Boron Nitride Substrate Research Articles

Kinetics of monolayer MoS2-encapsulated nanobubbles on hexagonal boron nitride substrates

Understanding the kinetics of nanobubbles encapsulated by ultrathin two-dimensional (2D) layered van der Waals crystal membranes on atomically flat substrates is important to the applications of 2D materials and the pursuit of 2D nanobubble technologies. Here, we investigate the controlled motion of monolayer molybdenum disulfide (MoS2)-encapsulated nanobubbles on flat hexagonal boron nitride substrates using atomic force microscopy (AFM). Our study reveals a distinct transition from standstill bubble deformations to stable, stepwise bubble translations on flat substrates. The membrane tension-dominated 2D nanobubble behaves like an elastic soft body in its collision interaction with the AFM tip. This delicate motion-control technique enables neighboring 2D nanobubbles to move closer and eventually coalesce into larger nanobubbles. These findings pave the way for high-precision manipulation of nanobubbles and facilitate the exploration of their emerging applications.

Transport properties of multilayer NbxMo1−xS2/MoS2 in-plane heterostructure tunnel FETs on hexagonal boron nitride substrate

In-plane heterostructures based on transition metal dichalcogenides are promising for applications in tunnel field-effect transistors (TFETs). However, the transport properties of the in-plane heterostructures have not been fully understood due to the presence of generation current derived from the in-gap state of the heterointerface. For further performance improvement, it is important to identify and suppress the origin of the in-gap states at the heterointerface. In this work, we investigated the transport properties of TFETs based on multilayer NbxMo1−xS2/MoS2 in-plane heterostructures on atomically flat hexagonal boron nitride substrate. We observed a transition from staggered gap to broken gap band alignment by electron doping to MoS2 and that band-to-band tunneling current was dominant below 80 K, a higher temperature compared with the heterostructure on an SiO2 surface. These results indicate that the use of atomically flat substrates helps reduce generation current from strain-derived in-gap states in NbxMo1−xS2/MoS2 in-plane heterostructures.

Bilayer C60 Polymer/h-BN Heterostructures: A DFT Study of Electronic and Optic Properties.

Interest in fullerene-based polymer structures has renewed due to the development of synthesis technologies using thin C60 polymers. Fullerene networks are good semiconductors. In this paper, heterostructure complexes composed of C60 polymer networks on atomically thin dielectric substrates are modeled. Small tensile and compressive deformations make it possible to ensure appropriate placement of monolayer boron nitride with fullerene networks. The choice of a piezoelectric boron nitride substrate was dictated by interest in their applicability in mechanoelectric, photoelectronic, and electro-optical devices with the ability to control their properties. The results we obtained show that C60 polymer/h-BN heterostructures are stable compounds. The van der Waals interaction that arises between them affects their electronic and optical properties.

Role of carbon substitutional and vacancy in tailoring the H2 adsorption energy over a hexagonal boron nitride monolayer: an ab initio study

The effect of the substitutional and vacancy type defects on the H2 adsorption energy over a monolayer hexagonal boron nitride (h-BN) substrate has been studied by using the van der Waals density functional theory calculations. Carbon doping at the boron site or formation of boron vacancy can be an effective way to increase the adsorption energy value of a pristine h-BN substrate. The repulsive lateral interaction present in between the two H2 molecules plays a vital role in case of multiple H2 molecule adsorption over the substrate. Also, the carbon cluster formation during doping can have a favorable effect in the overall storage capacity of the h-BN substrate.

Spatial shifts of reflected rotating elliptical Gaussian beams from surface phonon polaritons in hyperbolic materials

