Solar cells based on a high-efficiency silicon nanostructure (SNS) were developed using a two-step metal-assisted electroless etching (MAEE) technique, phosphorus silicate glass (PSG) doping and screen printing. This process was used to produce solar cells with a silver nitrate (AgNO3) etching solution in different concentrations. Compared to cells produced using the single MAEE technique, SNS-based solar cells produced with the two-step MAEE technique showed an increase in silicon surface coverage of ?181.1% and a decrease in reflectivity of ?144.3%. The performance of the SNS-based solar cells was found to be optimized (?11.86%) in an SNS with a length of ?300 nm, an aspect ratio of ?5, surface coverage of ?84.9% and a reflectivity of ?6.1%. The ?16.8% increase in power conversion efficiency (PCE) for the SNS-based solar cell indicates good potential for mass production. Copyright 2014 IOP Publishing Ltd.