Zend Framework + Doctrine ORM
this is what i am using now. it maybe a bit hard to learn at the start. but i think its worth it. Zend Framework 2 is coming up (1st Dev Milestone of ZF2 is out). and it supports PHP 5.3 "true" namespaces. i use Zend Framework 1.10 + Doctrine 2 currently. i really like the way its components can be customized easily to fit your needs.
it has many classes that i use (that may not be available in other frameworks). eg. classes for navigation, pagination, view helpers, (PHPUnit) unit testing via Zend_Test etc. logging to even FireBug/FirePHP using Zend_Log.
Rapid Development & Prototyping if you mean scaffolding, there's Zend_Tool, a CLI application that allows you to create components like controllers, actions, models, etc. via CLI commands
i am not sure about scalability. but i heard .NET is used commonly in the enterprise so it must be more scalable. but i am not sure.
if your choose this option, some great learning resources are:
ASP.NET MVC 2
i haven't used ASP.NET MVC to create any real applications yet. but i am watching its development. MVC 3 is comming up ... link & link & link ... it looks good with the addition of the razor view engine (its something like a light weight templating engine). C# can be used and i find it to be a very powerful language, with Entity Framework (ORM), lambdas, LINQ etc.
i think ASP.NET Web Forms is great for prototying but not good with its messy code (in my opinion) and i don't think its good for scalability
resources for these options: