My local garage offers the forte diesel treatment and engine flush (for £25) whenever my car goes in for servicing.
I can't imagining them phoning up anyone who takes up this offer and saying, sorry we can't supply the diesel treatment because you have a full tank of fuel.
That aside, with other fuel treatments (eg Redex) it suggests adding it to a full tank of fuel.
In short, I can't see it makes any difference when you use it, but using it on a nearly empty tank of fuel will mean its more concentrated.