High-temperature Molecular Beam Epitaxy Research Articles

High-temperature Brown-Zak oscillations in graphene/hBN moiré field effect transistor fabricated using molecular beam epitaxy

Graphene placed on hexagonal boron nitride (hBN) has received significant interest due to its excellent electrical performance and physics phenomena, such as superlattice Dirac points. Direct molecular beam epitaxy growth of graphene on hBN offers an alternative fabrication route for hBN/graphene devices. Here, we investigate the electronic transport of moiré field effect transistors (FETs) in which the conducting channel is monolayer graphene grown on hexagonal boron nitride by high temperature molecular beam epitaxy (HT-MBE). Alignment between hBN and HT-MBE graphene crystal lattices gives rise to a moiré-fringed hexagonal superlattice pattern. Its electronic band structure takes the form of a “Hofstadter butterfly”. When a strong magnetic field B is applied perpendicular to the graphene layer, the electrical conductance displays magneto-oscillations, periodic in B−1, over a wide range of gate voltages and temperatures up to 350 K. We attribute this behaviour to the quantisation of electronic charge and magnetic flux within each unit cell of the superlattice, which gives rise to so-called Brown-Zak oscillations, previously reported only in high-mobility exfoliated graphene. Thus, this HT-MBE graphene/hBN heterostructure provides a platform for observation of room temperature quantum effects and device applications.

Growth kinetics and substrate stability during high-temperature molecular beam epitaxy of AlN nanowires

We study the molecular beam epitaxy of AlN nanowires between 950 °C and 1215 °C, well above the usual growth temperatures, to identify optimal growth conditions. The nanowires are grown by self-assembly on TiN(111) films sputtered onto Al2O3. Above 1100 °C, the TiN film is seen to undergo grain growth and its surface exhibits {111} facets where AlN nucleation preferentially occurs. Modeling of the nanowire elongation rate measured at different temperatures shows that the Al adatom diffusion length maximizes at 1150 °C, which appears to be the optimum growth temperature. However, analysis of the nanowire luminescence shows a steep increase in the deep-level signal already above 1050 °C, associated with O incorporation from the Al2O3 substrate. Comparison with AlN nanowires grown on Si, MgO and SiC substrates suggests that heavy doping of Si and O by interdiffusion from the TiN/substrate interface increases the nanowire internal quantum efficiency, presumably due to the formation of a SiN x or AlO x passivation shell. The outdiffusion of Si and O would also cause the formation of the inversion domains observed in the nanowires. It follows that for optoelectronic and piezoelectric applications, optimal AlN nanowire ensembles should be prepared at 1150 °C on TiN/SiC substrates and will require an ex situ surface passivation.

Graphene nanoribbons with hBN passivated edges grown by high-temperature molecular beam epitaxy

Integration of graphene and hexagonal boron nitride (hBN) in lateral heterostructures has provided a route to broadly engineer the material properties by quantum confinement of electrons or introduction of novel electronic and magnetic states at the interface. In this work we demonstrate lateral heteroepitaxial growth of graphene nanoribbons (GNRs) passivated by hBN using high-temperature molecular beam epitaxy (HT-MBE) to grow graphene in oriented hBN trenches formed ex-situ by catalytic nanoparticle etching. High-resolution atomic force microscopy (AFM) reveals that GNRs grow epitaxially from the etched hBN edges, and merge to form a GNR network passivated by hBN. Using conductive AFM we probe the nanoscale electrical properties of the nanoribbons and observe quasiparticle interference patterns caused by intervalley scattering at the graphene/hBN interface, which carries implications for the potential transport characteristics of hBN passivated GNR devices.

A Platform for Addressing Individual Magnetite Islands Grown Epitaxially on Ru(0001) and Manipulating Their Magnetic Domains.

We have grown high-quality magnetite micrometric islands on ruthenium stripes on sapphire through a combination of magnetron sputtering (Ru film), high-temperature molecular beam epitaxy (oxide islands), and optical lithography. The samples have been characterized by atomic force microscopy, Raman spectroscopy, X-ray absorption and magnetic circular dichroism in a photoemission microscope. The magnetic domains on the magnetite islands can be modified by the application of current pulses through the Ru stripes in combination with magnetic fields. The modification of the magnetic domains is explained by the Oersted field generated by the electrical current flowing through the stripes underneath the magnetite nanostructures. The fabrication method is applicable to a wide variety of rock salt and spinel oxides.

