Previous versions of PostgreSQL relied only on strcoll, which is horribly broken on BSD and macOS. On platforms where it wasn't completely broken, it had the potential for subtle data corruption bugs (eg. an update to glibc might change sort order, causing indexes to become corrupt).
Now, you can optionally use ICU for collations, which gives you reliable, versioned collations. This is a big step forward!
ICU collations are not the default, you need to add them with CREATE COLLATION. You have a lot more collations available to choose from, but I think it's not yet possible to change any of the advanced settings that ICU provides.
(Also, when I tried it, it seems that the ICU collations are case insensitive -- but I think case insensitive collations aren't fully supported yet.)