Each of the functions $\phi_n$ is Borel, therefore the set $A$ of all points $x$ such that $\phi_n(x)$ diverges is a Borel set (standard exercise). But there exist null sets $S$ that are not Borel; for instance, all of the $2^{\mathbb{c}}$ subsets of the Cantor set are null, but there are only $\mathfrak{c}$ many Borel sets in total. See also Is there a null set that is not a Borel set?, Lebesgue measurable but not Borel measurable. So if we take $S$ to be such a set, then there cannot exist any sequence of step functions $\phi_n$, nor indeed any sequence of Borel functions, such that $\phi_n(x)$ diverges iff $x \in S$.
In other words, if $S$ is such a set, Weir's result will show you can find an increasing sequence of step functions $\phi_n$ such that $\phi_n(x)$ diverges for every $x \in S$ and $\int \phi_n$ converges, but there will always also be some $x \notin S$ (indeed, uncountably many) for which $\phi_n(x)$ diverges as well.
With a little more care, one can show that for step functions $\phi_n$, the set $A$ is necessarily a countable intersection of countable unions of closed sets, denoted $F_{\sigma \delta}$ or $\mathbf{\Pi}^0_3$ in the Borel hierarchy. Since the Borel hierarchy doesn't collapse, I think this shows there are Borel subsets of the Cantor set which are not $F_{\sigma \delta}$ and therefore one could find Borel counterexamples as well.
I think Weir's terminology "characterization" is not wrong, in that it does give a necessary and sufficient condition for a set to be null, but it has to be interpreted carefully. The following statement is what he proved:
A set $S$ is null if and only if there exists an increasing sequence of step functions $\phi_n$, with $\int \phi_n$ convergent, such that $x \in S \implies \phi_n(x)\text{ diverges}$.
You seem to be thinking of the following different statement, which is false:
(FALSE) A set $S$ is null if and only if there exists an increasing sequence of step functions $\phi_n$, with $\int \phi_n$ convergent, such that $x \in S \Longleftrightarrow \phi_n(x)\text{ diverges}$.