Any square matrix is invertible if all column vectors are linearly independent. For an $n\times n$ matrix filled with $0$'s and $1$'s, consider how many choices there are for the first column: all it has to be is not all $0$, so there are $2^n-1$ choices. For the second column, all it has to be is linearly independent to the first column, so there are
$\displaystyle{2^n-\underbrace{1}_{\text{the zero vector}}-\underbrace{1}_{\text{whatever the first column vector was}}=2^n-2}$
choices (assuming we're working in a field of characteristic 2). Carrying on, we get
$\displaystyle{(2^n-1)(2^n-2)\cdots(2^n-2^{n-1})}$
ways to build this matrix. Just a quick check, this formula gives 6 for $2\times 2$ matrices, which is correct.
The answer only works in fields of characteristic 2.