Methods of selective deposition and chemical delivery systems
Systems and methods of selectively depositing metal oxide on an exposed metal surface relative to a dielectric material on a substrate by pre-treatment with a hydroxy species-generating plasma prior to inhibition of the metal surface with an inhibitor, and subsequent metal oxide deposition on the dielectric material are disclosed. Exemplary inhibitors include low vapor pressure inhibitors. Exemplary systems include heated ampoules and gas lines for delivering inhibitors or other processing chemicals.
1 . A method for selective metal oxide deposition on a dielectric material relative to an exposed metal surface on a substrate, the method comprising the steps of:
(a) providing the substrate comprising the dielectric material and the exposed metal surface;
(b) contacting the substrate with a plasma generated from a hydrogen-containing source and an oxygen-containing source to generate hydroxy species, wherein the hydroxy species react with the dielectric material to form a hydroxy-terminated dielectric material and react with the exposed metal surface to form an oxidized metal surface;
(c) exposing the oxidized metal surface and the hydroxy-terminated dielectric material to a deposition inhibitor that selectively modifies the oxidized metal surface, forming an inhibited metal surface; and then
(d) selectively depositing metal oxide on the hydroxy-terminated dielectric material relative to the inhibited metal surface on the substrate.
2 . The method of claim 1 , wherein a metal of the exposed metal surface comprises copper, cobalt, tungsten, ruthenium, tantalum, titanium, hafnium, zirconium, molybdenum or a combination thereof.
3 . The method of claim 1 , wherein the metal oxide comprises zirconium oxide, hafnium oxide, aluminum oxide, titanium oxide, tantalum oxide, yttrium oxide, lanthanum oxide or a combination thereof.
4 . The method of claim 3 , wherein the metal oxide is aluminum oxide.
5 . The method of claim 4 , wherein the aluminum oxide is deposited by an aluminum oxide precursor comprising trimethylaluminum, dimethylaluminum chloride, aluminum chloride, dimethylaluminum isopropoxide or triethylaluminium.
6 . The method of claim 1 , wherein the deposition inhibitor comprises sulfur-containing compounds, phosphorus-containing compounds or silicon-containing compounds.
7 . The method of claim 1 , wherein the selective metal oxide deposition comprises chemical vapor deposition.
8 . The method of claim 1 , further comprising treating the inhibited metal surface to remove inhibitor.