Heterogeneous Pyrolysis: A Route for Epitaxial Growth of hBN Atomic Layers on Copper Using Separate Boron and Nitrogen Precursors
G Siegel and CV Ciobanu and B Narayanan and M Snure and SC Badescu, NANO LETTERS, 17, 2404-2413 (2017).
Growth of hBN on metal substrates is often performed via chemical vapor deposition from a single precursor (e.g., borazine) and results in hBN monolayers limited by the substrates catalyzing effect. Departing from this paradigm, we demonstrate close control over the growth of mono-, bi-, and trilayers of hBN on copper using triethylborane and ammonia as independent sources of boron and nitrogen. Using density functional theory (DFT) calculations and reactive force field molecular dynamics, we show that the key factor enabling the growth beyond the first layer is the activation of ammonia through heterogeneous pyrolysis with boron- based radicals at the surface. The hBN layers grown are in registry with each other and assume a perfect or near perfect epitaxial relation with the substrate. From atomic force microscopy (AFM) characterization, we observe a moire superstructure in the first hBN layer with an apparent height modulation and lateral periodicity of similar to 10 nm. While this is unexpected given that the moire pattern of hBN/Cu(111) does not have a significant morphological corrugation, our DFT calculations reveal a spatially modulated interface dipole layer which determines the unusual AFM response. These findings have improved our understanding of the mechanisms involved in growth of hBN and may help generate new growth methods for applications in which control over the number of layers and their alignment is crucial (such as tunneling barriers, ultrathin capacitors, and graphene-based devices).
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