TECHNOLOGY FOCUS - INORGANIC CHEMISTRY - Preferred Method: The method further comprises: subjecting the molecules of the molecularly self-assembled layer to hydrolysis; and cleaning the surface of the porous dielectric material prior to forming the molecularly self-assembled layer on the surface of the porous dielectric material. The molecules of the molecularly self-assembled layer are crosslinked. The head groups are covalently bound to hydroxyl groups of the dielectric material. The barrier layer is formed using atomic layer deposition and the molecularly self-assembled layer is configured to bind a precursor used to form the barrier layer and to prevent the precursor from contacting the surface of the porous dielectric. The step of cleaning the surface of the porous dielectric material comprises delivering a cleaning solution to the surface of the porous dielectric material. The molecularly self-assembled layer is formed on selected portions of the surface of the porous dielectric material while remaining portions of the surface are free from the molecularly self-assembled layer. Preferred Components: The porous dielectric material has a volumetric pore fraction of less than or equal to 50%. The chain lengths are less than or equal to 25 Angstrom , preferably less than or equal to 10 Angstrom . The barrier layer comprises: a titanium-based material, a tantalum based material, a ruthenium based material or a tungsten-based material; and one of tantalum, tantalum nitride, tantalum carbon nitride, tungsten nitride, tungsten carbon nitride or ruthenium. The precursor used to form the barrier layer comprises one of tetrakis(dimethylamino)titanium, tetrakis diethyl amido titanium, pentakis(dimethylamino)tantalum, (tert- butylimido)tris(diethylamido) tantalum, tertbutylimido-tris(ethylmethylamido)-tantalum, tungsten hexafluoride, ruthenocene and/or their derivatives.    TECHNOLOGY FOCUS - ORGANIC CHEMISTRY - Preferred Components: The molecules further comprise terminal groups having a structure of formula (NRx). The molecules of the molecularly self-assembled layer comprise one or more thiols having a structure of formula (R1-SH). The thiols are functionalized with metals. The molecules of the molecularly self-assembled layer comprise one or more organosilanes having a structure of formula (R2n-Si-X4-n).Rx = H or one or more organic groups;R1 = alkyl, aryl, heteroaryl, fluorinated alkyl, fluorinated aryl, fluorinated heteroaryl, functionalized alkyl, functionalized aryl, or functionalized heteroaryl;R2 = H, alkyl, alkenyl, alkynyl, aryl, fluoroalkyl, heteroaryl, fluoroheteroaryl, alcohol, thiol, amine, amide, imine, carboxylic acid, thiocarboxylic acid, thiocarbamate, ester, ether, sulfide or nitrile;X = halide, carboxylate, amine, alkoxide, sulfide, heteroaryl or fluororoaryl; andn = 1-3.