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In just over two hours, a feisty Lehecka thwarted Nadal's hopes of reaching his 100th Masters 1000 quarterfinals.
This will be the 22-time Grand Slam champion's fourth appearance at the three-day team tournament, which pits six top men's players from Europe against six of their counterparts from the rest of the world.
Alcaraz became the first man to defend a championship in the California desert since Novak Djokovic won three straight between 2014 and 2016.
Alcaraz came from behind to beat Jannik Sinner before Medvedev edged out American Tommy Paul 1-6, 7-6(3), 6-2 in the second semifinal.
Third seed Coco Gauff served up 17 double faults but still managed to beat China's Yuan Yue 6-4, 6-3 to reach the women's semifinals in the Californian desert for the first time.
Humbert became only the third player in the professional era to win his first six tour-level finals, matching the achievement of Latvia's Ernests Gulbis and Slovakia's Martin Klizan.
A Russian-speaking official appeared to accuse him of using an obscenity, while he screamed at the line judge.
Carlos Alcaraz, Jannik Sinner, Daniil Medvedev and Holger Rune will also play at the 'Six Kings Slam', which will form part of the Saudi cultural and entertainment festival Riyadh Season.
The 22-year-old fourth seed is the first Italian to win the Melbourne Park title.
Sinner broke for a 3-1 lead in the fourth set and ran away with the match to snap the Serb's 33-match winning run at Melbourne Park and end his quest for a record 25th major.