title: Van der Waals Epitaxial Growth of Two-Dimensional Single-Crystalline GaSe Domains on Graphene.
abstract: Two-dimensional (2D) van der Waals (vdW) heterostructures are a family of artificially structured materials that promise tunable optoelectronic properties for devices with enhanced functionalities. Compared to transferring, direct epitaxy of vdW heterostructures is ideal for clean interlayer interfaces and scalable device fabrication. Here we report the synthesis and preferred orientations of 2D GaSe atomic layers on graphene (Gr) by vdW epitaxy. GaSe crystals are found to nucleate predominantly on random wrinkles or grain boundaries of graphene, share a preferred lattice orientation with underlying graphene, and grow into large (tens of micrometers) irregularly shaped, single-crystalline domains. The domains are found to propagate with triangular edges that merge into the large single crystals during growth. Electron diffraction reveals that approximately 50% of the GaSe domains are oriented with a 10.5 ± 0.3° interlayer rotation with respect to the underlying graphene. Theoretical investigations of interlayer energetics reveal that a 10.9° interlayer rotation is the most energetically preferred vdW heterostructure. In addition, strong charge transfer in these GaSe/Gr vdW heterostructures is predicted, which agrees with the observed enhancement in the Raman E(2)1g band of monolayer GaSe and highly quenched photoluminescence compared to GaSe/SiO2. Despite the very large lattice mismatch of GaSe/Gr through vdW epitaxy, the predominant orientation control and convergent formation of large single-crystal flakes demonstrated here is promising for the scalable synthesis of large-area vdW heterostructures for the development of new optical and optoelectronic devices.
authors.affiliation: Center for Nanophase Materials Sciences, Oak Ridge National Laboratory , Oak Ridge, Tennessee 37831, United States.
authors.forename: Xufan
authors.initials: X
authors.lastname: Li
authors.affiliation: Center for Nanophase Materials Sciences, Oak Ridge National Laboratory , Oak Ridge, Tennessee 37831, United States.|Departamento de Física, Escuela Politécnica Nacional , Quito 170525, Ecuador.
authors.forename: Leonardo
authors.initials: L
authors.lastname: Basile
authors.affiliation: Center for Nanophase Materials Sciences, Oak Ridge National Laboratory , Oak Ridge, Tennessee 37831, United States.
authors.forename: Bing
authors.initials: B
authors.lastname: Huang
authors.affiliation: Center for Nanophase Materials Sciences, Oak Ridge National Laboratory , Oak Ridge, Tennessee 37831, United States.
authors.forename: Cheng
authors.initials: C
authors.lastname: Ma
authors.affiliation: Center for Nanophase Materials Sciences, Oak Ridge National Laboratory , Oak Ridge, Tennessee 37831, United States.
authors.forename: Jaekwang
authors.initials: J
authors.lastname: Lee
authors.affiliation: Energy & Transportation Science Division, Oak Ridge National Laboratory , Oak Ridge, Tennessee 37831, United States.
authors.forename: Ivan V
authors.initials: IV
authors.lastname: Vlassiouk
authors.affiliation: Center for Nanophase Materials Sciences, Oak Ridge National Laboratory , Oak Ridge, Tennessee 37831, United States.
authors.forename: Alexander A
authors.initials: AA
authors.lastname: Puretzky
authors.affiliation: Center for Nanophase Materials Sciences, Oak Ridge National Laboratory , Oak Ridge, Tennessee 37831, United States.
authors.forename: Ming-Wei
authors.initials: MW
authors.lastname: Lin
authors.affiliation: Center for Nanophase Materials Sciences, Oak Ridge National Laboratory , Oak Ridge, Tennessee 37831, United States.
authors.forename: Mina
authors.initials: M
authors.lastname: Yoon
authors.affiliation: Center for Nanophase Materials Sciences, Oak Ridge National Laboratory , Oak Ridge, Tennessee 37831, United States.
authors.forename: Miaofang
authors.initials: M
authors.lastname: Chi
authors.affiliation: Center for Nanophase Materials Sciences, Oak Ridge National Laboratory , Oak Ridge, Tennessee 37831, United States.
authors.forename: Juan C
authors.initials: JC
authors.lastname: Idrobo
authors.affiliation: Center for Nanophase Materials Sciences, Oak Ridge National Laboratory , Oak Ridge, Tennessee 37831, United States.
authors.forename: Christopher M
authors.initials: CM
authors.lastname: Rouleau
authors.affiliation: Center for Nanophase Materials Sciences, Oak Ridge National Laboratory , Oak Ridge, Tennessee 37831, United States.|Computer Science and Mathematics Division, Oak Ridge National Laboratory , Oak Ridge, Tennessee 37831, United States.
authors.forename: Bobby G
authors.initials: BG
authors.lastname: Sumpter
authors.affiliation: Center for Nanophase Materials Sciences, Oak Ridge National Laboratory , Oak Ridge, Tennessee 37831, United States.
authors.forename: David B
authors.initials: DB
authors.lastname: Geohegan
authors.affiliation: Center for Nanophase Materials Sciences, Oak Ridge National Laboratory , Oak Ridge, Tennessee 37831, United States.
authors.forename: Kai
authors.initials: K
authors.lastname: Xiao
keywords: GaSe; chemical vapor deposition; graphene; heterostructures; van der Waals epitaxy