The 33-year-old Spaniard becomes the first player, man or woman, to win the same Slam 12 times after seeing off a brave challenge from a weary Thiem of Austria in a repeat of the 2018 final.
Two-time defending champion Rafael Nadal remains on course for a record 12th French Open men's singles title after beating quarter-final opponent Kei Nishikori in straight sets.
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