Low-energy Electron Diffraction Data Research Articles

Self-Assembly of N-Rich Triimidazoles on Ag(111): Mixing the Pleasures and Pains of Epitaxy and Strain.

In the present report, homochiral hydrogen-bonded assemblies of heavily N-doped (C9H6N6) heterocyclic triimidazole (TT) molecules on an Ag(111) substrate were investigated using scanning tunneling microscopy (STM) and low energy electron diffraction (LEED) techniques. The planar and prochiral TT molecules, which exhibit a threefold rotation symmetry and lack mirror symmetry when assembled on the substrate, carry multiple hydrogen-bonding donor and acceptor functionalities, inevitably leading to the formation of hexameric two-dimensionally extended assemblies that can be either homo- (RR/SS) or heterochiral (RS). Experimental STM data showing well-ordered homochiral domains and experimental LEED data are consistent with simulations assuming the R19.1° overlayer on the Ag(111) lattice. Importantly, we report the unexpected coincidence of spontaneous resolution with the condensation of neighboring islands in adjacent "Janus pairs". The islands are connected by a characteristic fault zone, an observation that we discuss in the context of the fairly symmetric molecule and its propensity to compromise and benefit from interisland bonding at the expense of lattice mismatches and strain in the defect zone. We relate this to the close to triangular shape and the substantial but weak bonding scheme beyond van der Waals (vdW) of the TT molecules, which is due to the three N-containing five-membered imidazole rings. Density functional theory (DFT) calculations show clear energetic differences between homochiral and heterochiral pairwise interactions, clearly supporting the experimental results.

Increasing the scan speed in high resolution, low energy electron diffraction measurements by presetting the gate time.

We report on a speed-up data acquisition routine for recording intensities in reciprocal space (k-space) with increased scan speed by a single point detector. It is designed for recording low energy electron diffraction (LEED) data with high resolution by a spot profile analysis LEED instrument. It counteracts the problem of long acquisition times that are encountered when larger areas in the reciprocal space are scanned. It exploits the fact that in typical LEED images of ordered surfaces, more than 90% of the data points in k-space belong to the low-intense background, which is often not of interest. Only about 10% of the data points are related to the relevant diffraction features, namely, the LEED spots. Often it is not necessary to measure the background with the same statistical significance as measuring those points that contain information. The data points belonging to the LEED spots can be discriminated from those of the background by their higher intensities. An acquisition routine that sets an increased gate time for the counting in response to higher intensities thus safeguards good statistics for data points of the LEED spots and saves measurement time when recording data points of the background with small gate times. For typical LEED images, a reduction of the total acquisition time by a factor of about 10 is obtained. We give examples of one- and two-dimensional scans from current experiments, recorded with and without the speed-up routine. We further discuss how the routine supports the measurement of energy dependent reciprocal space maps.

Plasma Functionalization of Silica Bilayer Polymorphs.

Ultrathin silica films are considered suitable two-dimensional model systems for the study of fundamental chemical and physical properties of all-silica zeolites and their derivatives, as well as novel supports for the stabilization of single atoms. In the present work, we report the creation of a new model catalytic support based on the surface functionalization of different silica bilayer (BL) polymorphs with well-defined atomic structures. The functionalization is carried out by means of in situ H-plasma treatments at room temperature. Low energy electron diffraction and microscopy data indicate that the atomic structure of the films remains unchanged upon treatment. Comparing the experimental results (photoemission and infrared absorption spectra) with density functional theory simulations shows that H2 is added via the heterolytic dissociation of an interlayer Si-O-Si siloxane bond and the subsequent formation of a hydroxyl and a hydride group in the top and bottom layers of the silica film, respectively. Functionalization of the silica films constitutes the first step into the development of a new type of model system of single-atom catalysts where metal atoms with different affinities for the functional groups can be anchored in the SiO2 matrix in well-established positions. In this way, synergistic and confinement effects between the active centers can be studied in a controlled manner.

