a) Direct growth of 2D-materials-based vertical heterostructures by CVD with (i) h-BN by exploiting ammonia borane as precursor and ii) graphene onto the as-grown h-BN layers. b) Growth by either CVD or MBE of individual 2D materials and subsequent dry transfer using pick and place techniques enabling, in principle, any combination of different 2D materials. c) The relative orientation of the different layers of 2D materials is key and mandatory to be controlled to design i) vertically aligned and ii) controlled twist heterostructures. d) Lateral heterostructures can be realized i) by seeding an already grown 2D material template, ii) grow a second 2D material by using the appropriate precursors; and iii) by a proper placement of seeds through either a pattern and etch process or a mask, which can allow the realization of different lateral heterostructures such as linear, zigzag and donut-like shape. e) i) Direct growth of h-BN on graphene edges; ii) Scanning electron microscopy image showing a concentric h-BN/graphene heterostructure; iii) Optical image of a graphene/h-BN array of circles, with graphene circles embedded in an h-BN matrix. Panel i) in c) Courtesy of Profs. M. Kim and E. Tutuc, panel ii) and iii) in e) adapted from Ref. .