Yes, on both counts. (Spoilers for post-GoF)
Cruciatus curse
The Cruciatus curse gets used by Harry on Bellatrix Lestrange, as she flees the Department of Mysteries in Order of the Phoenix:
Hatred rose in Harry such as he had never known before; he flung himself out from behind the fountain and bellowed, “Crucio!”
Bellatrix screamed: the spell had knocked her off her feet, but she did not writhe and shriek with pain as Neville had - she was already back on her feet, breathless, no longer laughing. Harry dodged behind the golden fountain again. Her counter-spell hit the head of the handsome wizard, which was blown off and landed twenty feet away, gouging long scratches into the wooden floor.
“Never used an Unforgivable Curse before, have you, boy?” she yelled. She had abandoned her baby voice now. “You need to mean them, Potter! You need to really want to cause pain – to enjoy it – righteous anger won’t hurt me for long – I’ll show you how it is done, shall I? I’ll give you a lesson—”
This is after Bellatrix has killed Sirius, Harry’s only remaining family member, so he’s understandably angry.
If that doesn’t count, then Bellatrix also uses it on Neville in the same fight:
Bellatrix raised her wand. “Crucio!”
Neville screamed, his legs drawn up to his chest so that the Death Eater holding him was momentarily holding him off the ground. The Death Eater dropped him and he fell to the floor, twitching and screaming in agony.
Imperius curse
The Imperius curse is used (also by Harry) when the trio break into Gringotts bank. At the time, one of the goblins is about to blow their cover, so Harry needs to stop him doing so. (At this point, the trio have been branded criminals, and in disguise.)
Harry raised the hawthorn wand beneath the cloak, pointed it at the old goblin, and whispered, for the first time in his life, “Imperio!”
A curious sensation shot down Harry’s arm, a feeling of tingling warmth that seemed to flow from his mind, down the sinews and veins connecting him to the wand and the curse it had just cast.
There are plenty of other instances where the curses are used throughout the books (and films), but hopefully the two examples above are sufficient to show that yes, all three curses were used.