The best you can do, in terms of small size and entries, is a $5\times5$ matrix with four $1$s and the rest $0$s, e.g. $$A=\begin{pmatrix}0&1&0&0&0\\0&0&1&0&0\\1&0&0&0&0\\0&0&0&0&1\\0&0&0&0&0\end{pmatrix}$$ Edit:
There are no $4\times4$ matrices with the desired properties.
Proof:
If you have a nonnegative $4\times4$ matrix with $0$s on the diagonal, then its characteristic polynomial's constant term is $\leq0.$ If it has a real eigenvalue with algebraic multiplicity two and two nonreal eigenvalues, then its characterisitic polynomial is a product of two monic quadratics, one of which has a constant term $\geq0,$ corresponding to the real eigenvalue with algebraic multiplicity two, and one of which has a positive constant term, corresponding to the two nonreal eigenvalues. Contra-diction.
The minimal number of nonzero entries is four.
Proof:
If you have a nonnegative $5\times5$ matrix $A$ with $0$s on the diagonal, then its monic characteristic polynomial's cubic term coefficient is $\leq0.$ If the number of nonzero entries in $A$ is less than four, then it has at least two zero rows and columns, hence the nullity of $A$ is at least two, and $0$ has algebraic multiplicity three. But now the remaining two eigenvalues are also real.
There are other configurations. Choose a quadratic term from the characteristic polynomial; the entries in its coefficient are $1$s. Next, choose an entry that's not in the span of the previous three, and not on the diagonal; it's a $1.$ The rest are $0$s.