Growth and Properties of Graphene and Graphene Nanoribbons on Ge

The synthesis of graphene directly on Ge and on Ge deposited on Si provides a scalable route toward integrating graphene onto conventional semiconductors. This presentation will first survey the growth modes of graphene on Ge(001), Ge(011), Ge(111), Ge(112), Ge(001)-6°, and Ge(001)-9° via chemical vapor deposition (CVD), reporting on the effect of Ge surface orientation on graphene island formation and shape, strain in large-area graphene films, and the nanofaceting of the Ge below graphene.[1] We will then focus on the anisotropic growth of semiconducting graphene nanoribbons on Ge(001) and Ge(001)-9° and of nominally single crystal graphene on Ge(110).On Ge(001), we have discovered how to drive graphene crystal growth with a large shape anisotropy through control of kinetics.[2-6] This discovery enables the direct synthesis of narrow, armchair, semiconducting nanoribbons. The ribbons are self-orienting, self-defining, and have smooth edges. The ribbons exhibit excellent transport properties (e.g., high on-state conductance and on/off ratio at room temperature) and provide a promising pathway towards the direct integration of high-performance nanocarbon electronics onto conventional semiconductor wafer platforms.On Ge(001), nominally single crystal graphene has been reported in limited cases; however, conflicting studies have evidenced polycrystallinity. Here, the factors affecting the mosaicity of graphene on Ge(110) will be elucidated using low energy electron diffraction and microscopy data.[7][1] R. M. Jacobberger, D. E. Savage, X. Zheng, P. Sookchoo, R. R. Delgado, M. G. Lagally, M. S. Arnold, SUBMITTED (2022).[2] R. M. Jacobberger, M. S. Arnold, et al., Direct Oriented Growth of Armchair Graphene Nanoribbons on Germanium, NATURE COMMUNICATIONS, 6, 8006 (2015).[3] B. Kiraly, M. S. Arnold, M. C. Hersam, N. P. Guisinger et al., Sub-5 nm, Globally Aligned Graphene Nanoribbons on Ge (001), APPLIED PHYSICS LETTERS, 108, 213101 (2016).[4] A. J. Way, R. M. Jacobberger, M. S. Arnold, Seed-Initiated Anisotropic Growth of Unidirectional Armchair Graphene Nanoribbon Arrays on Germanium, NANO LETTERS, 18, 898 (2018).[5] V. Saraswat, Y. Yamamoto, H.J. Kim, R.M. Jacobberger, K.R. Jinkins, A.J. Way, N.P. Guisinger, M.S. Arnold Synthesis of armchair graphene nanoribbons on germanium-on-silicon, THE JOURNAL OF PHYSICAL CHEMISTRY C 123 (30), 18445-18454 (2019).[6] A. J. Way, R. M. Jacobberger, N. P. Guisinger, V. Saraswat, X. Zheng, A. Suresh, J. H. Dwyer, P. Gopalan, Michael S. Arnold, SUBMITTED (2022).[7] R. M. Jacobberger, Z. Miao, T. Yu, V. Saraswat, M. G. Lagally, M. S. Altman, M. S. Arnold, SUBMITTED (2022).

Identifying the alloy structures of germanene grown on Al(111)

While the growth of germanene has been extensively claimed on many substrates, their exact crystal structures remain controversial. Herein, we systematically explore the surface structures of Ge deposition onto the Al(111) surface by theoretical calculations combined with available scanning tunneling microscopy (STM) and low-energy electron diffraction data. We show that the formation of germanene on Al(111) is energetically unfavorable by $ab\phantom{\rule{0.16em}{0ex}}initio$ evolutionary simulations and high-level random-phase approximation calculations, and the two experimental phases are identified as honeycomb alloys ${\mathrm{Al}}_{3}{\mathrm{Ge}}_{3}/\mathrm{Al}(\sqrt{7}\ifmmode\times\else\texttimes\fi{}\sqrt{7})$ and ${\mathrm{Al}}_{3}{\mathrm{Ge}}_{4}/\mathrm{Al}(3\ifmmode\times\else\texttimes\fi{}3)$. It is interesting to find a vacancy at the interface of ${\mathrm{Al}}_{3}{\mathrm{Ge}}_{4}/\mathrm{Al}(3\ifmmode\times\else\texttimes\fi{}3)$, which is responsible for the dark clover pattern in STM experiments. Our results clarify the structural controversy of the Ge/Al(111) system and indicate that the fabrication of germanene on Al(111) remains challenging.

Solid state dewetting application for In/ (0001) Sb2Te3 2D layered semiconductor nanosystem formation

The (0001) surface of Sb2Te3 layered semiconductor crystal is used as a template for the formation of indium nanostructures by solid state dewetting (SSD). The initial surfaces for the SSD procedure obtained by cleavage have got perfect crystalline structure, both on a macro scale, according to low energy electron diffraction (LEED) data, and on a nanoscale according to scanning tunneling microscopy (STM) studies. Sb2Te3 samples were also characterized by X-ray diffraction and X-ray photoelectron spectroscopy. Thermally deposited indium in the SSD process forms on (0001) surface of Sb2Te3 self-organized ordered array of 0D nanostructures, due to the directing action of the surface relief, which is not smooth on a nanoscale.STM shows that the triangular shape and spatial arrangement of indium induced nanostructures are consistent with the surface lattice symmetry due to SSD processes. The scanning tunneling spectroscopy reveals correlation between indium coverage and high quantity of DOS within the band gap of Sb2Te3.

