We develop a general nonperturbative formalism and propose a specific scheme for maximally efficient generation of biphoton states by parametric decay of single photons. We show that the well-known critical coupling concept of integrated optics can be generalized to the nonlinear coupling of quantized photon modes to describe the nonperturbative optimal regime of a single-photon nonlinearity and establish a fundamental upper limit on the nonlinear generation efficiency of quantum-correlated photons, which approaches unity for low enough absorption losses.