The characterization of a wide range of luminescent thin films can be a long and tedious endeavor. With reactive combinatorial sputtering of multiple metal targets, it possible to fabricate thin films with a gradient in composition simply by not rotating the substrate. In this work, combinatorically sputtered thin films of Cr³⁺ and Nd³⁺ doped in the Al₂O₃–Y₂O₃ system (YAlO) are studied for thin film based luminescent solar concentrators (TFLSCs) application. Contrary to mm's thick plate type LSC's, TFLSCs of just several 100 nm thick require much higher Cr³⁺ concentration to achieve 40% absorption which can enable several 10's of W/m² LSC power efficiencies. Our transmission measurements on a Cr₂O₃ film with a thickness gradient result in an absorption cross section at 460 nm of 1.3 ± 0.7 × 10⁻¹⁹ cm² showing that the TFLSC absorption requirement can be fulfilled provided that the Cr³⁺ concentration is in the order of 10²² ions/cm³. The Y:Al ratio of the YAlO host in our films ranged between 0.5 and 3.5, thereby including the monoclinic (Y₄Al₂O₉), perovskite (YAlO₃) and garnet (Y₃Al₅O₁₂) stoichiometry's on a single film. Position dependent XRD, EDX, excitation, emission and lifetime measurements of Cr³⁺ and Nd³⁺ show that the unique gradient film sputtering method is able to characterize thin films as a function of host composition and doping concentration. Energy transfer between Cr³⁺ and Nd³⁺ in co-doped YAlO films is concluded from Cr³⁺ excitation bands observed while monitoring Nd³⁺ emission and from the matching of the rise-time of Nd³⁺ 1340 nm emission (⁴F_3/2 -> ⁴I_11/2) and the decay time of Cr³⁺ 840 nm emission (⁴T₂ -> ⁴A₂). Nd³⁺ lifetime systematically decreases from 0.24 to 0.05 ms with increasing Cr³⁺ concentration in Y₃Al_5-xCr_xO₁₂:Nd (0.05 < x < 2). The constraints of heavily doped Cr³⁺ thin films for enabling adequate absorption and energy transfer to Nd³⁺ in TFLSC applications are the subjects of the discussion.