Epitaxy of boron nitride monolayers for graphene-based lateral heterostructures

Monolayers of hexagonal boron nitride (hBN) are grown on graphite substrates using high-temperature molecular beam epitaxy (HT-MBE). The hBN monolayers are observed to grow predominantly from step edges on the graphite surface and exhibit a strong dependence of the morphology, including the dominant crystallographic edge, of the hBN monolayers, on the growth temperature, as well as systematic variations in growth rate and coverage, and significant differences in the growth at monolayer and multilayer graphite steps. At graphite monolayer steps hBN grows laterally across the surface on the lower terrace, but hBN growth on the upper side of the graphite step is more limited and is nucleated by three-dimensional clusters. Multilayer graphite steps exhibit a much higher density of non-planar hBN aggregates and growth on both the upper and lower terraces occurs. The results show that the hBN monolayer growth edge type, hBN island shape and the presence of hBN aggregates can be controlled in HT-MBE, with the highest quality layers grown at a substrate temperature of about 1390 °C. Sequential HT-MBE growth of hBN, graphene (G) and a second cycle of hBN growth results in the formation of monolayer thick lateral hBN–G–hBN heterostructures, in which a strip of G is embedded between monolayers of hBN.

Step-flow growth of graphene-boron nitride lateral heterostructures by molecular beam epitaxy

Integration of graphene and hexagonal boron nitride (hBN) into lateral heterostructures has drawn focus due to the ability to broadly engineer the material properties. Hybrid monolayers with tuneable bandgaps have been reported, while the interface itself possesses unique electronic and magnetic qualities. Herein, we demonstrate lateral heteroepitaxial growth of graphene and hBN by sequential growth using high-temperature molecular beam epitaxy (MBE) on highly oriented pyrolytic graphite (HOPG). We find, using scanning probe microscopy, that graphene growth nucleates at hBN step edges and grows across the surface to form nanoribbons with a controlled width that is highly uniform across the surface. The graphene nanoribbons grow conformally from the armchair edges of hexagonal hBN islands forming multiply connected regions with the growth front alternating from armchair to zigzag in regions nucleated close to the vertices of hexagonal hBN islands. Images with lattice resolution confirm a lateral epitaxial alignment between the hBN and graphene nanoribbons, while the presence of a moiré pattern within the ribbons indicates that some strain relief occurs at the lateral heterojunction. These results demonstrate that high temperature MBE is a viable route towards integrating graphene and hBN in lateral heterostructures.

Strain-free ultrathin AlN epilayers grown directly on sapphire by high-temperature molecular beam epitaxy

High-quality AlN ultrathin films on sapphire substrate were grown by molecular beam epitaxy using an in situ high-temperature annealing approach. From transmission electron microscopy studies, it was found that the AlN epilayers are strain relaxed within the first nm, thus growing nearly strain free. Many of the dislocations generated at the AlN/sapphire interface are reduced within the first 50 nm of growth. Epitaxial films grown directly on sapphire, which are ∼100 nm thick, show X-ray diffraction (002) and (102) rocking curve peaks with full widths at half maximum of less than 150 and 1400 arc sec, respectively, which are the narrowest linewidths reported for AlN of this thickness. Detailed photoluminescence studies further showed that such AlN epilayers exhibit relatively high luminescence efficiency and strong near-band edge emission without defect-related transitions.

Development of thermoelectric thin films and characterization methods

This work reports on the fabrication of thin films of inorganic thermoelectric materials like borides, germanides, manganese compounds, and characterization of their thermoelectric properties. We have utilized a unique high temperature molecular beam epitaxy (MBE) apparatus to grow hexaboride thin films and manganese germanides. Magnetic manganese based alloy thin films were also grown using sputtering, since we are interested in the possibilities of utilizing magnetism to develop thermoelectric materials.

Direct band-gap crossover in epitaxial monolayer boron nitride

Hexagonal boron nitride is a large band-gap insulating material which complements the electronic and optical properties of graphene and the transition metal dichalcogenides. However, the intrinsic optical properties of monolayer boron nitride remain largely unexplored. In particular, the theoretically expected crossover to a direct-gap in the limit of the single monolayer is presently not confirmed experimentally. Here, in contrast to the technique of exfoliating few-layer 2D hexagonal boron nitride, we exploit the scalable approach of high-temperature molecular beam epitaxy to grow high-quality monolayer boron nitride on graphite substrates. We combine deep-ultraviolet photoluminescence and reflectance spectroscopy with atomic force microscopy to reveal the presence of a direct gap of energy 6.1 eV in the single atomic layers, thus confirming a crossover to direct gap in the monolayer limit.

