Charge Neutrality Point Research Articles

State-space modeling for dynamic response of graphene FET biosensors

Graphene field effect transistor (G-FET) biosensors exhibit high sensitivity owing to their high electron/hole mobilities and unique 2D nature. However, a baseline drift is observed in their response in aqueous environment, making it difficult to analyze their response against target molecules. Here, we present a computational approach to build state-space models (SSMs) for the time-series data of a G-FET biosensor; the approach helps separate the response against target molecules from the baseline drift. The charge neutral point of the G-FET sensor was continuously measured while sensing target molecules. The obtained time-series data were modeled using the proposed SSMs. The model parameters were estimated through Markov chain Monte Carlo methods. The SSMs were evaluated using the widely-applicable Bayesian information criterion. The SSMs well fitted the time-series data of the G-FET biosensor, and the sensor response to target molecules was extracted from the baseline-drift data.

Persistent and reversible electrostatic control of doping in graphene/hexagonal boron nitride heterostructures

Since its first application as a substrate for graphene field effect transistors (FETs), hexagonal boron nitride (hBN) has become a prominent component in two-dimensional (2D) material devices. In addition, hBN has been shown to host defects that can be manipulated to change the electronic properties of adjacent 2D materials. Despite the wide use of such defect manipulations, no focused efforts have been made to further the understanding of defect excitations and their influence in graphene/hBN FETs. In this study, we explore the effect of high electric fields (∼10V/nm) on graphene/hBN FETs and find that persistent and reversible shifts in graphene's charge neutrality point (CNP) occur. By increasing the applied electric field and temperature of our device, we find that this CNP shift is enhanced. With this insight, we propose a mechanism that explains these observations based on Poole–Frenkel emissions from defects in hBN. Finally, we show that such an effect may be suppressed by using graphite as a backgate, thus preventing unintended changes in the electrical properties of graphene/hBN FETs.

1/f critical current noise in short ballistic graphene Josephson junctions

Short ballistic graphene Josephson junctions sustain superconducting current with a non-sinusoidal current-phase relation up to a critical current threshold. The current-phase relation, arising from proximitized superconductivity, is gate-voltage tunable and exhibits peculiar skewness observed in high quality graphene superconductors heterostructures with clean interfaces. These properties make graphene Josephson junctions promising sensitive quantum probes of microscopic fluctuations underlying transport in two-dimensions. We show that the power spectrum of the critical current fluctuations has a characteristic 1/f dependence on frequency, f, probing two points and higher correlations of carrier density fluctuations of the graphene channel induced by carrier traps in the nearby substrate. Tunability with the Fermi level, close to and far from the charge neutrality point, and temperature dependence of the noise amplitude are clear fingerprints of the underlying material-inherent processes. Our results suggest a roadmap for the analysis of decoherence sources in the implementation of coherent devices by hybrid nanostructures.

Tunable room-temperature spin galvanic and spin Hall effects in van der Waals heterostructures

Spin-orbit coupling stands as a powerful tool to interconvert charge and spin currents and to manipulate the magnetization of magnetic materials through spin-torque phenomena. However, despite the diversity of existing bulk materials and the recent advent of interfacial and low-dimensional effects, control of this interconversion at room temperature remains elusive. Here, we demonstrate strongly enhanced room-temperature spin-to-charge interconversion in graphene driven by the proximity of WS2. By performing spin precession experiments in appropriately designed Hall bars, we separate the contributions of the spin Hall and the spin galvanic effects. Remarkably, their corresponding conversion efficiencies can be tailored by electrostatic gating in magnitude and sign, peaking near the charge neutrality point with an equivalent magnitude that is comparable to the largest efficiencies reported to date. Such electric-field tunability provides a building block for spin generation free from magnetic materials and for ultra-compact magnetic memory technologies.

Bias dependent variability of low-frequency noise in single-layer graphene FETs.

