So, $W$ is the space given by
$$
W = \left\{\pmatrix{2t&0\\0&-t}: t \in \Bbb R\right\}
$$
What we are looking for is $W^\perp$, which by definition is
$$
W^\perp = \left\{V \in M_{2 \times 2}: \langle U,V \rangle = 0 \text{ for every } U \in W \right\}
$$
However, applying all of the above definitions, we can rewrite this statement as
$$
W^\perp = \left\{\pmatrix{a_1 & a_2\\a_3 & a_4}:
(2t)a_1 + (0)a_2 + (0)a_3 + (-t)a_4 = 0 \text{ for every } t \in \Bbb R \right\}
$$
That is, we want to find the set of quadruples ("vectors") $(a_1,a_2,a_3,a_4)$ such that
$$
2ta_1 + -ta_4 = 0 \text{ for every } t \in \Bbb R
$$
which is to say that we want the set of vectors $(a_1,a_2,a_3,a_4)$ such that
$$
2a_1 - a_4 = 0
$$
Equivalently, we want to find the solution set of the matrix equation
$$
\pmatrix{2 & 0 & 0 & -1} \pmatrix{a_1\\a_2\\a_3\\a_4} = 0
$$
You should be able to find a basis consisting of $3$ elements.