Heat the oven to 350°F, lightly grease a 9-inch square baking pan, and line it with parchment paper. The parchment should cover the bottom and make lifting the chilled bars out of the pan much easier later.
Place the butter and 1 cup of chocolate chips in a large microwave-safe bowl and melt them in 20-second bursts, stirring after each round, until smooth and fully combined, about 2 minutes total. Stop as soon as the mixture is glossy and fluid so the chocolate does not scorch or separate.
Whisk the cocoa powder into the warm chocolate mixture, then add the granulated sugar, brown sugar, eggs, egg yolk, brewed coffee, and vanilla extract. The batter should look dark, thick, and shiny once everything is evenly mixed.
Fold in the flour and salt with a spatula just until no dry streaks remain, then scoop ½ cup of batter into a small bowl. Keep the mixing brief here so the brownie layer stays dense and fudgy instead of tough.
Stir the remaining ⅓ cup of chocolate chips into the main batter and spread it into the prepared pan. The layer will be thick, and smoothing it into the corners helps the base bake evenly.
Bake the brownie base for 20 minutes for a very fudgy result or 30 minutes for a more cakey result. While it bakes, stir the hot water into the reserved batter until it is still thick but slowly drips from a spoon like loose cake batter, adding a bit more water if needed.