Google treats some ccTLDs (such as .tv, .me, etc.) as gTLDs, as we've found that users and webmasters frequently see these more generic than country-targeted. Here is a list of those ccTLDs (note that this list may change over time).
Google treats the following as gTLDs that can be geotargeted in Webmaster Tools.
Generic Top Level Domains (gTLDs)