Is it possible to create a default fourth field such as keyword in Library?

You can have up to 10 search lines when using the Search Library command.

You can use the plus sign on the right to add the additional lines and use the minus sign to remove lines.

Please see the attached screenshot. Search Window.png

If you do have additional question you can also contact Technical Support directly

1-800-336-4474 option 4 then 1

or
https://endnote.com/contact/