Edge Doping Research Articles

Nonlinear Plasmonics in Nanostructured Phosphorene.

Phosphorene has emerged as an atomically thin platform for optoelectronics and nanophotonics due to its excellent optical properties and the possibility of actively tuning light-matter interactions through electrical doping. While phosphorene is a two-dimensional semiconductor, plasmon resonances characterized by pronounced anisotropy and strong optical confinement are anticipated to emerge in highly doped samples. Here we show that the localized plasmons supported by phosphorene nanoribbons (PNRs) exhibit high tunability in relation to both edge termination and doping charge polarity and can trigger an intense nonlinear optical response at moderate doping levels. Our explorations are based on a second-principles theoretical framework, employing maximally localized Wannier functions constructed from ab initio electronic structure calculations, which we introduce here to describe the linear and nonlinear optical response of PNRs on mesoscopic length scales. Atomistic simulations reveal the high tunability of plasmons in doped PNRs at near-infrared frequencies, which can facilitate the synergy between the electronic band structure and plasmonic field confinement to drive efficient high-harmonic generation. Our findings establish nanostructured phosphorene as a versatile atomically thin material candidate for nonlinear plasmonics.

Electronic and optical properties of chemically modified 2D GaAs nanoribbons

We employed density functional theory calculations to investigate the electronic and optical characteristics of finite GaAs nanoribbons (NRs). Our study encompasses chemical alterations including doping, functionalization, and complete passivation, aimed at tailoring NR properties. The structural stability of these NRs was affirmed by detecting real vibrational frequencies in infrared spectra, indicating dynamical stability. Positive binding energies further corroborated the robust formation of NRs. Analysis of doped GaAs nanoribbons revealed a diverse range of energy gaps (approximately 2.672 to 5.132 eV). The introduction of F atoms through passivation extended the gap to 5.132 eV, while Cu atoms introduced via edge doping reduced it to 2.672 eV. A density of states analysis indicated that As atom orbitals primarily contributed to occupied molecular orbitals, while Ga atom orbitals significantly influenced unoccupied states. This suggested As atoms as electron donors and Ga atoms as electron acceptors in potential interactions. We investigated excited-state electron–hole interactions through various indices, including electron–hole overlap and charge-transfer length. These insights enriched our understanding of these interactions. Notably, UV–Vis absorption spectra exhibited intriguing phenomena. Doping with Te, Cu, W, and Mo induced redshifts, while functionalization induced red/blue shifts in GaAs-34NR spectra. Passivation, functionalization, and doping collectively enhanced electrical conductivity, highlighting the potential for improving material properties. Among the compounds studied, GaAs-34NR-edg-Cu demonstrated the highest electrical conductivity, while GaAs-34NR displayed the lowest. In summary, our comprehensive investigation offers valuable insights into customizing GaAs nanoribbon characteristics, with promising implications for nanoelectronics and optoelectronics applications.

Toward High-Peak-to-Valley-Ratio Graphene Resonant Tunneling Diodes.

The resonant tunneling diode (RTD) is one of the very few room-temperature-operating quantum devices to date that is able to exhibit negative differential resistance. However, the reported key figure of merit, the current peak-to-valley ratio (PVR), of graphene RTDs has been up to only 3.9 at room temperature thus far. This remains very puzzling, given the atomically flat interfaces of the 2D materials. By varying the active area and perimeter of RTDs based on a graphene/hexagonal boron nitride/graphene heterostructure, we discovered that the edge doping can play a dominant role in determining the resonant tunneling, and a large area-to-perimeter ratio is necessary to obtain a high PVR. The understanding enables establishing a novel design rule and results in a PVR of 14.9, which is at least a factor of 3.8 higher than previously reported graphene RTDs. Furthermore, a theory is developed allowing extraction of the edge doping depth for the first time.

