The present invention relates to asymmetric molecular bilayers for the use in the junctions of electronic devices, such as crossbar junctions, comprising the general structure ET-MT( )MB-EB, wherein ET and EB denote a top and a bottom electrode, MT and MB represent functional molecules both forming a self-assembled monolayer (SAM) on said top or bottom electrode, and the symbol ( ) denotes a non-covalent interaction between the two monolayers, resulting in a molecular bilayer, sandwiched between the two electrodes. The electrodes are solid state electrodes and stationary with respect to each other. The present invention also relates to a method of producing such assemblies.