The effect of surface phonon polaritons (SPhPs) on Goos-Hänchen (GH) and Imbert-Fedorov (IF) shifts of reflected rotating elliptical Gaussian beams (REGBs) is investigated in the Otto configuration with a naturally hyperbolic material (NHM) substrate. The spatial shifts are enhanced significantly and adjusted by tuning the REGBs and the optical axis orientation of NHM. The magnitude of GH and IF shifts is easily evaluated by timing the elliptical parameter b02 on the basis of the spatial shift at b0=1.0 when η(=a0/b0)≥2.0. The attenuation total reflection (ATR) spectra are simulated for a hexagonal boron nitride (hBN) substrate. To better understand the impact of SPhPs on the GH and IF shifts, the dispersion curves of SPhPs are calculated. The features of GH and IF shifts around SPhPs can be observed through the frequency scanning along the dispersion curves at a fixed incident angle. The comparison between the ATR spectra and the dispersion curves demonstrates that the enhancement of GH and IF shifts with higher reflection always occurs in the reststrahlen bands (RBs) of NHM once SPhPs are excited. In RB-I, the magnitudes of GH and IF shifts attributable to the SPhPs are located between the peak and dip of a shift curve within a very narrow frequency region. However, in RB-II, the positive maximum values of GH and IF shifts just coincide with the SPhPs. As a result, it is predicted that a relatively large spatial shift will be observed along the frequency scanning line. The large shifts accompanied by the higher reflection may show potential applications in optical or optoelectronic technologies.

High-Field Electron Transport and High Saturation Velocity in Multilayer Indium Selenide Transistors.

Creating a high-frequency electron system demands a high saturation velocity (υsat). Herein, we report the high-field transport properties of multilayer van der Waals (vdW) indium selenide (InSe). The InSe is on a hexagonal boron nitride substrate and encapsulated by a thin, noncontinuous In layer, resulting in an impressive electron mobility reaching 2600 cm2/(V s) at room temperature. The high-mobility InSe achieves υsat exceeding 2 × 107 cm/s, which is superior to those of other gapped vdW semiconductors, and exhibits a 50-60% improvement in υsat when cooled to 80 K. The temperature dependence of υsat suggests an optical phonon energy (ℏωop) for InSe in the range of 23-27 meV, previously reported values for InSe. It is also notable that the measured υsat values exceed what is expected according to the optical phonon emission model due to weak electron-phonon scattering. The superior υsat of our InSe, despite its relatively small ℏωop, reveals its potential for high-frequency electronics, including applications to control cryogenic quantum computers in close proximity.

Tuning Landau level gap in bilayer graphene on polar substrates

We study the effect of carrier interactions with surface optical phonons on the band properties of graphene bilayers induced by polar substrates within the presence of a magnetic field. Employing an analytical method grounded in Lee-Low-Pines theory, we calculate the Hamiltonian spectrum of the Fröhlich type. Our primary focus is on the examination of the alteration in the band gap within the zero-energy Landau level, arising from the substrate’s polaron effect. This gap assumes significance when utilizing hexagonal boron nitride (h-BN) substrates, manifesting a 50 meV deviation compared to graphene sheet. The present work reports the tunability of the energy gap by manipulating substrate polarization and controlling the separation distance between the graphene bilayer and the polar substrate. This tunability is ascribed to the interaction between charge carriers and surface optical phonons, resulting in discernible changes in the band properties of the graphene bilayer.

Multiresistance states in ferro- and antiferroelectric trilayer boron nitride

Stacking two atomic layers together can induce interlayer (sliding) ferroelectricity that is absent in their naturally occurring crystal forms. With the flexibility of two-dimensional materials, more layers could be assembled to give rise to even richer polarization states. Here, we show that three-layer boron nitride can host ferro- and antiferroelectric domains in the same sample. When used as a tunneling junction, the polarization of these domains could be switched in a layer-by-layer procedure, producing multiple resistance states. Theoretical investigation reveals an important role played by the interaction between the trilayer boron nitride and graphene substrate. These findings reveal the great potential and unique properties of 2D sliding ferroelectric materials.

Origin of dielectric polarization suppression in confined water from first principles.

It has long been known that the dielectric constant of confined water should be different from that in bulk. Recent experiments have shown that it is vanishingly small, however the origin of the phenomenon remains unclear. Here we used ab initio molecular dynamics simulations (AIMD) and AIMD-trained machine-learning potentials to understand water's structure and electronic properties underpinning this effect. For the graphene and hexagonal boron-nitride substrates considered, we find that it originates in the spontaneous anti-parallel alignment of the water dipoles in the first two water layers near the solid interface. The interfacial layers exhibit net ferroelectric ordering, resulting in an overall anti-ferroelectric arrangement of confined water. Together with constrained hydrogen-bonding orientations, this leads to much reduced out-of-plane polarization. Furthermore, we directly contrast AIMD and simple classical force-field simulations, revealing important differences. This work offers insight into a property of water that is critical in modulating surface forces, the electric-double-layer formation and molecular solvation, and shows a way to compute it.

