OK, all fixed. Thanks for your help.
I tried everything, but ended up changing the chip, which was an SMT device so had to pick up my hot air iron from work.
Replaced the chip and reprogrammed, everything now working as expected.
Must have had something very strange going on with just that pin, because it still read correctly with a high or low, but just always measured 0.7V
I reprogrammed the old one first but it made no difference.
Anyway, all good now
Thanks