Investigation on the Edge Doping Process of Nitrogen-Doped Carbon Materials by In Situ Pyrolysis Mass Spectrometry and Laser-Induced Acoustic Desorption Mass Spectrometry

Nitrogen-doped carbon materials demonstrate high performance as electrodes in fuel cells and higher oxygen reduction reactivity than traditional Pt-based electrodes. However, the formation process of nitrogen-doped carbon materials has long been a mystery. In this study, the formation mechanism of nitrogen-doped carbon materials from polyaniline (PANI) pyrolysis was studied by the combination of in situ pyrolysis vacuum ultraviolet photoionization time-of-flight mass spectrometry (Py-VUVPI-TOF MS) and substrate-enhanced, laser-induced acoustic desorption source time-of-flight mass spectrometry (SE-LIAD-TOF MS). The initial pyrolysis species, including free radicals and intermediates, were investigated via in situ Py-VUVPI-TOF MS during the temperature-programmed desorption process (within tens of microseconds). The pyrolysis residues were collected and further investigated via SE-LIAD-TOF MS, revealing the product information of the initial pyrolysis products. The results show that the edge doping of carbon materials depends on free radical reactions rather than the direct substitution of carbon atoms by nitrogen atoms. Meanwhile, pyrrole nitrogen and pyridine nitrogen are formed by the free radical cyclization reaction and the amino aromatization reaction at the initial stage of pyrolysis, while the formation of graphitic nitrogen depends on the further polymerization reaction of pyrrole nitrogen and pyridine nitrogen.

Comparative DFT study on the H2 adsorption and the sensing properties of BN-, BP-, AlN-, and AlP-decorated graphene nanoflakes

In this research, the application of BN, BP, AlN, and AlP edge-doped graphene nanoflakes as sensor for sensing of H 2 molecule was studied by DFT approach. The M06-2X/6-311G++(d,p) level of theory have been used in the calculations. The results showed that the adsorption of H 2 molecule on the BN, BP, and AlN was very weak (−0.97, −0.16, and −1.14 kcal.mol −1 , respectively). By considering the acceptable adsorption of H 2 molecule on the AlP-doped graphene with −5.03 kcal.mol −1 , further calculations were performed on this sheet. Upon adsorption of H 2 molecule, the HOMO–LUMO gap ( E g ) of the AlP-doped graphene nanoflake decreased slightly from 2.01 to 1.92 eV. Therefore, the electrical conductivity of AlP-doped graphene sheet increased. Moreover, Δ H ad = −3.38 kcal.mol −1 and Δ G ad = −1.38 kcal.mol −1 show that the adsorption of H 2 molecule on the AlP-doped graphene is an exothermic and spontaneous phenomenon at room temperature. The NCI-RDG analyses verifies the presence of vdW interactions between H 2 molecule and the AlP-doped graphene. Finally, according to the very low recovery time as 4.65 ns, AlP-doped graphene might be utilized as an effective and fast sensor for H 2 molecule at room temperature. • The effect of BN, BP, AlN, and AlP edge doping of graphene on the H 2 sensing is studied. • Adsorption of H 2 molecule on the AlP-edge doped graphene occurs thermodynamically effective. • NCI-RDG analysis shows that the H 2 adsorption on the AlP-edge doped graphene occurs via vdW interactions. • AlP-edge doped graphene can be considered as an ultrafast H 2 sensor with 4.65 ns recovery time.

Novel channel edge doping for hump reduction in LTPS TFTs

We proposed a new channel edge doping (CED) technique for hump reduction in n-type low-temperature polycrystalline silicon (LTPS) thin-film transistors (TFTs) and validated it through experiments and technology computer-aided design (TCAD) simulations. The TCAD simulations indicate that the hump effect in LTPS TFTs is due to the high electron (e−) concentration (∼1016 cm−3) induced by an enhanced electric field (e-field) at the channel edge region along the width direction. In order to reduce the hump effect, we focused on decreasing the e− concentration at the channel edge. The CED process led to the selective control of the e− concentration at the channel edge. The decrease in the maximum e− concentration from 3.4 × 1016 to 2.9 × 1014 cm−3 at the channel edge using CED led to an effective reduction in the hump characteristic of LTPS TFTs. Furthermore, the CED process does not require any additional masks and is highly effective in hump reduction, rendering it beneficial for manufacturing active-matrix organic light-emitting diode displays.

