Thinking too small - for a $100M raise to make sense, valuation has to be $1B or higher, and need a 10x total market for VCs to be interested. So $10B to $100B is the target, and they need very large goals to justify it.
[Edit - I guessed $1B-$10B valuation; WSJ says unnamed source cites $750M. If true, congratulations to A16Z, they got a steal.]
Most of github's mission is removing friction in collaboration around code.
Following this theme, likely expansions: removing transactional overhead to add liquidity to the development market ( http://en.wikipedia.org/wiki/Coase_theorem ) which is badly inelastic in the face of great demand. Less audacious, they may just domainate the recruiting market.
Still on the theme, continuing to push on the need to colocate to be productive - online editing, tools in support of code review, user testing, in-app feedback, platform building/distribution.
Build farms, integration tooling, and support markets also seem plausible but more difficult to see (in the current market) how they could get sufficient uptake to justify the target valuation.
One more, less optimistic: IP/patent/code provenance - lots of money attached to those things.