Michael Piller
Episode 3x01, Evolution
Piller was called by one of the lead writers during Season 2 of TNG to write a few episodes; his first work, Evolution (the Opening of Season 3), and some subsequent episodes he wrote were appreciated so much that he eventually became one of the main writers and producers, not only in TNG but also in DS9 and VOY.
Some of the most appreciated episodes of the whole show, like Yesterday's Enterprise and especially The Best of both Worlds were written by him.
Reference: Memory Alpha
René Echevarria
Episode 3x16, The Offspring
Echevarria sent the unsolicited script for The Offspring while working as a waiter. He then become a regular writer for both TNG and DS9. Some of his most notable works for TNG are I, Borg, True Q, Face of the Enemy, Second Chances and Lower Decks.
Reference: Memory Alpha
Brannon Braga, Joe Menosky, Naren Shankar
These three writers joined TNG as interns during Season 4, and mostly had roles of story editors. Thus, they don't strictly have a single "first episode" that made the producers aware of their talents, but all of them afterwards had major writing and producing roles on TNG and subsequent series.
Some notable episodes:
- Braga: Cause and Effect, Timescape, Parallels, All Good Things...
- Menosky: Darmok, The Chase
- Shankar: The First Duty, The Quality of Life, Gambit
Reference: Memory Alpha - Braga - Menosky - Shankar