A 20s cadence Transiting Exoplanet Survey Satellite monitoring campaign of 226 low-mass flare stars during Cycle 3 recorded 3792 stellar flares of >=10^32^erg. We explore the time-resolved emission and substructure in 440 of the largest flares observed at high signal-to-noise, 97% of which released energies of >=10^33^erg. We discover degeneracy present at 2 minute cadence between sharply peaked and weakly peaked flares is common, although 20s cadence breaks these degeneracies. We better resolve the rise phases and find 46% of large flares exhibit substructure during the rise phase. We observe 49 candidate quasi-periodic pulsations (QPP) and confirm 17 at >=3{sigma}. Most of our QPPs have periods less than 10 minutes, suggesting short-period optical QPPs are common. We find QPPs in both the rise and decay phases of flares, including a rise-phase QPP in a large flare from Proxima Cen. We confirm that the Davenport+ (2014ApJ...797..122D) template provides a good fit to most classical flares observed at high cadence, although 9% favor Gaussian peaks instead. We characterize the properties of complex flares, finding 17% of complex flares exhibit "peak-bump" morphologies composed of a large, highly impulsive peak followed by a second, more gradual Gaussian peak. We also estimate the UVC surface fluences of temperate planets at flare peak and find one-third of 10^34^erg flares reach the D90 dose of Deinococcus radiodurans in just 20s in the absence of an atmosphere.

Cone search capability for table J/ApJ/926/204/stars (List of the 146 unique stars extracted from Tables 1+2; table added by CDS)