Molecular dynamics simulation on the dielectric properties of water confined in a nanospace between graphene and a h-BN substrate

Using a molecular dynamics simulation, we theoretically investigate the dielectric response of confined water intruded between graphene and a hexagonal boron nitride (h-BN) substrate. The dielectric constant of confined water with a thickness of 1 nm is only ε r ∼ 2, which is much smaller than that of bulk water ( εrbulk=72.89 ). As the thickness h increases, ε r begins to increase as well when h exceeds a few nanometers and then approaches εrbulk . The results of rotational autocorrelation functions suggest that the dielectric constant of the confined water is small because of the limited rotational degrees of freedom of the water on the graphene and h-BN substrate surfaces. In addition, the saturation electric field of the confined water with h < 100 nm is much higher than the breakdown electric field of the h-BN substrate (0.7 V/nm).

Tip Growth of Quasi-Metallic Bilayer Graphene Nanoribbons with Armchair Chirality.

Graphene nanoribbons (GNRs), quasi one-dimensional (1D) narrow strips of graphene, have shown promise for high-performance nanoelectronics due to their exceptionally high carrier mobility and structurally tunable bandgaps. However, producing chirality-uniform GNRs on insulating substrates remains a big challenge. Here, we report the successful growth of bilayer GNRs with predominantly armchair chirality and ultranarrow widths (<5 nm) on insulating hexagonal boron nitride (h-BN) substrates using chemical vapor deposition (CVD). The growth of GNRs is catalyzed by transition metal nanoparticles, including Fe, Co, and Ni, through a unique tip-growth mechanism. Notably, GNRs catalyzed by Ni exhibit a high purity (97.3%) of armchair chirality. Electron transport measurements indicate that the ultrathin bilayer armchair GNRs exhibit quasi-metallic behavior. This quasi-metallicity is further supported by density functional theory (DFT) calculations, which reveal a significantly reduced bandgap in bilayer armchair GNRs. The chirality-specific GNRs reported here offer promising advancements for the application of graphene in nanoelectronics.

Sharp zero-phonon lines of single organic molecules on a hexagonal boron-nitride surface

Single fluorescent molecules embedded in the bulk of host crystals have proven to be sensitive probes of the dynamics in their nano environment, thanks to their narrow (about 30–50 MHz or 0.1–0.2 μeV) optical linewidth of the 0-0 zero-phonon line (0-0 ZPL) at cryogenic temperatures. However, the optical linewidths of the 0-0 ZPL have been found to increase dramatically as the single molecules are located closer to a surface or interface, while no 0-0 ZPL has been detected for single molecules on any surface. Here we study single terrylene molecules adsorbed on the surface of hexagonal boron-nitride (hBN) substrates. Our low-temperature results show that it is possible to observe the 0-0 ZPL of fluorescent molecules on a surface. We compare our results for molecules deposited on the surfaces of annealed and non-annealed hBN flakes and we see a marked improvement in the spectral stability of the emitters after annealing.

Low Ohmic contact resistance and high on/off ratio in transition metal dichalcogenides field-effect transistors via residue-free transfer.

Beyond-silicon technology demands ultrahigh performance field-effect transistors. Transition metal dichalcogenides provide an ideal material platform, but the device performances such as the contact resistance, on/off ratio and mobility are often limited by the presence of interfacial residues caused by transfer procedures. Here, we show an ideal residue-free transfer approach using polypropylene carbonate with a negligible residue coverage of ~0.08% for monolayer MoS2 at the centimetre scale. By incorporating a bismuth semimetal contact with an atomically clean monolayer MoS2 field-effect transistor on hexagonal boron nitride substrate, we obtain an ultralow Ohmic contact resistance of ~78 Ω µm, approaching the quantum limit, and a record-high on/off ratio of ~1011 at 15 K. Such an ultra-clean fabrication approach could be the ideal platform for high-performance electrical devices using large-area semiconducting transition metal dichalcogenides.

Collective States in Molecular Monolayers on 2D Materials.

