Okay, here's what I have so far: Pick $n-1$ linearly independent vectors in $\mathbb{R}^n$: $v_1,v_2,\ldots,v_{n-1}$. Then consider a small $U$ neighborhood of:
$$M_0 = \left(\begin{array}{ccccc} & & & & \\ v_1 & v_2 & \cdots & v_{n-1} & 0 \\ & & & & \end{array}\right)$$
And consider $U \cap X$, where $X$ is our set of matrices that have determinant zero. If $U$ is small enough, for every matrix in $U \cap X$ the first $n-1$ vectors will be linearly independent. That means for $M \in U \cap X$ there exist unique real numbers $a_1(M),a_2(M),\ldots,a_{k-1}(M)$ such that the nth column of $M \in U \cap X$ (let's write it as $v_n(M)$) can be written:
$$v_n(M) = a_1(M)v_1(M) + a_2(M)v_2(M) + \cdots + a_{n-1}(M)v_{n-1}(M)$$
And furthermore it is clear that the $a_i(M)$ depend continuously on $M$ (In fact, the $a_i$ should just be rational functions of the elements of $M$, so they should be smooth as well). Adding in variations of the first $n-1$ vectors, each of which looks like an open subset of $\mathbb{R}^n$, we get that $U \cap X$ is homeomorphic to an open subset of $\mathbb{R}^{n^2 - 1}$
Now, by looking at a neighborhood of another point (the origin?) we should be able to determine that $X$ is not a manifold... though I cannot figure out a proof.