A new approach for synthesis of epitaxial nano-thin [formula omitted] alloy via intercalation underneath a graphene

In the present study we synthesized nano-thin epitaxial PtxGd alloys on Pt(111) single crystal surface covered with well-oriented graphene and investigated their electronic and atomic structure at different stages of synthesis. Low-energy electron diffraction, photoelectron spectroscopy and scanning tunneling microscopy data suggest that deposition of Gd on the graphene/Pt(111) system and its further intercalation at 1080 °C lead to formation of nano-thin Pt5Gd alloy covered with a quasi-freestanding graphene. We demonstrate that atomically flat alloy surface is terminated by Pt atomic layer with “kagome” structure. Control of graphene doping through variation of the alloy stoichiometry may open up new opportunities in developing advanced electronics. Owing to a well-known catalytic activity of Pt5Gd alloy, our thin-film system is promising for low-cost production of catalysts in the near future.

Experimental evidence of monolayer arsenene: an exotic 2D semiconducting material

Group V element analogues of graphene have attracted a lot of attention recently due to their semiconducting band structures and several other interesting properties predicted by theoretical investigations in the literature. In this study, we present atomic and electronic structure data of an arsenic (As) layer on Ag(1 1 1). Low-energy electron diffraction and scanning tunneling microscopy data provide evidence for an ordered layer with a lattice constant of 3.6 Å. This value fits with the theoretical range of 3.54–3.64 Å for buckled arsenene, which is the structure consistently predicted by various theoretical studies. The electronic structure obtained by angle-resolved photoelectron spectroscopy shows the existence of three 2D electron bands within 4 eV below the Fermi level. The number of bands and the agreement between experimental band dispersions and the theoretical band structure provide further evidence for the formation of monolayer buckled arsenene on Ag(1 1 1).

The role of surfactant in two−components structures formation on Si(111) surface

Surface structures and thermal stability of the ultrathin In films adsorbed on two different (α(√3 × √3) and β(√3 × √3)) Pb/Si(111) surfaces, varying in initial reconstructions, are investigated in situ with Low Energy Electron Diffraction (LEED) and X−ray Photoemission Spectroscopy (XPS). For the In/Si(111)−α(√3 × √3)−Pb system, In atoms invert their initial positions with the Pb surfactant at 470 K, resulting in formation of disordered mixed (In,Pb) overlayers. Moreover, Pb atoms located on the topmost layer desorb easily until the critical coverage is reached. Unreconstructed mixed (In,Pb) layers are also observed on the In/Si(111)−β(√3 × √3)−Pb system at room temperature due to In adsorption on Si surface in positions located between Pb atoms. Increasing the temperature of the samples yielded an arrangement of the adsorbate and surfactant atoms to 2D compounds with various periodic array. The new surface structures identified as (2 × 2) (4 × 1), and (√3 × √3) have been found to be formed in both systems. The detailed analyses of combining XPS and LEED data reveal that the phases can be built by either pure In or (In,Pb) compounds.

Ultrathin Chromia on a Hexagonally-Ordered d0 Ferromagnet: Evidence of Interfacial Exchange Bias at the Cr2O3/TiO2-x Interface.

Heterostructures consisting of 10 Å thick chromia films and 50 Å thick titania films display significant exchange bias at and above room temperature. Chromia films ∼10 Å thick were deposited by molecular beam epitaxy (MBE) of Cr at room temperature in ultrahigh vacuum on 50 Å thick TiO2-x(111) films (x < 0.3) also deposited epitaxially by MBE on Al2O3(0001). Cr deposition yields increased Ti(III) formation in the titania substrate and the formation of a Cr2O3 overlayer, without Cr/Ti interfacial mixing, as determined by in situ photoelectron spectroscopy (XPS) and electron energy loss spectroscopy (EELS). In situ low-energy electron diffraction (LEED) and XPS data indicate that the chromia overlayer is hexagonally ordered and ∼10 Å thick. Longitudinal and polar magneto-optic Kerr effect (MOKE) measurements at 285-315 K provide evidence of strong exchange bias between the boundary layer magnetization of chromia and the ferromagnetic substrate. These data demonstrate the robust room-temperature interaction of the boundary layer magnetization of a multiferroic antiferromagnet with a d0 ferromagnetic substrate.