Low-frequency noise (LFN) variability in graphene transistors (GFETs) is for the first time researched in this work under both experimental and theoretical aspects. LFN from an adequate statistical sample of long-channel solution-gated single-layer GFETs is measured in a wide range of operating conditions while a physics-based analytical model is derived that accounts for the bias dependence of LFN variance with remarkable performance. LFN deviations in GFETs stem from the variations of the parameters of the physical mechanisms that generate LFN, which are the number of traps (Ntr) for the carrier number fluctuation effect (ΔN) due to trapping/detrapping process and the Hooge parameter (αH) for the mobility fluctuations effect (Δμ). ΔN accounts for an M-shape of normalized LFN variance versus gate bias with a minimum at the charge neutrality point (CNP) as it was the case for normalized LFN mean value while Δμ contributes only near the CNP for both variance and mean value. Trap statistical nature of the devices under test is experimentally shown to differ from classical Poisson distribution noticed at silicon-oxide devices, and this might be caused both by the electrolyte interface in GFETs under study and by the premature stage of the GFET technology development which could permit external factors to influence the performance. This not fully advanced GFET process growth might also cause pivotal inconsistencies affecting the scaling laws in GFETs of the same process.

Topological properties and orbital magnetism in twisted graphene systems

We review and discuss the electronic structures, topological properties and orbital magnetism in twisted bilayer (TBG) and multilayer graphene systems. Moiré pattern is formed in twisted bilayer graphene due to the mutual twist of the two graphene layers. The moiré potential induced by the twist can generate opposite pseudo magnetic fields in the Moiré supercell, which are coupled with the Dirac fermions and generate two sets of pseudo Landau levels with opposite Chern numbers <inline-formula><tex-math id="M2">\begin{document}$\pm1$\end{document}</tex-math><alternatives><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="14-20200506_M2.jpg"/><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="14-20200506_M2.png"/></alternatives></inline-formula>. The two flat bands for each valley each spin of TBG are equivalent to the two zeroth pseudo Landau levels with opposite Chern numbers and opposite sublattice polarizations. Such a pseudo-Landau-level representation has significant implications on the quantum anomalous Hall states observed at integer fillings of the flat bands in TBG at the magic angle. The origin of the magic angle can also be naturally explained by using the pseudo-Landau-level picture. We further discuss twisted multilayer graphene systems, and show that topological flat bands generally exist in the twisted multilayer graphene systems. These topological flat bands have nonzero valley Chern numbers, which can be described by a succinct formula under certain approxmations. These topological flat bands in twisted bilayer and multilayer graphene systems are associated with orbital magnetism. A valley polarized state in the twist graphene system is an orbital magnetic state with nontrivial current-loop pattern in the moiré supercell. The experimentally observed correlated insulating states at <inline-formula><tex-math id="M3">\begin{document}$\pm 1/2$\end{document}</tex-math><alternatives><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="14-20200506_M3.jpg"/><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="14-20200506_M3.png"/></alternatives></inline-formula> fillings and at charge neutrality point of magic-angle TBG can be valley polarized states, which are associated with compensating current loops and induce staggered orbital magnetizations on the moiré length scale. If <inline-formula><tex-math id="M4">\begin{document}$C_{2z}$\end{document}</tex-math><alternatives><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="14-20200506_M4.jpg"/><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="14-20200506_M4.png"/></alternatives></inline-formula> symmetry is broken due to the alignment of hexagonal boron nitride substrate, then a valley-polarized ground state would be a moiré orbital ferromagnetic state, which exhibits not only (quantum) anomalous Hall effect, but also novel magneto-optical and nonlinear optical responses.

Electron-hole hybridization in bilayer graphene.

Band structure determines the motion of electrons in a solid, giving rise to exotic phenomena when properly engineered. Drawing an analogy between electrons and photons, artificially designed optical lattices indicate the possibility of a similar band modulation effect in graphene systems. Yet due to the fermionic nature of electrons, modulated electronic systems promise far richer categories of behaviors than those found in optical lattices. Here, we uncovered a strong modulation of electronic states in bilayer graphene subject to periodic potentials. We observed for the first time the hybridization of electron and hole sub-bands, resulting in local band gaps at both primary and secondary charge neutrality points. Such hybridization leads to the formation of flat bands, enabling the study of correlated effects in graphene systems. This work may provide a novel way to manipulate electronic states in layered systems, which is important to both fundamental research and application.

