See Sloane, A046747 for the number of singular (0,1)-matrices. It doesn't seem like there's an exact formula, but it's conjectured that the probability that a random (0,1)-matrix is singular is asymptotic to $n^2/2^n$.

Over $F_2$ the probability that a random matrix is nonsingular, as $n \to \infty$, approaches the product $(1/2)(3/4)(7/8)\cdots = 0.2887880951$, and so the probability that a random large matrix is singular is only around 71 percent. I should note that a matrix is singular over $F_2$ if its real determinant is even, so this tells us that determinants of 0-1 matrices are more likely to be even than odd.

See Sloane, A046747 for the number of singular (0,1)-matrices. It doesn't seem like there's an exact formula, but it's conjectured that the probability that a random (0,1)-matrix is singular is asymptotic to $n^2/2^n$.

Over $F_2$ the probability that a random matrix is nonsingular, as $n \to \infty$, approaches the product $(1/2)(3/4)(7/8)\cdots = 0.2887880951$, and so the probability that a random large matrix is singular is only around 71 percent. I should note that a matrix is singular over $F_2$ if its real determinant is even, so this tells us that determinants of 0-1 matrices are more likely to be even than odd.