It's worth knowing the different usages of "on" and "at". If you are "at" the border between two countries, you are in the general area of the border. You could be waiting to go through customs, for example. However, if you are "on" the border, you are physically on it, probably standing on it. In some places, you can stand with one leg either side of the line, "on" the border.
When speaking figuratively, it is usual to say "on" and not "at".
We don't usually say "on the border of" but use synonyms like "edge", "verge" and "brink". I don't know why, but we don't usually say : "He is on the border of e.g. madness.
But it is common to say : "He is bordering on e.g. madness".