Collective excited states form in organic two-dimensional layers through Coulomb coupling of the molecular transition dipole moments. They manifest as characteristic strong and narrow peaks in the excitation and emission spectra that are shifted to lower energies compared with the monomer transition. We study experimentally and theoretically how robust the collective states are against homogeneous and inhomogeneous broadening, as well as spatial disorder that occurs in real molecular monolayers. Using a microscopic model for a two-dimensional dipole lattice in real space, we calculate the properties of collective states and their extinction spectra. We find that the collective states persist even for 1-10% random variation in the molecular position and in the transition frequency, with a peak position and integrated intensity similar to those for the perfectly ordered system. We measured the optical response of a monolayer of the perylene derivative MePTCDI on two-dimensional materials. On the wide-band-gap insulator hexagonal boron nitride, it shows strong emission from the collective state with a line width that is dominated by the inhomogeneous broadening of the molecular state. When the semimetal graphene is used as a substrate, however, the luminescence is completely quenched. By combining optical absorption, luminescence, and multiwavelength Raman scattering, we verify that the MePTCDI molecules form very similar collective monolayer states on hexagonal boron nitride and graphene substrates, but on graphene the line width is dominated by nonradiative excitation transfer from the molecules to the substrate. Our study highlights the transition from the localized molecular state of the monomer to a delocalized collective state in the two-dimensional molecular lattice that is entirely based on Coulomb coupling between optically active excitations of the electrons and molecular vibrations. The excellent properties of organic monolayers make them promising candidates for components of soft-matter optoelectronic devices.

Insulators at fractional fillings in twisted bilayer graphene partially aligned to hexagonal boron nitride

At partial fillings of its flat electronic bands, magic-angle twisted bilayer graphene (MATBG) hosts a rich variety of competing correlated phases that show sample-to-sample variations. Divergent phase diagrams in MATBG are often attributed to the sublattice polarization energy scale, tuned by the degree of alignment of the hexagonal boron nitride (hBN) substrates typically used in van der Waals devices. Unaligned MATBG exhibits unconventional superconductor and correlated insulator phases, while nearly perfectly aligned MATBG/hBN exhibits zero-field Chern insulating phases and lacks superconductivity. Here we use scanning tunneling microscopy and spectroscopy (STM/STS) to observe gapped phases at partial fillings of the flat bands of MATBG in a new intermediate regime of sublattice polarization, observed when MATBG is only partially aligned (θGr-hBN ≈ 1.65°) to the underlying hBN substrate. Under this condition, MATBG hosts not only phenomena that naturally interpolate between the two sublattice potential limits, but also unexpected gapped phases absent in either of these limits. At charge neutrality, we observe an insulating phase with a small energy gap (Δ &amp;lt; 5 meV) likely related to weak sublattice symmetry breaking from the hBN substrate. In addition, we observe new gapped phases near fractional fillings ν = ±1/3 and ν = ±1/6, which have not been previously observed in MATBG. Importantly, energy-resolved STS unambiguously identifies these fractional filling states to be of single-particle origin, possibly a result of the super-superlattice formed by two moiré superlattices. Our observations emphasize the power of STS in distinguishing single-particle gapped phases from many-body gapped phases in situations that could be easily confused in electrical transport measurements, and demonstrate the use of substrate engineering for modifying the electronic structure of a moiré flat-band material.

Tunable growth of one-dimensional graphitic materials: graphene nanoribbons, carbon nanotubes, and nanoribbon/nanotube junctions

Graphene nanoribbons (GNRs) and carbon nanotubes (CNTs), two representative one-dimensional (1D) graphitic materials, have attracted tremendous research interests due to their promising applications for future high-performance nanoelectronics. Although various methods have been developed for fabrication of GNRs or CNTs, a unified method allowing controllable synthesis of both of them, as well as their heterojunctions, which could largely benefit their nano-electronic applications, is still lacking. Here, we report on a generic growth of 1D carbon using nanoparticles catalyzed chemical vapor deposition (CVD) on atomically flat hexagonal boron nitride (h-BN) substrates. Relative ratio of the yielded GNRs and CNTs is able to be arbitrarily tuned by varying the growth temperature or feeding gas pressures. The tunability of the generic growth is quantitatively explained by a competing nucleation theory: nucleation into either GNRs or CNTs by the catalysts is determined by the free energy of their formation, which is controlled by the growth conditions. Under the guidance of the theory, we further realized growth of GNR/CNT intramolecular junctions through changing H2 partial pressure during a single growth process. Our study provides not only a universal and controllable method for growing 1D carbon nanostructures, but also a deep understanding of their growth mechanism, which would largely benefit future carbon-based electronics and optoelectronics.