Magnetotransport study of the mini-Dirac cone in AB-stacked four- to six-layer graphene under perpendicular electric field

Landau levels of AB-stacked four- to six-layer graphene were studied experimentally in the presence of a perpendicular electric field. The Landau levels at a low magnetic field showed a characteristic structure that originated from the mini-Dirac cones created by the perpendicular electric fields. Six-fold or twelve-fold degenerate Landau levels arising from the mini-Dirac cones were observed in the vicinity of the charge neutrality point as a radial structure in a plot of their Landau fan diagrams. The structure of four-layer graphene had approximate electron-hole symmetry near the charge neutrality point, while the five- and six-layer graphene showed asymmetry. Numerical calculations of the dispersion relation and Landau level spectra indicated that trigonal warping played an essential role in forming the experimentally observed Landau level structure in low magnetic fields. In high magnetic fields, trigonal warping becomes less significant and the Landau level spectra become simpler, approaching those that were calculated without considering trigonal warping. The appearance of mini-Dirac cones in a perpendicular electric field would be a common feature of AB-stacked multilayer graphene.

Functionalized graphene transistor for ultrasensitive detection of carbon quantum dots

Ubiquitous carbon nanomaterials have great potential for emerging technologies, but they also pose a threat to human health at the end of their lifecycle, especially when they are introduced into waste or ground waters. Graphene field-effect transistors (GFET) and real time in situ confocal Raman microscopy (CRM) were employed to detect a submonolayer of carbon quantum dots (CQDs) in water. An effective GFET channel was formed on exfoliated and chemical vapor deposited (CVD) graphene. The adsorption of CQDs was monitored by measuring conductance changes in GFETs. The graphene channel was functionalized with (3-aminopropyl) triethoxysilane (APTES), which allowed for easy observation of a shift in the charge neutrality point (CNP) when the graphene channel was exposed to CQDs. The affinity of the CQD’s carboxyl terminal groups to the aminofunctionalized channel enabled a highly sensitive CQD detection based on changes in the GFET conductivity. The adsorption of the CQDs induced a positive shift of the CNP with a limit of detection at concentrations of 239 ppm and 62 ppm for the exfoliated and CVD graphene, respectively. A supporting study of graphene functionalization and CQD adsorption was performed by real time in situ CRM, ellipsometry, and ex situ X-ray photoelectron spectroscopy.

Velocity Saturation Effect on Low Frequency Noise in Short Channel Single Layer Graphene Field Effect Transistors

Graphene devices for analog and RF applications are prone to Low Frequency Noise (LFN) due to its upconversion to undesired phase noise at higher frequencies. Such applications demand the use of short channel graphene transistors that operate at high electric fields in order to ensure a high speed. Electric field is inversely proportional to device length and proportional to channel potential so it gets maximized as the drain voltage increases and the transistor length shrinks. Under these conditions though, short channel effects like Velocity Saturation (VS) should be taken into account. Carrier number and mobility fluctuations have been proved to be the main sources that generate LFN in graphene devices. While their contribution to the bias dependence of LFN in long channels has been thoroughly investigated, the way in which VS phenomenon affects LFN in short channel devices under high drain voltage conditions has not been well understood. At low electric field operation, VS effect is negligible since carriers velocity is far away from being saturated. Under these conditions, LFN can be precicely predicted by a recently established physics-based analytical model. The present paper goes a step furher and proposes a new model which deals with the contribution of VS effect on LFN under high electric field conditions. The implemented model is validated with novel experimental data, published for the first time, from CVD grown back-gated single layer graphene transistors operating at gigahertz frequencies. The model accurately captures the reduction of LFN especially near charge neutrality point because of the effect of VS mechanism. Moreover, an analytical expression for the effect of contact resistance on LFN is derived. This contact resistance contribution is experimentally shown to be dominant at higher gate voltages and is accurately described by the proposed model.