Rotationally aligned hexagonal boron nitride on sapphire by high-temperature molecular beam epitaxy

Hexagonal boron nitride (hBN) has been grown on sapphire substrates by ultra-high temperature molecular beam epitaxy (MBE). A wide range of substrate temperatures and boron fluxes have been explored, revealing that high crystalline quality hBN layers are grown at high substrate temperatures, $>$1600$^\circ$C, and low boron fluxes, $\sim1\times10^{-8}$ Torr beam equivalent pressure. \emph{In-situ} reflection high energy electron diffraction (RHEED) revealed the growth of hBN layers with $60^\circ$ rotational symmetry and the $[11\bar20]$ axis of hBN parallel to the $[1\bar100]$ axis of the sapphire substrate. Unlike the rough, polycrystalline films previously reported, atomic force microscopy (AFM) and transmission electron microscopy (TEM) characterization of these films demonstrate smooth, layered, few-nanometer hBN films on a nitridated sapphire substrate. This demonstration of high-quality hBN growth by MBE is a step towards its integration into existing epitaxial growth platforms, applications, and technologies.

An atomic carbon source for high temperature molecular beam epitaxy of graphene

We report the use of a novel atomic carbon source for the molecular beam epitaxy (MBE) of graphene layers on hBN flakes and on sapphire wafers at substrate growth temperatures of ~1400 °C. The source produces a flux of predominantly atomic carbon, which diffuses through the walls of a Joule-heated tantalum tube filled with graphite powder. We demonstrate deposition of carbon on sapphire with carbon deposition rates up to 12 nm/h. Atomic force microscopy measurements reveal the formation of hexagonal moiré patterns when graphene monolayers are grown on hBN flakes. The Raman spectra of the graphene layers grown on hBN and sapphire with the sublimation carbon source and the atomic carbon source are similar, whilst the nature of the carbon aggregates is different - graphitic with the sublimation carbon source and amorphous with the atomic carbon source. At MBE growth temperatures we observe etching of the sapphire wafer surface by the flux from the atomic carbon source, which we have not observed in the MBE growth of graphene with the sublimation carbon source.

Deep ultraviolet emission in hexagonal boron nitride grown by high-temperature molecular beam epitaxy

We investigate the opto-electronic properties of hexagonal boron nitride grown by high temperature plasma-assisted molecular beam epitaxy. We combine atomic force microscopy, spectroscopic ellipsometry, and photoluminescence spectroscopy in the deep ultraviolet to compare the quality of hexagonal boron nitride grown either on sapphire or highly oriented pyrolytic graphite. For both substrates, the emission spectra peak at 235 nm, indicating the high optical quality of hexagonal boron nitride grown by molecular beam epitaxy. The epilayers on highly oriented pyrolytic graphite demonstrate superior performance in the deep ultraviolet (down to 210 nm) compared to those on sapphire. These results reveal the potential of molecular beam epitaxy for the growth of hexagonal boron nitride on graphene, and more generally, for fabricating van der Waals heterostructures and devices by means of a scalable technology.

Hexagonal Boron Nitride Tunnel Barriers Grown on Graphite by High Temperature Molecular Beam Epitaxy

We demonstrate direct epitaxial growth of high-quality hexagonal boron nitride (hBN) layers on graphite using high-temperature plasma-assisted molecular beam epitaxy. Atomic force microscopy reveals mono- and few-layer island growth, while conducting atomic force microscopy shows that the grown hBN has a resistance which increases exponentially with the number of layers, and has electrical properties comparable to exfoliated hBN. X-ray photoelectron spectroscopy, Raman microscopy and spectroscopic ellipsometry measurements on hBN confirm the formation of sp2-bonded hBN and a band gap of 5.9 ± 0.1 eV with no chemical intermixing with graphite. We also observe hexagonal moiré patterns with a period of 15 nm, consistent with the alignment of the hBN lattice and the graphite substrate.

Strain-Engineered Graphene Grown on Hexagonal Boron Nitride by Molecular Beam Epitaxy.

Graphene grown by high temperature molecular beam epitaxy on hexagonal boron nitride (hBN) forms continuous domains with dimensions of order 20 μm, and exhibits moiré patterns with large periodicities, up to ~30 nm, indicating that the layers are highly strained. Topological defects in the moiré patterns are observed and attributed to the relaxation of graphene islands which nucleate at different sites and subsequently coalesce. In addition, cracks are formed leading to strain relaxation, highly anisotropic strain fields, and abrupt boundaries between regions with different moiré periods. These cracks can also be formed by modification of the layers with a local probe resulting in the contraction and physical displacement of graphene layers. The Raman spectra of regions with a large moiré period reveal split and shifted G and 2D peaks confirming the presence of strain. Our work demonstrates a new approach to the growth of epitaxial graphene and a means of generating and modifying strain in graphene.