Transport evidence of superlattice Dirac cones in graphene monolayer on twisted boron nitride substrate

Strong band engineering in two-dimensional (2D) materials can be achieved by introducing moiré superlattices, leading to the emergence of various novel quantum phases with promising potential for future applications. Presented works to create moiré patterns have been focused on a twist embedded inside channel materials or between channel and substrate. However, the effects of a twist inside the substrate materials on the unaligned channel materials are much less explored. In this work, we report the realization of superlattice multi-Dirac cones with the coexistence of the main Dirac cone in a monolayer graphene (MLG) on a ∼0.14° twisted double-layer boron nitride (tBN) substrate. Transport measurements reveal the emergence of three pairs of superlattice Dirac points around the pristine Dirac cone, featuring multiple metallic or insulating states surrounding the charge neutrality point. Displacement field tunable and electron–hole asymmetric Fermi velocities are indicated from temperature dependent measurements, along with the gapless dispersion of superlattice Dirac cones. The experimental observation of multiple Dirac cones in MLG/tBN heterostructure is supported by band structure calculations employing a periodic moiré potential. Our results unveil the potential of using twisted substrate as a universal band engineering technique for 2D materials regardless of lattice matching and crystal orientations, which might pave the way for a new branch of twistronics.

One-dimensional magnetism and Rashba-like effects in zigzag bismuth nanoribbons

Discoveries of low-dimensional quantum materials have renewed interest in some of the fundamental phenomena, such as magnetism and Rashba-type spin orbit coupling. In particular, exploring these phenomena by themselves and/or in combination within one-dimensional (1D) systems is of interest for fields as disparate as spintronics and biology. For example, a better understanding of Rashba-type spin orbit coupling in 1D systems may be used to explain spin-selective electron transport in long helical molecules. In this paper, using first principle calculations, we show that each edge of a zigzag nanoribbon composed of a bismuth (Bi) bilayer is a truly 1D structure that naturally combines both 1D magnetism and Rashba-type spin orbit coupling in a single system. In particular, we study the combined effects of exchange and spin-orbit coupling in nanoribbons that are: (i) ideal freestanding, (ii) placed on a hexagonal boron nitride substrate, and (iii) decorated with N atoms. The edges of the Bi zigzag NRs can display ferromagnetic, antiferromagnetic, or noncollinear ordering, resulting in a broken quantum spin Hall state. The interplay of Rashba and exchange effects in different magnetic phases can result in different spin-dependent transport regimes.

Wiedemann-Franz law in graphene

We analyze a well-known experimental work [J. Crossno et al., Science 351, 1058 (2016)] which reported on the failure of the Wiedemann-Franz law in graphene at $T\ensuremath{\sim}10\text{--}100\phantom{\rule{4pt}{0ex}}\mathrm{K}$, attributing this failure to the non-Fermi liquid nature of the Dirac fluid associated with undoped intrinsic graphene. In spite of serious theoretical efforts, the reported observations remain unexplained. Our detailed quantitative analysis based on Fermi liquid considerations, which apply to extrinsic doped graphene, establishes that one possible explanation for the reported observations is the opening of a gap at the Dirac point, induced perhaps by the boron nitride substrate. We suggest that more experiments are necessary to resolve the issue, and we believe that the experiment may not actually have anything to do with Dirac fluid hydrodynamics but relates to finite-temperature low-density bipolar diffusive transport by electrons and holes in the presence of short- and long-range disorder, and phonons.

Anomalous optical response of graphene on hexagonal boron nitride substrates

Graphene/hBN heterostructures can be considered as one of the basic building blocks for the next-generation optoelectronics mostly owing to the record-high electron mobilities. However, currently, the studies of the intrinsic optical properties of graphene are limited to the standard substrates (SiO2/Si, glass, quartz) despite the growing interest in graphene/hBN heterostructures. This can be attributed to a challenging task of the determination of hBN’s strongly anisotropic dielectric tensor in the total optical response. In this study, we overcome this issue through imaging spectroscopic ellipsometry utilizing simultaneous analysis of hBN’s optical response with and without graphene monolayers. Our technique allowed us to retrieve the optical constants of graphene from graphene/hBN heterostructures in a broad spectral range of 250–950 nm. Our results suggest that graphene’s absorption on hBN may exceed the one of graphene on SiO2/Si by about 60%.