Let's say we have the congruence: $b \equiv a \mod 20$
Is it then correct to say that $(b \equiv a \mod 20 )= \mathbb{Z}_{20}$ where $\mathbb{Z}_{20}$ is the set of residue classes or set of equivalence classes of the congruence $b \equiv a \mod 20?$ (So $\mathbb{Z}_{20}=\{{[0],[1],[2],[3],[4], ..., [19]}$}
No, that is not proper notation. It seems you wish to state that all possible remainders yields a complete set of representatives for $\,\Bbb Z_{20}.\,$ This can be stated (close to your presentation) as follows:
$$\{\, b\in \Bbb Z\ :\ b = (a\bmod 20)\ \ \text{for some } a \in \Bbb Z\} = \Bbb Z_{20}$$
Equivalently, $\ \Bbb Z\bmod 20 = \Bbb Z_{20}\,$ if you define $\bmod$ on sets (but some may object to such notation).
If you wish to work with equivalence (congruence) classes vs. remainders then it is simpler
$$\{ \,[\,a\,]_{20}\ :\ a\in \Bbb Z\} = \Bbb Z_{20} = \Bbb Z/20\Bbb Z$$