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A silicon-based lifeform is a corporeal lifeform that uses silicon as the basis of its structure and life functions rather than carbon. Silicon-based lifeforms generally do not evolve on M class planets. (ENT: "Observer Effect")
In 2151, Captain Jonathan Archer of Enterprise NX-01 tried to convince Commander Charles Tucker III that Starfleet had sent them to a planet to meet with a silicon-based lifeform, when Tucker was hallucinating "people coming out of the rock face." (ENT: "Strange New World")
Silicon-based life was thought to be physiologically impossible before the discovery of the Horta of Janus VI in 2267. It is not possible for silicon life to evolve in an oxygen atmosphere. (TOS: "The Devil in the Dark")
In 2269, the USS Enterprise encountered Yarnek, a representative of the Excalbians, a shapeshifting silicon-based species native to the planet Excalbia, described as being "almost mineral" and "like living rock with heavy fore-claws." (TOS: "The Savage Curtain")