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Recent work has demonstrated excellent p-type field-effect switching in exfoliated black phosphorus, but type control has remained elusive. Here, we report unipolar n-type black phosphorus transistors with switching polarity control via contact-metal engineering and flake thickness, combined with oxygen and moisture-free fabrication. With aluminium contacts to black phosphorus, a unipolar to ambipolar transition occurs as flake thickness increases from 3 to 13 nm. The 13-nm aluminium-contacted flake displays graphene-like symmetric hole and electron mobilities up to 950 cm 2  V −1  s −1  at 300 K, while a 3 nm flake displays unipolar n-type switching with on/off ratios greater than 10 5  (10 7 ) and electron mobility of 275 (630) cm 2  V −1  s −1  at 300 K (80 K). For palladium contacts, p-type behaviour dominates in thick flakes, while 2.5–7 nm flakes have symmetric ambipolar transport. These results demonstrate a leap in n-type performance and exemplify the logical switching capabilities of black phosphorus.

High-performance n-type black phosphorus transistors with type control via thickness and contact-metal engineering