(0, 0) is top left
(width - 1, height -1) is bottom right
However, when you use sf::Points primitive, you have to consider that a pixel is still an area, while it can't be resolved any further by your screen, OpenGL still handles it as float, so the top left pixel starts at position (0, 0) and spawns up to the point (1, 1). So if you want to render a point on that pixel, you need to center the point, setting its position to (0.5f, 0.5f).
Illustration
Red = Point at (0, 0)
Blue = Point at (0.5f, 0.5f)