We consider periodic homogenization of the linear elliptic equation \(-A(x/\varepsilon ):D^2 u^{\varepsilon } = f\) posed in a smooth domain \(\Omega \) subject to the Dirichlet boundary condition \(u^{\varepsilon } = g\) on \(\partial \Omega \) . It is known that, while the optimal \(L^{\infty }\) -rate for the convergence of \((u^{\varepsilon })_{\varepsilon > 0}\) to the solution of the homogenized problem is generically only \(\mathcal {O}(\varepsilon )\) , those diffusion matrices A for which the symmetric part of the third-order homogenized tensor vanishes lead to a \(L^{\infty }\) -rate of \(\mathcal {O}(\varepsilon ^2)\) for all sufficiently regular f and g. In this work, we seek more explicit characterizations of such “type- \(\varepsilon ^2\) diffusion matrices" than the one via the third-order homogenized tensor. We start by providing a new class of type- \(\varepsilon ^2\) diffusion matrices, confirming an open conjecture. Thereafter, we give a complete characterization of diagonal type- \(\varepsilon ^2\) diffusion matrices in two dimensions and a systematic study in higher dimensions.