I dearly love Lush-101. Not a lot of third party sounds available, but the ones that are available are wonderfully musical.
Alchemy I love just for the engineering brilliance, even though most sounds tend to be a bit too "sound-scape-y" for my purposes. Also, it's got the best documentation of any synth ever.
Synthmaster has a *ton* of add-on sounds that are great. None of the libraries are overly expensive, so you can painlessly build your collection over time. Synthmaster is probably the best all-around value going right now, bang-for-the-buck-wise.
Zebra 2 is totally wonderful, and there is quite a wide selection of third party content to purchase. DIVA is incredible sounding - it doesn't have many of the usual soft-synth bells and whistles but it sounds very convincingly like the real hardware thing.
I just watched a Groove 3 tutorial series on NI's Massive. I'm more than a little intrigued to dig into that one far more that I've done to date.