Tuning Insulator-Semimetal Transitions in 3D Topological Insulator thin Films by Intersurface Hybridization and In-Plane Magnetic Fields.

A pair of Dirac points (analogous to a vortex-antivortex pair) associated with opposite topological numbers (with ±π Berry phases) can be merged together through parameter tuning and annihilated to gap the Dirac spectrum, offering a canonical example of a topological phase transition. Here, we report transport studies on thin films of BiSbTeSe_{2}, which is a 3D topological insulator that hosts spin-helical gapless (semimetallic) Dirac fermion surface states for sufficiently thick samples, with an observed resistivity close to h/4e^{2} at the charge neutral point. When the sample thickness is reduced to below ∼10 nm thick, we observe a transition from metallic to insulating behavior, consistent with the expectation that the Dirac cones from the top and bottom surfaces hybridize (analogous to a "merging" in the real space) to give a trivial gapped insulator. Furthermore, we observe that an in-plane magnetic field can drive the system again towards a metallic behavior, with a prominent negative magnetoresistance (up to ∼-95%) and a temperature-insensitive resistivity close to h/2e^{2} at the charge neutral point. The observation is consistent with a predicted effect of an in-plane magnetic field to reduce the hybridization gap (which, if small enough, may be smeared by disorder and give rise to a metallic behavior). A sufficiently strong magnetic field is predicted to restore and split again the Dirac points in the momentum space, inducing a distinct 2D topological semimetal phase with two single-fold Dirac cones of opposite spin-momentum windings.

Intrinsic band gap and electrically tunable flat bands in twisted double bilayer graphene

We present atomistic calculations on structural and electronic properties of twisted double bilayer graphene (TDBG) consisting of two sets of rotationally misaligned Bernal-stacked bilayer graphene. Obtained equilibrium atomic structures exhibit in-plane strains and the modulation of the interlayer distances at the rotationally mismatched interface layers. We find that the electronic structure of TDBG can have an intrinsic band gap at the charge neutral point for a large range of the twist angle theta. Near theta = 1.25 degree, the intrinsic band gap disappears and TDBG hosts flat bands at the Fermi level that are energetically well separated from higher and lower energy bands. We also show that the flat bands are easily tunable by applying vertical electric fields, and extremely narrow bandwidths less than 10 meV can be achieved for the electron-side flat bands in a wide range of the twist angle. Our results serve as a theoretical guide for exploring emergent correlated electron physics in this versatile moire superlattice system.

Unexpected Hole Doping of Graphene by Osmium Adatoms

AbstractThe electronic transport of monolayer graphene devices is studied before and after in situ deposition of a sub‐monolayer coating of osmium adatoms. Unexpectedly, and unlike all other metallic adatoms studied to date, osmium adatoms shift the charge neutrality point to more positive gate voltages. This indicates that osmium adatoms act as electron acceptors and thus leave the graphene hole‐doped. Analysis of transport data suggest that Os adatoms behave as charged impurity scatterers, albeit with a surprisingly low charge‐doping efficiency. The charge neutrality point of graphene is found to vary non‐monotonically with gate voltage as the sample is warmed to room temperature, suggesting that osmium diffuses on the surface but is not completely removed.

Papain Adsorption on Latex Particles: Charging, Aggregation, and Enzymatic Activity.

The effect of papain adsorption on the surface charge properties and aggregation mechanism of sulfate-functionalized polystyrene latex particles was studied. The positively charged enzyme possessed a high affinity to the oppositely charged particles, giving rise to charge neutralization and charge reversal at appropriate papain concentrations. The tendency in the particle aggregation rates at different enzyme doses revealed that the colloidal stability of the samples is governed by interparticle forces of electrostatic origin. The aggregation mechanism was qualitatively described within the classical DLVO theory, and unstable dispersions were detected near the charge neutralization point, while particle aggregation was not observed at low and elevated papain concentrations. The relatively high dispersion stability of the bare latex particles was maintained upon the formation of an enzyme layer on the surface, and the obtained latex-papain composite showed notable resistance against salt-induced aggregation. Remarkable hydrolytic and antioxidant activities of the immobilized enzyme were observed in probe reactions; therefore, the obtained hybrid can be considered as a multifunctional biocatalytic system with great promise in applications in industrial manufacturing processes.

