If $Y,Z\sim U(0,1)$ then $S=Y+Z$ is distributed as $$f_S(s)=\left\{\begin{array}{cc} s & 0<s<1\\ 2-s,& 1<s<2,\\ 0&\text{else}\end{array}\right.$$ (See for instance Density of sum of two independent uniform random variables on $[0,1]$. ) For intuition, note that the diagonal range of your blue/red square starts at zero in one corner, rises linearly towards the middle of the square, and then returns to zero. As such, it should be reasonable that $S$ has a triangular distribution.
As such, our problem is now to compute $\text{Pr}(X>S)$ where $X\sim U(0,1)$ and $S$ is distributed as above. The corresponding blue/red picture is similar, but the vertical width of the blue stripe (corresponding to the smaller variable) is $2$ rather than $1$. Moreover, we have to account for the variable density of $S$. Life is made simpler, however, by the fact that we only care about $s<x<1$ and so can take $f_S(s)=s$. Keeping this in mind, we have
$$\text{Pr}(X>S)=\int_{x=0}^1\int_{s=0}^x f_S(s)f_X(x)\,ds\,dx=\int_0^1\int_0^x s^2\,ds\,dx=\int_0^1 \frac13 x^2\,dx=\frac{1}{6}$$
in agreement with the geometric answer.