In this study, MgNd intermetallic is deposited as a thin film using magnetron sputtering. Ultraviolet photoelectron spectroscopy (UPS) is employed to determine the work function of the MgNd thin film. It is found that the MgNd thin film has a low work function of 3.5 eV, leading to its application in hybrid poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) (PEDOT:PSS)/n-Si solar cells as a back surface field (BSF) material. By introducing a MgNd thin film into the back Si/electrode interface of a hybrid solar cell, obvious improvements in the open circuit voltage (V-oc) and fill factor (FF) of the device are observed, leading to an increase by more than 26% in power conversion efficiency (PCE). Temperature-dependent current density voltage (J-V) and V-oc light intensity measurements demonstrate that the introduction of a MgNd thin layer increases the built-in voltage at the rear interface and decreases the recombination current in the device. These improvements are attributed to the efficacy of the MgNd thin film as a BSF by reducing minority carrier recombination and enhancing majority carrier transport.