Edge Doping Engineering of High-Performance Graphene Nanoribbon Molecular Spintronic Devices.

We study the quantum transport properties of graphene nanoribbons (GNRs) with a different edge doping strategy using density functional theory combined with nonequilibrium Green’s function transport simulations. We show that boron and nitrogen edge doping on the electrodes region can substantially modify the electronic band structures and transport properties of the system. Remarkably, such an edge engineering strategy effectively transforms GNR into a molecular spintronic nanodevice with multiple exceptional transport properties, namely: (i) a dual spin filtering effect (SFE) with 100% filtering efficiency; (ii) a spin rectifier with a large rectification ratio (RR) of 1.9 ×; and (iii) negative differential resistance with a peak-to-valley ratio (PVR) of 7.1 ×. Our findings reveal a route towards the development of high-performance graphene spintronics technology using an electrodes edge engineering strategy.

Conductive Nanodiamond-Based Detection of Neurotransmitters: One Decade, Few Sensors.

Nanodiamond (ND) is a class of carbon nanomaterial with covalently connected sp3 carbon atoms in its core and an sp2 carbon adorned surface via edge defects or doping. Endogenous chemicals that provoke physiological responses in the human system called neurotransmitters (NTs) have been detected with several sensors with carbon-based nanomaterials. Nanodiamonds (NDs), another class of carbon nanomaterial, have shown the requisite surface area and electrocatalytic activity toward NTs in the past decade. Surprisingly, only a few electrochemical ND based NT sensors are available. This work briefly looked into the performance of the available sensors, NT and ND interactions, and the possible reason for data paucity on the subject matter.

Enhanced photocatalytic properties of a chemically modified blue phosphorene.

It is high time to placate the peak demand for an efficient, economic and green fuel in the form of H2 through photocatalytic water splitting. Several low dimensional materials have been explored for their photocatalytic properties on account of their surface to volume ratio. The present study illustrates the excellent photocatalytic potential of a two-dimensional material, viz. a chemically tempered blue-phosphorene sheet, with single atom thickness and high carrier mobility. Metal-free element, sulphur, is explored as a dopant in a 32-atom blue-phosphorene sheet. The dopant is inserted at three locations viz. central, edge and central edge positions with varying concentrations from 3.125% to 18.75% (corresponding to n = 1 to 6 sulphur atoms within a 32-atom blue-phosphorene sheet, P32−nSn). The cohesive energy studies predict the higher stability of even number S doped sheets as compared to their odd counterparts. Photocatalytic activity is studied in terms of band gap and band alignment for different concentrations of the former. Studies reveal that edge doping demonstrates better water molecule activation independent of S atom concentration. The edge doped systems not only provide the chemical activity to activate water, but also show feasible HER overpotentials of 1.24–1.29 eV at neutral medium. Finally, this work opens up a driving lead of non-corrosive catalysts for water molecule splitting.

On the Origin of Photocurrents in Pristine Graphene

Recently Ma et al. (Nature Nanotech. 14, 145, 2019) reported an intrinsic photocurrent in graphene, which occurs as the authors believe “in a different parameter regime from all the previously observed photothermoelectric or photovoltaic photocurrents in graphene”. Here we present an alternative – obvious and transparent explanation of such experiments. We demonstrate that the photo effect occurs in the p–n junctions formed in graphene samples containing two regions of different widths with different particle concentrations. This difference in concentration for various sample widths is found to result from edge doping of samples.

Enhanced Oxygen Reduction Catalysis of Carbon Nanohybrids from Nitrogen-Rich Edges.

