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As someone who knows nothing about this, how is something like "Tungsten disulfide/boron nitride" selected? Is it based on some models? Or, is it more of a random walk?

They're two materials that 2D materials people commonly stock. BN is thought to be a pretty innocuous insulator. Might as well be the lettuce of the sandwich. However, it's now showing that it has effects on the nearby layers, so people are playing with it in heterobilayer devices.

A large part of the field of 2D materials is just trying stuff.

They are choosing from a subset of materials that can form stable 2D crystals in order to test effects of relative twist angles on their energy bands.

Are 2d crystals the depth of 1 molecule?

One layer of somewhat coplanar atoms.

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