the amount of charge transferred to delocalized states (i.e., doping efficiency) depends on position as well as edge chirality. We apply a self-consistent tight-binding model to analyze this problem focusing on substitutional nitrogen and boron doping. Using a Green's-function technique, very large structures can be studied, and artificial interactions between dopants in periodically repeated simulations cells are avoided. We find pronounced signatures of edges in the local impurity density of states. Importantly, the doping efficiency is found to oscillate with sublattice position, in particular, for dopants near zigzag edges. Finally, to assess the effect of electron-electron interactions, we compute the self-energy corrected Green's function.

Sulfur‐Annulated Hexa‐peri‐hexabenzocoronene Decorated with Phenylthio Groups at the Periphery

AbstractThe chemical nature of the edge periphery essentially determines the physical properties of graphene. As a molecular‐level model system, large polycyclic aromatic hydrocarbons, that is, so‐called nanographenes, can be chemically modified through either edge functionalization or doping with heteroatoms. Although the synthetic methods for edge substitution are well‐developed, incorporation with heteroatoms by the bay annulation of large PAHs remains an enormous challenge. In this study, we present a feasible peripheral sulfur annulation of hexa‐peri‐hexabenzocoronene (HBC) by thiolation of perchlorinated HBC. The tri‐sulfur‐annulated HBC and di‐sulfur‐annulated HBC decorated with phenylthio groups were obtained and characterized by X‐ray diffraction, revealing their distinct sulfur‐annulated peripheral structure. Associated with theoretical calculations, we propose that the regioselective sulfur annulation results from the minimization of strain in the aromatic backbone. We further demonstrate the structure‐correlated property modulation by sulfur annulation, manifested by a decrease in band gap and tunable redox activity.

Sulfur-annulated hexa-peri-hexabenzocoronene decorated with phenylthio groups at the periphery.

The chemical nature of the edge periphery essentially determines the physical properties of graphene. As a molecular-level model system, large polycyclic aromatic hydrocarbons, that is, so-called nanographenes, can be chemically modified through either edge functionalization or doping with heteroatoms. Although the synthetic methods for edge substitution are well-developed, incorporation with heteroatoms by the bay annulation of large PAHs remains an enormous challenge. In this study, we present a feasible peripheral sulfur annulation of hexa-peri-hexabenzocoronene (HBC) by thiolation of perchlorinated HBC. The tri-sulfur-annulated HBC and di-sulfur-annulated HBC decorated with phenylthio groups were obtained and characterized by X-ray diffraction, revealing their distinct sulfur-annulated peripheral structure. Associated with theoretical calculations, we propose that the regioselective sulfur annulation results from the minimization of strain in the aromatic backbone. We further demonstrate the structure-correlated property modulation by sulfur annulation, manifested by a decrease in band gap and tunable redox activity.

Carbon doping induced peculiar transport properties of boron nitride nanoribbons p-n junctions

By applying nonequilibrium Green's function combined with density functional theory, we investigate the electronic transport properties of carbon-doped p-n nanojunction based on hexagonal boron nitride armchair nanoribbons. The calculated I-V curves show that both the center and edge doping systems present obvious negative differential resistance (NDR) behavior and excellent rectifying effect. At low positive bias, the edge doping systems possess better NDR performance with larger peak-to-valley ratio (∼105), while at negative bias, the obtained peak-to-valley ratio for both of the edge and center doping systems can reach the order of 107. Meanwhile, center doping systems present better rectifying performance than the edge doping ones, and giant rectification ratio up to 106 can be obtained in a wide bias range. These outstanding transport properties are explained by the evolution of the transmission spectra and band structures with applied bias, together with molecular projected self-consistent Hamiltonian eigenvalues and eigenstates.

Doping effect on the adsorption of NH3 molecule onto graphene quantum dot: From the physisorption to the chemisorption

The adsorption of ammonia molecule onto a graphene hexagonal flake, aluminum (Al) and boron (B) doped graphene flakes (graphene quantum dots, GQDs) are investigated using density functional theory. We found that NH3 molecule is absorbed to the hollow site through the physisorption mechanism without altering the electronic properties of GQD. However, the adsorption energy of NH3 molecule onto the Al- and B-doped GQDs increases with respect GQD resulting chemisorption. The adsorption of NH3 onto the Al-doped and B-doped GQDs makes graphene locally buckled, i.e., B- doped and Al-doped GQDs are not planar. The adsorption mechanism onto a GQD is different than that of graphene. This study reveals important features of the edge passivation and doping effects of the adsorption mechanism of external molecules onto the graphene quantum dots.

A First-Principles Study of the Role of Quaternary-N Doping on the Oxygen Reduction Reaction Activity and Selectivity of Graphene Edge Sites

Density functional theory (DFT) was used to investigate O2 chemisorption on the edge sites of graphene doped with quaternary nitrogen (N-graphene). The location of the doped quaternary N within the graphene cluster was systematically varied to determine the effect of interior versus edge doping on the reactivity of the edge graphene sites. Model 1b, where a quaternary-N atom is at the zigzag edge of the graphene cluster, is found to be the most favored structure and strongly adsorbs O2 molecule via a “two feet” geometry. For this most stable O2 binding configuration, the potential-dependent free energy of reaction for the subsequent oxygen reduction reaction (ORR) steps was evaluated. The favored four electron-proton transfer mechanism passes through a dissociative O*+OH* state instead of an OOH* intermediate, followed by a series of reduction steps to produce water. At the equilibrium potential for ORR of 1.23 V-NHE, the protonation of O* and OH* both show uphill steps, but the production of O* is facile with a small overpotential. An applied potential of −0.15 V-NHE is required to facilitate the protonation of OH* to water, a larger overpotential than observed experimentally. While solvent effects may reduce this overpotential, our results suggest that the edge of the N-graphene is very active towards activation of O2 and production of O* and OH* but because of strong binding of the oxygen atom, the subsequent steps of the ORR reaction will be hindered. Mechanisms that have OH* formed at the edge site and then move to adjacent sites for more facile protonation will have to be explored in the future.