Self-limited growth of an oxyhydroxide phase at the Fe3O4(001) surface in liquid and ambient pressure water.

Atomic-scale investigations of metal oxide surfaces exposed to aqueous environments are vital to understand degradation phenomena (e.g., dissolution and corrosion) as well as the performance of these materials in applications. Here, we utilize a new experimental setup for the ultrahigh vacuum-compatible dosing of liquids to explore the stability of the Fe3O4(001)-(√2 × √2)R45° surface following exposure to liquid and ambient pressure water. X-ray photoelectron spectroscopy and low-energy electron diffraction data show that extensive hydroxylation causes the surface to revert to a bulklike (1 × 1) termination. However, scanning tunneling microscopy (STM) images reveal a more complex situation, with the slow growth of an oxyhydroxide phase, which ultimately saturates at approximately 40% coverage. We conclude that the new material contains OH groups from dissociated water coordinated to Fe cations extracted from subsurface layers and that the surface passivates once the surface oxygen lattice is saturated with H because no further dissociation can take place. The resemblance of the STM images to those acquired in previous electrochemical STM studies leads us to believe that a similar structure exists at the solid-electrolyte interface during immersion at pH 7.

Structure determination of the Si(111)−7×3−In atomic-layer superconductor

The atomic structure of a superconducting atomic sheet of indium grown on Si(111) surface, i.e., $\mathrm{In}/\mathrm{Si}(111)\text{\ensuremath{-}}\sqrt{7}\ifmmode\times\else\texttimes\fi{}\sqrt{3}$, is determined by using surface x-ray diffraction (SXRD) and low-energy electron diffraction (LEED). The structure consists of double layers of In atoms with a rectangular arrangement, verifying a theoretical prediction [J. W. Park and M. H. Kang, Phys. Rev. Lett. 109, 166102 (2012)]. For the so-called hexagonal phase, which has been considered to be a different $\sqrt{7}\ifmmode\times\else\texttimes\fi{}\sqrt{3}$ structure and to undergo a transition to the $\sqrt{7}\ifmmode\times\else\texttimes\fi{}\sqrt{7}$ structure below 265 K, LEED data indicate that the structural basis is $\sqrt{7}\ifmmode\times\else\texttimes\fi{}\sqrt{7}$ even at room temperature. The SXRD data are well reproduced by single-layer In with the In coverage of 10/7 In atoms per Si surface atom, proposed by a theory [J. W. Park and M. H. Kang, Phys. Rev. Lett. 117, 116102 (2016)].

Growth and electronic structure of 2D hexagonal nanosheets on a corrugated rectangular substrate

Graphene and h-BN are grown by chemical vapor deposition in ultra high vacuum conditions on the Pt(110) surface. Scanning tunneling microscopy measurements and low-energy electron diffraction data indicate that graphene forms a variety of differently oriented incommensurate domains although with a strong preference to align its direction with the direction of Pt. Meanwhile, h-BN exhibits a c(8 × 10) commensurate superstructure, which presents a high level of defectivity that implies local variation of the periodicity (i.e. mixed c(8 × 10) and c(8 × 12) patches) and the introduction of local defects. The combination of advanced photoemission spectroscopy data (angle-resolved photoemission spectroscopy from the valence band) and ab initio calculations indicates that both 2D materials interact weakly with the substrate: graphene exhibits neutral doping and is morphologically flat, even if it nucleates on the relatively highly corrugated rectangular (110) surface. In the case of h-BN, the interaction is slightly stronger and is characterized by a small electron transfer from surface Pt atoms to nitrogen atoms. The (110) termination of Pt is therefore a quite interesting surface for the growth of 2D materials because given its low symmetry, it may favor the growth of selectively oriented domains but does not affect their pristine electronic properties.