High temperature MBE of graphene on sapphire and hexagonal boron nitride flakes on sapphire

The discovery of graphene and its remarkable electronic properties has provided scientists with a revolutionary material system for electronics and optoelectronics. Here, the authors investigate molecular beam epitaxy (MBE) as a growth method for graphene layers. The standard dual chamber GENxplor has been specially modified by Veeco to achieve growth temperatures of up to 1850 °C in ultrahigh vacuum conditions and is capable of growth on substrates of up to 3 in. in diameter. To calibrate the growth temperatures, the authors have formed graphene on the Si-face of SiC by heating wafers to temperatures up to 1400 °C and above. To demonstrate the scalability, the authors have formed graphene on SiC substrates with sizes ranging from 10 × 10 mm2 up to 3-in. in diameter. The authors have used a carbon sublimation source to grow graphene on sapphire at substrate temperatures between 1000 and 1650 °C (thermocouple temperatures). The quality of the graphene layers is significantly improved by growing on hexagonal boron nitride (h-BN) substrates. The authors observed a significant difference in the sticking coefficient of carbon on the surfaces of sapphire and h-BN flakes. Our atomic force microscopy measurements reveal the formation of an extended hexagonal moiré pattern when our MBE layers of graphene on h-BN flakes are grown under optimum conditions. The authors attribute this moiré pattern to the commensurate growth of crystalline graphene on h-BN.

Low defect-mediated reverse-bias leakage in (0001) GaN via high-temperature molecular beam epitaxy

Conductive atomic force microscopy, scanning electron microscopy, and x-ray diffraction were used to determine the effects of Ga/N flux ratio on the conductivity of current leakage paths in GaN grown by molecular beam epitaxy. Our data reveal a band of fluxes near Ga/N≈1 for which these pathways ceased to be observable. We conclude that changes in surface defects surrounding or impurities along screw-component threading dislocations are responsible for their conductive nature. These observations suggest a method for controlling the primary source of reverse-bias Schottky contact leakage in n-type GaN grown by molecular beam epitaxy.

Ultrahigh Strength Single Crystalline Nanowhiskers Grown by Physical Vapor Deposition

The strength of metal crystals is reduced below the theoretical value by the presence of dislocations or by flaws that allow easy nucleation of dislocations. A straightforward method to minimize the number of defects and flaws and to presumably increase its strength is to increase the crystal quality or to reduce the crystal size. Here, we describe the successful fabrication of high aspect ratio nanowhiskers from a variety of face-centered cubic metals using a high temperature molecular beam epitaxy method. The presence of atomically smooth, faceted surfaces and absence of dislocations is confirmed using transmission electron microscopy investigations. Tensile tests performed in situ in a focused-ion beam scanning electron microscope on Cu nanowhiskers reveal strengths close to the theoretical upper limit and confirm that the properties of nanomaterials can be engineered by controlling defect and flaw densities.

Growth and magnetic properties of zb-type MnAs films on GaAs substrates by high-temperature MBE

We have grown MnAs films on GaAs(1 1 1)B substrates by high-temperature molecular beam epitaxy (MBE) and have investigated their crystal structures and magnetic properties. X-ray diffraction (XRD) and grazing incidence X-ray diffraction (GIXD) results showed that two kinds of zb-type MnAs films with lattice constants of 5.73 and 5.96 Å were grown. The zb-type MnAs films show higher Curie temperature than 350 K and larger magnetization than the reported zb-type MnAs. At the initial stage of MnAs growth, Ga 1− x Mn x As was grown and this Ga 1− x Mn x As layer might play an important role of a buffer layer to enable the zb-MnAs growth.

Gallium desorption behavior at AlGaAs/GaAs heterointerfaces during high-temperature molecular beam epitaxy

A Monte Carlo simulation study is performed to investigate the Ga desorption behavior during AlGaAs-on-GaAs heterointerface formation by molecular beam epitaxy. The transients in the Ga desorption rate upon opening the Al shutter are shown to be associated with the concurrent reduction in the V/III flux ratio. Monte Carlo simulations employing a constant V/III flux ratio yield a “steplike” variation in the Ga desorption rate with the resulting interfaces closer in abruptness to the ideal AlGaAs-on-GaAs interface. Further details on the stoichiometry of the interface and its relationship with predicted Ga desorption profiles is presented.

High-resistivity GaAs grown by high-temperature molecular-beam epitaxy

It is shown that when grown by molecular-beam epitaxy at high temperatures around 700 °C, undoped GaAs layers display high resistivity. Preliminary results seem to imply that Ga-related inclusions that produce internal Schottky diodes might be responsible for this effect rather than the presence of deep centers. It is proposed that Ga-related inclusions that produce internal Schottky diodes might possibly be responsible for this effect rather than the presence of deep centers.