Electrically tuning many-body states in a Coulomb-coupled InAs/InGaSb double layer

We study the transport properties of an electron-hole double layer consisting of barrier-separated InAs/InGaSb quantum wells. We focus on measurements of four-terminal resistivity of a Hall-bar sample as a function of electron $(n)$ and hole $(p)$ density, that are being tuned by a pair of top and bottom gates. In zero magnetic field, we clearly observe an insulating phase which occurs at a charge neutral point, below a critical carrier density $n=pl1\phantom{\rule{4pt}{0ex}}\ifmmode\times\else\texttimes\fi{}{10}^{11}\phantom{\rule{0.16em}{0ex}}\mathrm{c}{\mathrm{m}}^{\ensuremath{-}2}$. This phase is characterized by a narrow and thermally activated resistance peak and an anomalous Hall resistance. This observation reinforces our previous finding of an excitonic insulator. Remarkably, when the layer densities are being tuned into imbalance, here $p\ensuremath{\gg}n$, a broader resistance peak emerges. We discuss this phase with respect to a possible (theoretically predicted) charge density wave ground state. Both phases can persist above \ensuremath{\sim}25 K, indicating robust correlations in the electron-hole double layers.

Enzymatically Synthesized DNA Polymer as Co-carrier for Enhanced RNA Interference.

Polymerization of small interfering RNA (siRNA) has been demonstrated as a promising strategy to improve siRNA delivery, which will change the low-charge and rigid properties of single siRNA and enhance its electrostatic interactions with cationic polymers. For such polymerization strategy, a major breakthrough is still needed to fully eliminate chemical processes and further improve the nanocomplex-forming ability of polymerized siRNAs. Herein, the extremely strong interaction between the DNA product of rolling circle amplification (RCA) and linear poly(ether imide) (PEI) has been disclosed; accordingly, a stable nanocomplex is formed just at its charge neutralization point, which benefits from the high molecular weight of the RCA product (>3 000 000 Da). In addition, as the sequence of the RCA product is determined by the cyclic template, the programmable nature of DNA can simplify the optimization process and maximize the hybridization efficiency between RCA and sticky siRNAs, realizing a superior siRNA polymerization efficiency. Depending on these two effects, the RCA DNA is utilized as a cocarrier material to organize siRNA polymerization and substantially reduce the usage amount of PEI, which greatly improves RNAi efficiency of PEI/RCA-siRNA polyplex both in vitro and in vivo, providing evidence that RCA DNA is a promising material to promote the RNAi-based therapeutics.

Photosensing System Using Photosystem I and Gold Nanoparticle on Graphene Field-Effect Transistor.

In this study, a light sensor is fabricated based on photosystem I (PSI) and a graphene field-effect transistor (FET) that detects light at a high quantum yield under ambient conditions. We immobilized PSI on a micrometer-sized graphene FET using Au nanoparticles (AuNPs) and measured the I-V characteristics of the modified graphene FET before and after light irradiation. The source-drain current (Isd) increased upon illumination, exhibiting a photoresponsivity of 4.8 × 102 A W-1, and the charge neutrality point of graphene shifted by -12 mV. This system represents the first successful photosensing system based on proteins and a solution-gated graphene FET. The probable mechanism of this negative shift can be explained by the increase in negative charge carriers in graphene induced by a hole trap in the AuNP resulting from electron transfer from the AuNP to PSI. Photoresponses were only observed in the presence of two surface-active agents, n-hexyltrimethylammonium bromide and sodium dodecylbenzenesulfonate, because they caused the formation of a hydrophobic environment on the surface of the graphene. The lipid layer of these agents caused dissociation of ascorbate ions from the graphene sheet, thereby expanding the Debye screening length of the electrolyte solution. The hydrophobic environment above graphene also enhanced hole storage in the AuNP through electron transfer from the AuNP to PSI.