Epitaxial growth of cobalt oxide phases on Ru(0001) for spintronic device applications

Cobalt oxide films are of technological interest as magnetic substrates that may support the direct growth of graphene, for use in various spintronic applications. In this work, we demonstrate the controlled growth of both Co3O4(111) and CoO(111) on Ru(0001) substrates. The growth is performed by Co molecular beam epitaxy, at a temperature of 500 K and in an O2 partial pressure of 10−4 Torr for Co3O4(111), and 7.5 × 10−7 Torr for CoO(111). The films are distinguished by their dissimilar Co 2p x-ray photoemission (XPS) spectra, while XPS-derived O/Co stoichiometric ratios are 1.33 for Co3O4(111) and 1.1 for CoO(111). Electron energy loss (EELS) spectra for Co3O4(111) indicate interband transitions at ∼2.1 and 3.0 eV, while only a single interband transition near 2.0 eV is observed for CoO(111). Low energy electron diffraction (LEED) data for Co3O4(111) indicate twinning during growth, in contrast to the LEED data for CoO(111). For Co3O4(111) films of less than 20 Å average thickness, however, XPS, LEED and EELS data are similar to those of CoO(111). XPS data indicate that both Co oxide phases are hydroxylated at all thicknesses. The two phases are moreover found to be thermally stable to at least 900 K in UHV, while ex situ atomic force microscopy measurements of Co3O4(111)/Ru(0001) indicate an average surface roughness below 1 nm. Electrical measurements indicate that Co3O4(111)/Ru(0001) films exhibit dielectric breakdown at threshold voltages of ∼1 MV cm−1. Collectively, these data show that the growth procedures yield Co3O4(111) films with topographical and electrical characteristics that are suitable for a variety of advanced device applications.

A surface science compatible epifluorescence microscope for inspection of samples under ultra high vacuum and cryogenic conditions.

We modified an epi-illumination light microscope and mounted it on an ultra high vacuum chamber for investigating samples used in a surface science experiment. For easy access and bake out, all optical components are placed outside the vacuum and the sample is imaged through a glass window. The microscope can be operated in reflection brightfield or epifluorescence mode to image the sample surface or fluorescent dye molecules adsorbed on it. The homemade sample mounting was made compatible for the use under the microscope; sample temperatures as low as 6 K can be achieved. The performance of the microscope is demonstrated on two model samples: Brightfield-images of a well-prepared Ag(100) surface show a macroscopic corrugation of the surface, although low energy electron diffraction data indicate a highly ordered crystalline surface. The surface shows macroscopic protrusions with flat regions, about 20-200 μm in diameter, in between. Fluorescence images of diluted 3,4,9,10-perylene tetracarboxylicacid dianhydride (PTCDA) molecules adsorbed on an ultrathin epitaxial KCl film on the Ag(100) surface show a shading effect at surface protrusions due to an inclined angle of incidence of the PTCDA beam during deposition. For some preparations, the distribution of the fluorescence intensity is inhomogeneous and shows a dense network of bright patches about 5 μm in diameter related to the macroscopic corrugation of the surface. We propose that such a light microscope can aid many surface science experiments, especially those dealing with epitaxial growth or fluorescent materials.

Multitude of PTCDA Superstructures on Ag(111) and Vicinal Surfaces

Organic molecules that covalently bond to metal surfaces, like perylene tetracarboxylic acid dianhydride (PTCDA) on Ag, may cause large-scale reconstruction of the interface, in particular if the adsorption takes place on a “stepped” (i.e., vicinal) surface. Under certain conditions, such surfaces develop a large variety of high-index facets that are stabilized by superstructures of the PTCDA adsorbate. These superstructures can be commensurate, point-on-line, or incommensurate with respect to the substrate facets depending on facet orientation and step direction. The present scanning tunneling microscopy and low-energy electron diffraction data were taken from two different vicinal surfaces, Ag(775) and Ag(10 8 7), both inclined by 8.5° with respect to the (111) direction but in different azimuthal directions. Altogether, we identify and evaluate 18 new superstructures and correlate their data with the properties of the corresponding facets. The observed richness of superstructures and the occurrence of ...

Influence of Pb on an In/Si(111) surface on the phase transition and the surface structure

The influence of Pb atoms adsorbed on an In/Si(111) surface on the phase transition was investigated by using low-energy electron diffraction (LEED) and scanning tunneling microscopy (STM). LEED data showed that the transition temperature for the 4×1 → 8×2 structural phase transition decreased in proportion to the amount of Pb deposition. The Pb adatoms appeared as bright protrusions in an STM image taken at 90 K, suggesting that they were located high above the In atomic wires. The regions surrounding the Pb adatoms remained in the 4×1 phase while the other areas turned into the 8×2 or 4×2 phase at this temperature below the transition temperature. Near each Pb adatom, a Friedel-oscillation-like modulation with a double (×2) periodicity in the wire direction was developed. This ×2 modulation was found to be different in nature from the low-temperature 8×2 (or 4×2) phase. We suggest that a Pb-adatom-induced deep potential well is responsible for the Tc lowering and the ×2 modulation.

