Back when CDs were a new thing, there was this song I can't remember, that used something like a 21KHz tone as part of a "scream". By then I was old enough to barely hear up to 20KHz, but my dog jumped up and scowled at it.
There's a lot of high notes in pretty much anything from Kiske-era Helloween, particularly on the Keeper of the Seven Keys albums. Halloween is a nice example.
Similarly, a lot of stuff by Judas Priest when Rob Halford is on vocals, with Painkiller being a perfect example.
But Geoff Tate is one of the best, IMO, perfectly encapsulated in Queen of the Reich.
I don't know that any of them are the "highest" I've heard, exactly, but Geoff Tate is probably up there.
Pantera's Phil Anselmo on the Cemetary Gates outro, battling with Dimebag's pinch harmonics as the track is about to fade out is an insane powermove. I'd link with a timecode, but the track must be listened to from start to end: https://www.youtube.com/watch?v=RVMvART9kb8
While there are probably tons much more recent, here are some (old and non metal songs) that come to mind:
Prince in The Beautiful Ones, Steven Tyler in Dream On, Roger Daltry, in Won't Get Fooled Again.
The lead singer Michael Sweet of Stryper has one of the highest falsetto tenor voices I've ever heard. Though i am far from religious at all anymore, yes i needed clarify that first, I still love Stryper a christian glam metal band form the 80's. Mike could really wail, and still does. I still think they just all out ROCK even today.
He really showcases his highs in this song along with Oz Foxes shredding echoing his vocals kind of like Anselmo and Dime in Cemetary gates in this one. ( warning cheesey christian lyrics, but truly excellent voices and musicianship)
https://www.youtube.com/watch?v=ERMKZhFwGEU 80's