In this paper, we design constant modulus probing waveforms with good correlation properties for large-scale collocated multi-input multi-output (MIMO) radar systems. The main content is as follows: First, we formulate the design problem as a fourth-order polynomial minimization problem with unimodulus constraints. Then, by analyzing the geometric properties of the unimodulus constraints through Riemannian geometry theory and embedding them into the search space, we transform the original non-convex optimization problem into an unconstrained problem on a Riemannian manifold for solution. Second, we convert the objective function into the form of a large but finite number of loss functions and employ a customized R-SVRG algorithm to solve it. Third, we prove that the customized R-SVRG algorithm is theoretically guaranteed to converge if appropriate parameters are chosen. Numerical examples demonstrate the effectiveness of the proposed R-SVRG algorithm.