The ATA-66 spec allows 66 MB of data to be transferred per second, and ATA-100 allows 100MB/sec. Since even the best ATA drives have yet to break sequential transfer rates greater than even 40 MB/sec, ATA-100 isn't needed unless you are using multiple drives in a RAID setup. If you aren't using a RAID setup and are only using one ATA hard drive, ATA-66 (and in most cases, even ATA-33) interfaces will slightly run the drive with optimal performance.
Also, RAID setup is best used with SCSI drives and not ATA drives. I wouldn't recommend an ATA RAID setup because it will lower your already low access times, ATA drives don't multitask well, and SCSI RAID controllers are much better.