The edge doping effect would help improve the carbon-based electrocatalysis. Herein, we present an all-mechanical technique for the fabrication of cut, exfoliated N-doped carbon nanotubes (C, E-N-CNTs). Such nanohybrids with an edge-N-rich structure are obtained through sequential doping and mechanical treatments of the pristine bulk-CNTs. The C, E-N-CNT/carbon black (C, E-N-CNT/C) demonstrates exciting oxygen reduction reaction (ORR) electrocatalysis with exceptionally low-onset potential (E0, 913 mV versus RHE) and satisfactory half-wave potential (E1/2, merely -7.3 mV shift compared with that of commercial 20% platinum/C (Pt/C)). Besides, the C, E-N-CNT/C presents significantly enhanced durability and tolerance in chronoamperometry test with methanol injection compared with the Pt/C. Our work would facilitate the mass production and full exploration of nonmetallic electrocatalysts.

Generating pure spin current in zigzag graphene nanoribbons by a thermal gradient: the effect of edge doping with BN pairs

Based on density functional theory combined with non-equilibrium Green’s function method, we investigate the thermoelectric transport properties of zigzag-edged graphene nanoribbons (ZGNRs) co-doped by two BN pairs at one edge. By applying the co-doping scheme of BN pairs instead of single B and N atoms as reported in literature, the energy of the quasi-bound states gets very close to the Fermi level. Due to the back scattering from the quasi-bound states, transmission valleys appear around the Fermi level, which results in a large transmission slope and Seebeck thermopower for both spin channels. Interestingly, the signs of the Seebeck thermopower of the two spin channels are opposite and the magnitudes are nearly equal, which can be utilized for generating pure spin current with a thermal gradient. More importantly, the thermal spin current is robust against the change of the distance between the two BN pairs and the doping configuration. These findings suggest a fascinating strategy for thermal spin current generation using BN pair co-doping and will be significant for the design of spintronic devices based on graphene nanoribbons.

Carrier transport of rough-edged doped GNRFETs with metal contacts at various channel widths

Abstract Graphene nanoribbons (GNRs) have attracted much attention owing to their exotic electronic properties. However, it is impossible to fabricate GNRs with perfect edges. The edge roughness effect will degrade the performance of the field effect transistor (FET). Therefore, modelling GNR FETs (GNRFETs) with the line-edge roughness effect and doping is crucial for evaluating the performance metrics of these devices. In this research study, the carrier transport properties of double-gate, monolayer, doped, rough-edged armchair GNRFETs (AGNRFETs) with various channel widths, and metallic zigzag GNR (ZGNR) contacts are studied. The investigated width index originates from the 3p+1 family, and step and edge doping with nitrogen atoms (n-doping) and boron atoms (p-doping) are applied. In addition, the nearest-neighbour tight-binding method is employed to build the Hamiltonian matrix of the device. The self-consistent solutions of the Poisson and Schrodinger equations are computed with the recursive non-equilibrium Green's function (NEGF) method and successive over-relaxation (SOR) method to minimise the time consumption for convergence. The carrier transport properties of the pristine and non-pristine devices (e.g. the total density of states (DOS), transmission coefficient, energy-resolved current spectrum, and various current–voltage characteristics) are simulated. Based on the output, the performance metrics of the device, including the subthreshold swing, drain-induced barrier lowering (DIBL), threshold voltage, and on/off current ratio, are calculated. The results of different widths are compared separately and for the pristine and doped rough-edged channel devices. For narrower devices, the subthreshold swing and DIBL decrease, whereas the threshold voltage and on/off current ratio increase. The subthreshold swing and DIBL of the doped rough-edged channel device are superior to those of the pristine channel device. Moreover, the on-current, threshold voltage, and on/off current ratio of the rough-edged channel improve with dopants. N-doping achieves a much higher current in the on-state owing to the lighter electron mass and faster electron velocity compared with those of holes. Furthermore, the n-type rough-edged seven-armchair GNRFET with a length of 5 nm exhibits an outstanding subthreshold swing of approximately 85.2 mV/dec and a DIBL of 63.03 mV/V. Thereby, the narrower doped, rough-edged device is less affected by short-channel effects and exhibits lower leakage currents in the off-state. This results in a better switching performance, which makes it a potential candidate for future nano-electronic applications with low-power design.