Indexing moiré patterns of metal-supported graphene and related systems: strategies and pitfalls

We report on strategies for characterizing hexagonal coincidence phases by analyzing the involved spatial moiré beating frequencies of the pattern. We derive general properties of the moiré regarding its symmetry and construct the spatial beating frequency as the difference between two reciprocal lattice vectors of the two coinciding lattices. Considering reciprocal lattice vectors , with lengths of up to n times the respective (1, 0) beams of the two lattices, readily increases the number of beating frequencies of the nth-order moiré pattern. We predict how many beating frequencies occur in nth-order moirés and show that for one hexagonal lattice rotating above another the involved beating frequencies follow circular trajectories in reciprocal-space. The radius and lateral displacement of such circles are defined by the order n and the ratio x of the two lattice constants. The question of whether the moiré pattern is commensurate or not is addressed by using our derived concept of commensurability plots. When searching potential commensurate phases we introduce a method, which we call cell augmentation, and which avoids the need to consider high-order beating frequencies as discussed using the reported moiré of graphene on SiC(0001). We also show how to apply our model for the characterization of hexagonal moiré phases, found for transition metal-supported graphene and related systems. We explicitly treat surface x-ray diffraction-, scanning tunneling microscopy- and low-energy electron diffraction data to extract the unit cell of commensurate phases or to find evidence for incommensurability. For each data type, analysis strategies are outlined and avoidable pitfalls are discussed. We also point out the close relation of spatial beating frequencies in a moiré and multiple scattering in electron diffraction data and show how this fact can be explicitly used to extract high-precision data.

Atomic layer deposition of h-BN(0001) on RuO2(110)/Ru(0001)

The direct epitaxial growth of multilayer BN by atomic layer deposition is of critical significance for two dimensional device applications. To date, however, epitaxial growth has only been reported on graphene or on transition metal surfaces. X-ray photoelectron spectroscopy (XPS) and low energy electron diffraction (LEED) demonstrate layer-by-layer BN epitaxy on a monolayer of RuO2(110) formed on a Ru(0001) substrate. Growth was accomplished with BCl3/NH3 cycles at 600 K substrate temperature and subsequent annealing in ultrahigh vacuum. This yielded stoichiometric BN layers, Cl impurities levels of ≲1 at. %, and an average BN film thickness linearly proportional to the number of BCl3/NH3 cycles. XPS data indicate negligible charge transfer or band bending for the BN/RuO2 interface. LEED data indicate a 30° rotation between the coincident BN and oxide lattices. The atomic layer epitaxy of BN on an oxide surface suggests new routes to the direct growth and integration of graphene and BN with industrially important substrates, including Si(100).

Atomic Layer Epitaxy of h-BN(0001) Multilayers on Co(0001) and Molecular Beam Epitaxy Growth of Graphene on h-BN(0001)/Co(0001)

The direct growth of hexagonal boron nitride (h-BN) by industrially scalable methods is of broad interest for spintronic and nanoelectronic device applications. Such applications often require atomically precise control of film thickness and azimuthal registry between layers and substrate. We report the formation, by atomic layer epitaxy (ALE), of multilayer h-BN(0001) films (up to 7 monolayers) on Co(0001). The ALE process employs BCl3/NH3 cycles at 600 K substrate temperature. X-ray photoelectron spectroscopy (XPS) and low energy electron diffraction (LEED) data show that this process yields an increase in h-BN average film thickness linearly proportional to the number of BCl3/NH3 cycles, with BN layers in azimuthal registry with each other and with the Co(0001) substrate. LEED diffraction spot profile data indicate an average BN domain size of at least 1900 Å. Optical microscopy data indicate the presence of some domains as large as ∼20 μm. Transmission electron microscopy (TEM) and ambient exposure studies demonstrate macroscopic and microscopic continuity of the h-BN film, with the h-BN film highly conformal to the Co substrate. Photoemission data show that the h-BN(0001) film is p-type, with band bending near the Co/h-BN interface. Growth of graphene by molecular beam epitaxy (MBE) is observed on the surface of multilayer h-BN(0001) at temperatures of 800 K. LEED data indicate azimuthal graphene alignment with the h-BN and Co(0001) lattices, with domain size similar to BN. The evidence of multilayer BN and graphene azimuthal alignment with the lattice of the Co(0001) substrate demonstrates that this procedure is suitable for scalable production of heterojunctions for spintronic applications.