I think the absolute top of the list has to be a crossover with the first 'The Flash' show that ran alongside 'Arrow' for years. CW's Flash, I mean. You can tell the writers had fun with it; there are dozens of episodes crossing over, and it spawned thousands of fic spin-offs. The ones where Barry vibrates Oliver into a wall to save him, or where Oliver is grouchy about magic and super-speed messing up his city, are classics. That dynamic of tech vs. powers, darkness vs. light, is basically built-in.
For a deeper cut, some of the Batman crossovers on AO3 are surprisingly effective, especially when they lean into the street-level detective angle. I read this one where Batman shows up in Star City to investigate a drug shipment, and he and Oliver spend half the fic posturing at each other on rooftops before grudgingly teaming up. It tapped into the whole "two broody vigilantes, but one is way more traumatized" thing that fans love. That's a really common niche, but when done well, it feels like it could be an actual comic arc.
A weird one I've got soft spot for: short fics crossing over with the Netflix 'Daredevil' series. It shouldn't work—different tones, different networks—but the Catholic guilt and no-kill rule of Matt Murdock clashing with Oliver's more lethal early-season methods creates amazing tension. I remember a fic where Foggy Nelson ends up defending one of Oliver's old victims in court, and Matt has to figure out who the Hood really is. That kind of legal drama mixed with vigilantism is pure catnip for a specific reader.