Edge Doping in Graphene Devices on SiO2 Substrates

The conductivity of single layer and bilayer graphene ribbons 0.5–4 μm in width fabricated by oxygen plasma etching is studied experimentally. The dependence of the electron concentration in graphene on the ribbon width is revealed. This effect is explained by the edge doping of graphene due to defects arranged in SiO2 near the ribbon edges. The method of the formation of abrupt p–n junctions in graphene and structures with a constant electron concentration gradient in the graphene plane with the help of edge doping is proposed.

Edge Doping Effect to the Surface Plasmon Resonances in Graphene Nanoribbons

In this work, we investigated the edge doping effect to graphene plasmon resonances in graphene nanoribbons (GNRs), which is known to affect the electronic doping of GNRs but has not been systematically studied. We found the Fermi levels, which reflect that the sheet charge carrier densities, extracted from the graphene plasmon resonance frequencies, vary across GNRs of different widths on the same sample. Using Raman spectroscopy, we confirmed that the variation of the sheet charge carrier density is caused by edge doping, which has a stronger effect on narrower GNRs. To further understand the edge doping effect, electron beam irradiation (EBI) is applied to modify the charge state of the edge. Using EBI, we successfully demonstrated the tuning of the graphene plasmon resonances due to the change of the edge doping states. These findings demonstrated the importance of the edge doping effect in determination of the surface plasmon frequency in GNRs.

Краевое легирование в графеновых приборах на подложках SiO-=SUB=-2-=/SUB=-

AbstractThe conductivity of single layer and bilayer graphene ribbons 0.5–4 μm in width fabricated by oxygen plasma etching is studied experimentally. The dependence of the electron concentration in graphene on the ribbon width is revealed. This effect is explained by the edge doping of graphene due to defects arranged in SiO_2 near the ribbon edges. The method of the formation of abrupt p – n junctions in graphene and structures with a constant electron concentration gradient in the graphene plane with the help of edge doping is proposed.

Transport properties of doped zigzag graphene nanoribbons

Numerous studies on materials have driven the development of modern nanoelectronic devices. And research also shown that the integrated circuits have entered the era of the nanoelectronic scales from the scale of microelectronics. But the limitations of copper as a traditional connection, such as the resistivity increases a lot, further causing a lot of heat in the interconnect, have been highlighted. Therefore, we need new materials as the substitution of copper. The metallic properties exhibited by the zigzag graphene nanoribbons (ZGNRs) can be controlled by the edge states, doping and different widths of the nanoribbons. In this paper, we applied simulation to dope copper atom chains on ZGNRs. We found an energetic phenomenon that after doping the nanoribbons conductivity have increased significantly than the original. In addition, the transmission channels are mainly concentrated near the doping position, and the width used for transmission is greatly reduced after doping. It is expected to be used as an inter-connect application in nano-integrated circuits in the future.

Investigation on Tunable Optical Properties and Structures of Graphene Quantum Dots Doped with Sulfur Heteroatoms