The role of charge transfer at reduced graphene oxide/organic semiconductor interface on the charge transport properties

The effect of 1-pyrenesulfonicacid sodium salt (1-PSA), tetracyanoethylene (TCNE) and tetrafluoro-tetracyanoquinodimethane (F4-TCNQ) on charge transport properties of reduced graphene oxide (RGO) is examined by measuring the transfer characteristics of field-effect transistors and co-planar time-of-flight photocurrent technique. Evidence of p-type doping and a reduction of mobility of electrons in RGO upon deposition of these materials is observed. Time-resolved photocurrent measurements show a reduction in electron mobility even at submonolayer coverage of these materials. The variation of transit time with different coverages reveals that electron mobility decreases with increasing the surface coverage of 1-PSA, TCNE and F4-TCNQ to a certain extent, while at higher coverage the electron mobility is slightly recovered. All three molecules show the same trend in charge carrier mobility variation with coverage, but with different magnitude. Among all three molecules, 1-PSA acts as weak electron acceptor compared to TCNE and F4-TCNQ. The additional fluorine moieties in F4-TCNQ provides excellent electron withdrawing capability compared to TCNE. The experimental results are consistent with the density functional theory calculations. • RGO FETs, exhibit a positive shift of the charge-neutrality point due to deposition of organic semiconductor layer. • The amount of shift varies with the molecule electron affinity. • The electron mobility is quenched by the presence of F4-TCNQ and TCNE, while 1-PSA don’t affect the electron mobility. • With increasing the coverage of 1-PSA, the electron mobility drops and then slightly recovers at higher coverages. • The change in the electron mobility is due to effect of teh RGO/organic-layer interface dipole field.

Valence Bond Orders at Charge Neutrality in a Possible Two-Orbital Extended Hubbard Model for Twisted Bilayer Graphene.

An extended Hubbard model on a honeycomb lattice with two orbitals per site at charge neutrality is investigated with unbiased large-scale quantum MonteCarlo simulations. The Fermi velocity of the Dirac fermions is renormalized as the cluster charge interaction increases, until a mass term emerges and a quantum phase transition from Dirac semimetal to valence bond solid (VBS) insulator is established. The quantum critical point is discovered to belong to the 3D N=4 Gross-Neveu chiral XY universality with the critical exponents obtained at high precision. Further enhancement of the interaction drives the system into two different VBS phases, the properties and transition between them are also revealed. Since the model is related to magic-angle twisted bilayer graphene, our results may have relevance towards the symmetry breaking order at the charge neutrality point of the material, and associate the wide range of universal strange metal behavior around it with quantum critical fluctuations.

Nanoscale graphene Hall sensors for high-resolution ambient magnetic imaging

A major challenge to routine non-invasive, nanoscale magnetic imaging is the development of Hall sensors that are stable under ambient conditions and retain low minimum detectable fields down to nanoscale dimensions. To address these issues we have fabricated and characterised chemical vapour deposition (CVD) graphene Hall sensors with wire widths between 50 nm and 1500 nm, in order to exploit the high carrier mobility and tuneability of this material. The measured Hall voltage noise is in good agreement with theoretical models and we demonstrate that minimum detectable fields at fixed drive current are lowest in the vicinity of the charge neutrality point. Our best performing deep sub-micron sensors, based on a wire width of 85 nm, display the excellent room temperature resolution of 59 µT/√Hz at a dc drive current of 12 µA and measurement frequency of 531 Hz. We observe a weak increase in minimum detectable field as the active sensor area is reduced while the Hall offset field is largely independent of size. These figures-of-merit significantly surpass prior results on larger probes in competing materials systems, with considerable scope for further optimisation. Our results clearly demonstrate the feasibility of using CVD graphene to realise very high spatial resolution nanosensors for quantitative room temperature magnetic imaging.