$n$ is prime iff $\binom{n^2}{n} \equiv n \pmod{n^4}$?
Unfortunately, it appears that the claim is false. My counterexample is $n=16843^2$. Note that $16843$ is a Wolstenholme prime. Henceforth set $p=16843$ (so that our counterexample is $n=p^2$).
Here is the "proof" of my counterexample, which seems to be too large to compute directly (crashed the Sage program and Wolfram didn't understand it directly, so more work was needed).
Note that it suffices to show $$\binom{p^4}{p^2}\equiv p^2\pmod{p^8}.$$ By CAMO 2020/2, since $p=16843>3$, then we have $$\binom{p^4}{p^2}\equiv \binom{p^3}p\pmod{p^9}$$ which is of course strong enough to tell us that $$\binom{p^4}{p^2}\equiv \binom{p^3}p\pmod{p^8}.$$
Now, Wolfram Alpha computes $$\binom{p^3}{p}-p^2\equiv 0\pmod{p^8},$$ which implies $$\binom{p^4}{p^2}\equiv p^2\pmod{p^8},$$ which proves that the counterexample $n=p^2$ works.
Note: With enough work, I think that it's possible to show without using computer aid that $n=p^2$ is a counterexample iff $p$ is a Wolstenholme prime.
EDIT: I have figured out a proof that all $n=p^2$ for $p$ a Wolstenholme prime are counterexamples. Follow the solution posted by TheUltimate123 here, and modify the falling factorial congruence lemma to hold modulo $p^{k+3}$. The proof works the exact same except for two changes: First, we prove the lemma only for $i=0$, as the $n$ in the problem is equal to 1 (as in $\binom{p^3}{p\cdot 1}$). Also, we use the fact that $p$ is a Wolstenholme prime to note $$\sum_{j=1}^{p-1} \frac1j\equiv 0\pmod{p^3},$$ so that the lemma may hold modulo $p^{k+3}$.
This gives us the following lemma: for Wolstenholme primes $p$, $$\binom{p^k}{p}\equiv p^{k-1}\pmod{p^{2k+2}}.$$
Now, to finish, note $$\binom{p^4}{p^2}\equiv\binom{p^3}p\pmod{p^{2\cdot 4+1}}$$ and $$\binom{p^3}{p}\equiv p^2\pmod{p^{2\cdot 3+2}}$$ which combined implies that for all Wolstenholme primes $p$, $$\binom{p^4}{p^2}\equiv p^2\pmod{p^8}.$$
Interesting Aside (delete if off-topic): CAMO 2020/2 tells us that all primes $p>3$ satisfy $$\binom{p^2}p\equiv p\pmod{p^5},$$ so perhaps a better question to ask would be: Is it true that for all natural numbers $n>3$, $$\binom{n^2}n\equiv n\pmod{n^5}\iff n\in\mathbb P?$$ Note that in this case $n=16843^2$ is not a counterexample (Wolfram Alpha confirms that the congruence does not even hold modulo $16843^9$)...
Note that $\displaystyle\binom{n^2}{n} = \frac{1}{(n - 1)!} \frac{n^2 (n^2 - 1) ... (n^2 - (n - 1))}{n} = \frac{1}{(n - 1)!} n (n^2 - 1) ... (n^2 - (n - 1))$
Consider a prime $p > 2$. Then $1, 2, ..., p - 1$ are all invertible modulo $p^4$; thus, so is $(p - 1)!$. Now consider $\displaystyle\binom{p^2}{p} = \frac{1}{(p - 1)!} p (p^2 - 1) ... (p^2 - (p - 1))$.
Define the polynomial $P(x) = x (x^2 - 1) (x^2 - 2) ... (x^2 - (p - 1))$. We wish to reduce $P(x)$ modulo $x^4$. We note that this will only have an $x$ and $x^3$ term since $P$ is odd. The $x$ term will clearly be $(p - 1)! x$; the $x^3$ term will be $-(p - 1)! x^3 \left(\frac{1}1 + \frac{1}2 + \cdots + \frac{1}{p - 1}\right)$. Then mod $p^4$, we have $\displaystyle \binom{p^2}{p} = p - p^3 \left(\frac{1}1 + \frac{1}2 + \cdots+ \frac{1}{p - 1}\right)$ (taking division modulo $p^4$ as well).
Note that when reducing $\mod p$, we have $\frac{1}1 + \frac{1}2 + \cdots + \frac{1}{p - 1} = 1 + 2 + ... + (p - 1)$, since every number from $1$ to $p - 1$ is a unit. And this sum is equal to $\frac{p (p - 1)}{2} \equiv 0 \pmod p$, since $p > 2$. Thus, we see that $\frac{1}1 + \frac{1}2 + \cdots + \frac{1}{p - 1}$ will be divisible by $p$ when the division is done $\mod p^4$ as well.
Thus, we have that for all $p>2$ prime, $\displaystyle \binom{p^2}{p} \equiv p \pmod {p^4}$.
I don't have anything going the other direction yet.
Iff $p$ is prime, you'll find that
$$\binom{p^{a+k}}{p^a}\equiv p^k \pmod{p^r}, \text{ for }k<r<8\text{ and }a>0\ .$$
So, for example $$\binom{n^7}{n^5} \equiv n^2 \pmod{n^{3}}$$ would work just as well.