Due to pronounced quantum confinement and edge effects, graphene quantum dots (GQDs) demonstrate numerous novel chemical and physical properties and thereby, have potential applications in optoelectronic devices, sensors and biomedical imaging. Doping GQDs with heteroatoms is an effective way to tailor their electronic and optical properties. However, due to different synthesis methods, the widespread use of GQDs doped with heteroatoms has been hindered by the poor understanding of their optical mechanisms. Recently, we studied optical properties of GQDs by employing theoretical calculations and experimental work, which demonstrated that theoretical studies can reveal optical mechanism of GQDs. In this work, the mechanisms underlying the tunable optical properties of GQDs doped with B and S are investigated using density functional theory and time-dependent density functional theory calculations. The electronic structures, optical spectra, molecular orbitals, and electronic density of GQDs are predicted to reveal electron transition processes. Especially, GQDs doped with different B and S patterns are designed to reveal the influence of the existence of O atoms on optical and electronic properties of GQDs. In general, electron-rich S atom increases the HOMO energy, while electron-deficient B atom lowers the LUMO energy, resulting in a decreased HOMO–LUMO gap. Edge doped effect analysis shows that B on GQDs induce a small red shift in absorption spectra whereas a large red shift occurs with surface doped GQDs. However, the absorption spectra of B and O co-doped GQDs exhibit an obvious blue shift and the absorption intensities enhance markedly. For S doped GQDs, the influences of surface and edge doping on absorption spectra of GQDs are almost opposite. Surface doped GQDs induces a small redshift in absorption spectra whereas a large redshift occurs with edge doped GQDs. The recombination of excited, well-separated electron hole pairs can result in enhanced absorption intensity. The heteroatoms doping on the basal plane can transform the sp2 hybridized carbon into the sp3 state. It is expected that this work will provide valuable knowledge for understanding and interpreting the electronic and optical properties of GQDs at atomic scale, and give important insights and guidance for the development of methods to controllably synthesize GQDs with well-defined and desirable properties towards specific purposes.

Armchair α-graphyne nanoribbons as negative differential resistance devices: Induced by nitrogen doping

Abstract Using non-equilibrium Green's functions (NEGF) in combination with tight-binding (TB) model, the electronic transport properties of pristine and nitrogen (N) doped armchair α-graphyne nanoribbons (A-α-GYNRs) are studied under finite bias. Initially, we have calculated the total energy in order to find the most stable place for N atom. Then we have investigated the effect of width (W) and length (L) of the ribbon and also the position (edge and center of the ribbon) and concentration of doping on the electronic transport properties. Our results reveal that, doping changes the semiconducting behavior of 3n and 3n+1 A-α-GYNRs to semi metallic. Moreover, it is observed that the electronic transport properties are more affected by central doping rather than the edge doping. Interestingly, both edge and central doped ribbons show negative differential resistance (NDR) in all widths. Our results show that doping concentration and the NDR are inversely proportional to each other. We have also found that, as the length of the central region of the device gets longer, the NDR reaches up to 159. Transmission spectrum, bandstructure of the electrodes, Bloch wave functions and density of states (DOS) are analyzed subsequently to more elucidate the electronic transport properties. Our findings could be used to develop the nano-scale NDR devices.

Growth of \u2018W\u2019 doped molybdenum disulfide on graphene transferred molybdenum substrate

In the present study, a novel method has been carried out to grow tungsten (W) doped molybdenum disulfide (MoS2) on the graphene transferred TEM grid in a chemical vapor deposition (CVD) setup. Tungsten trioxide (WO3) has been used as a source for ‘W’ while ‘Mo’ has been derived from Mo based substrate. Different experimental parameters were used in this experiment. Higher gas flow rate decreases the size of the sample flake and on other side increases the dopant concentrations. The interaction mechanism between Mo, S, W and oxygen (O) have been explored. The influence of oxygen seems to be not avoidable completely which also imposes effective growth condition for the reaction of Mo with incoming sulfur atoms. The difference in the migration energies of Mo, WO3, S clusters on the graphene and the higher reactivity of Mo clusters over other possibly formed atomic clusters on the graphene leads to the growth of W doped MoS2 monolayers. Formation of MoS2 monolayer and the nature of edge doping of ‘W’ is explained well with the crystal model using underlying nucleation principles. We believe our result provide a special route to prepare W doped MoS2 on graphene substrate in the future.