Ultrathin solar cells are efficient and captivating devices with unique technological and scientific features in terms of minimal material consumption, fast fabrication processes, and good compatibility with semi‐transparent applications. Such photovoltaic (PV) technologies can enable effective synergy between optical and electronic confinements with large tuning capabilities of all the optoelectronic characteristics. In this work, the implications of the optical design and the bandgap engineering in ultrathin hydrogenated amorphous Si/Ge multiple quantum well (MQW) solar cells featuring photonic nanocavity are analyzed based on experimental measurements and optoelectronic modelling. By changing the period thicknesses and the positions of QWs inside the deep‐subwavelength nanophotonic resonator, the spatial and spectral distributions of the optical field and the local absorption are strongly affected. This leads to a modulation of the absorption resonance condition, the absorption edge and the resulting photocurrent outputs. Because of quantum confinement effect, the change of MQW configurations with different individual QW periods while keeping similar total thickness of about 20 nm alters both the bandgap energy and the band offset at the QW/barrier heterojunctions. This in turn controls the photovoltage as well as the carrier collection efficiency in solar cells. The highest open circuit voltage and fill factor values are achieved by employing MQW device configuration with 2.5 nm‐thin QWs. A record efficiency above 5.5% is reached for such emerging ultrathin Si/Ge MQW solar cell technology using thinner QWs with sufficient number, because of the optimum trade‐off between all the optoelectronic characteristic outputs. The presented design rules for opaque ultrathin solar cells with quantum‐confined nanostructures integrated in a photonic nanocavity can be generalized for the engineering of relevant multifunctional semitransparent PV devices.
