Solution 1:[1]
If you mean the window itself, I am afraid that is not possible due to the fact that Tkinter needs to be supported by 3 different operating systems, all with different window handlers. If you wish to attempt to do this, you will need to find a OS-specific library to do this. If you mean having a canvas with a rounded rectangle inside it, this question, which jezza_99 mentioned, covers this quite nicely.
Sources
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Source: Stack Overflow
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