Aligning the Band Gap of Graphene Nanoribbons by Monomer Doping

Silicon-based field-effect transistors (FETs) are the building blocks of modern digital logic circuitry and therefore part of virtually every electronic device available today. Over the past decades, continuous downscaling of existing designs has met the rising performance requirements, but as the size of FETs approaches the regime of atomic structures, new concepts are required to maintain the current pace at which microelectronics is developing. At small gate channel lengths, the applicability of quantum mechanical principles results in several so-called short-channel effects (e.g. reduced carrier mobility). Since its experimental realization in 2004, graphene has been discussed intensively as a substitute for doped silicon in FETs because of its high charge carrier mobility and its unsurpassably low thickness. Graphene transistors have even been realized but cannot be put into the “off” state because of the lack of a band gap. However, there are concepts available for opening a band gap, for example, applying strain along the sheet or biasing bilayers of graphene. Also, lateral confinement in quasione-dimensional graphene nanoribbons (GNRs) leads to a band gap, which furthermore is highly sensitive to the width and edge shape of the GNR, thus opening possibilities to tailor the electronic properties of a device. Indeed, FETs built from nanoribbons show much higher on/off-ratios than graphene transistors, which makes them more suitable for integration into logic devices. However, the ability to control the electronic properties is essential: while the size of the gap can be engineered by varying the nanoribbon widths, the alignment of the GNR band structure with respect to the Fermi level of a metal electrode is equally important. Such a shifting of the entire band structure is observed both in two-dimensional graphene as well as in chemically synthesized or lithographically patterned GNRs upon doping, particularly with nitrogen atoms. Using present doping techniques, the distribution of dopant atoms will not be well-defined on the nanoscale and the band gap shift upon nitrogen doping depends on the site of the N atom, that is, the bonding configuration to neighboring carbon atoms. Generally, for doped and pristine GNRs, fabrication remains a challenge as well-established top-down approaches using lithography or unzipping of carbon nanotubes yield relatively wide ribbons with an undetermined edge structure. Particularly for small widths on the order of a few nanometers (where the band gap reaches a technologically relevant size) atomically precise edges are necessary and can be realized using Br-substituted precursor molecules, which are thermally activated on a surface and—in a bottom-up synthesis— covalently assemble to a specific nanostructure. In this study, we employed the latter approach to prepare GNRs with an atomically precise edge structure and doping pattern through polymerization of specific monomers directly on the Au(111) surface and studied the position and size of the band gap of these GNRs with surface-sensitive electron spectroscopies. Besides straight armchair edge GNRs, another type of chevron-shaped nanoribbons has previously been fabricated using an on-surface reaction. In this process adsorption of several layers of 6,11-dibromo-1,2,3,4-tetraphenyl-triphenylene (monomer 1 in Scheme 1) on Au(111) and heating at 250 8C leads to desorption of the second and higher layers as well as halogen dissociation and coupling of the resulting activated biradical monomers, yielding a sterically crowded and hence twisted polyphenylene. In a second heating step at 440 8C, this polymer undergoes a subsequent cyclodehydrogenation reaction providing access to the desired chevronshaped GNR with armchair edges. Selective substitution of the parent monomer 1 with either one or two N atoms provided monomers 2 and 3, respectively, which were used to generate GNRs with different doping levels (exemplarily shown for the doubly N doped GNR 5 in Scheme 1) and accordingly with potentially different electronic structure properties. Synthesis of the new monomers 2 and 3 was accomplished by Diels–Alder reactions of an appropriate cyclopentadienone with either mixed phenylpyridyl-acetylene or bispyridylacetylene, followed by immediate cheletropic CO extrusion (for details see the Supporting Information). [*] C. Bronner, S. Stremlau, A. Haase, Prof. Dr. P. Tegeder Fachbereich Physik, Freie Universit t Berlin Arnimallee 14, 14195 Berlin (Germany) E-mail: bronner@zedat.fu-berlin.de petra.tegeder@physik.fu-berlin.de

Effects of N doping and NH2grafting on the mechanical and wrinkling properties of graphene sheets

The effects of N doping and NH2 grafting on the mechanical and wrinkling properties of graphene sheets (GSs) have been investigated through molecular dynamics and molecular mechanics simulations. It is found that the Young's modulus of the N doped GS depends on the distribution manner and density of N dopants. Surface doping exhibits a much stronger influence on the Young's modulus than edge doping. The Young's moduli of the GSs gradually decreases with increasing distribution density. The degree of degradation of Young's moduli of GSs is more sensitive to NH2 grafting than to N, due to the larger local deformation caused by surface grafting. The wrinkling properties of functionalized GSs under shear deformation are also investigated, showing that the N doping and NH2 grafting also reduces the shear modulus and critical wrinkling strain. The general conclusions of this work can be helpful for nanomaterial synthesis and the characterization of functionalized GS-based nanosystems.