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Indexes are only part of the problem with a large scale application. You can have a great set of indexes on an otherwise bad data schema, and the database can pull your hole app down, no matter what logic tier language or framework you used. And a person can write a terrible schema just as easily in Oracle, MySql, MsSql, or just about anything else.
Asp and asp.net have some built in mechanisms that php doesn't have ... stuff that makes a high scale web site possible. Caching is the main one; in php, as far as I've ever been able to tell, there's no way to cache data at the application level. You can store things in a user session, but not an application. Things like the values in a bunch of drop-down lists are perfect for app-level caching, because they rarely change, and it's a waste to make a round-trip to the database for each of them, but also because it's also wasteful to store them in each user session. The more connections and transactions in the database, the more pressure it's under ... that doesn't hurt a normal web site, but limits how far it can scale.
Both languages have their strengths and weaknesses, neither is perfect, or we wouldn't have both. If you want to try one you haven't used before, that's probably a very good idea ... more in your bag of tricks.
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