The dopant-related issues are amongst the major performance bottleneck in crystalline silicon solar cells that can be alleviated via implementation of dopant-free layers. This work presents the implementation of tungsten oxide (WOx) and titanium oxide (TiOx) as hole- and electron-selective films for heterostructure solar cell design whereby n-type Si wafer has been passivated with ultrathin silicon oxide (SiO2) layer. Several designs have been investigated including passivated hydrogenated amorphous silicon (i-a-Si:H) and characterized by evaluating work function, electron affinity, interfacial charge, and layer thickness. The high work function of WOx induces significant upward band bending to permit holes transportation towards anode, whereas, low electron-affinity for TiOx reduces the barrier against electrons at the cathode. Smaller band offsets have been observed against minority carriers for devices that employ passivated i-a-Si:H film. However, incorporating SiO2 significantly improves the energy barrier height against minority carriers that leads to an enhancement in electric field along with reduction in recombination. The best-performance device with an optimum SiO2 thickness of 1 nm numerically validated V-oc of 751 mV, J(sc) 40.2 mA/cm(2), FF 79.7%, and rl of 24.06%. A comparative analysis with hole-selective vanadium oxide (V2Ox) demonstrated eta of 21.73% limited by the low work function of V2Ox. (C) 2021 Elsevier Ltd. All rights reserved.