Crystalline silicon solar cells produced by doping processes have intrinsic shortages of high Auger recombination and/or severe parasitic optical absorption. Dopant-free carrier-selective contacts (DF-CSCs) are alternative routines for the next generation of highly efficient solar cells. However, it is difficult to achieve both good passivating and low contact resistivity for most DF-CSCs. In this paper, a high-quality dopant-free electron-selective passivating contact made from ultra-low concentration water solution is reported. Both low recombination current (J₀) ~10 fA/cm² and low contact resistivity (ρ_c) ~31 mΩ·cm² are demonstrated with this novel contact on intrinsic amorphous silicon thin film passivated n-Si. The electron selectivity is attributed to relieving of the interfacial Fermi level pinning because of dielectric properties (decaying of the metal-induced gap states (MIGS)). The full-area implementation of the novel passivating contact shows 20.4% efficiency on a prototype solar cell without an advanced lithography process. Our findings offer a very simple, cost-effective, and efficient solution for future semiconductor devices, including photovoltaics and thin-film transistors.