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Do you have a paint program or a windows feature that can 'clip' and save data?
Use print screen, on your keyboard. IMMEDIATELY move from the game to the paint program, and paste the shot.
SOME games have their own independent screenshot or photo mode, so... look through their keybind options for that. Not all have one though, and some of them would save the images in a different folder than your steam userdata folders.
Otherwise check the game's screenshot settings, or use ALT+PRTSCR to screenshot into your clipboard, which you can then paste into photoshop/gimp/lviewpro/MS Paint/Discord/whatever.
Which again, you have to post into a program in order to actually SAVE. Otherwise, you're just spamming your system with useless clipboard stuff that vanishes the next time you click printscreen...
Your OP indicates without Steam overlay.
Without Steam overlay, their f12 obviously cannot exist. So... you have a choice. Use their overlay system and have it save in their file structure, or, as posted 3 times above, click printscreen or alt-printscreen and paste immediately into a paint program.
2) you can use other screenshot programs, but they won’t be integrated into Steam
The main point of taking screenshots in Steam is that it automatically get integrated in Steam itself. It is easy to just share screenshots directly in Steam. If you save your screens outside of the client then you have to upload them as "artwork" if you wish to share them with the community.