Semiconductors have numerous applications in both science and technology. Several methods have been developed to engineer their band gap, which is one of the most important parameters of semiconductors. Here, it is shown that the incorporation of various amino acids into the crystal lattice of copper (I) oxide, akin to the way living organisms incorporate organic macromolecules into minerals during biomineralization, leads to significant shrinkage in the volume of the host unit cell and a strong blueshift in the band gap of up to ≈18%. In examining the potential location of the bio‐organic molecules within the inorganic host's lattice, a very good fit between the proposed model of incorporation and experimental findings is found. The bioinspired phenomenon of band gap widening is thought to be attributable to the void‐induced quantum confinement effect, even though observed in micrometer‐sized crystals. This hypothesis is supported by developing a tight‐binding model that is found to fit well with the experimental data. The outcome of this research could profoundly impact the fields of light‐emitting and spin‐based devices as well as opens up a new bioinspired route to tune the band gap of semiconductors.

Biominerals are organic-inorganic nanocomposites exhibiting remarkable properties due to their unique configuration. Using optical spectroscopy and theoretical modeling, it is shown that the optical properties of a model bioinspired system, an inorganic semiconductor host (Cu 2 O) grown in the presence of amino acids (AAs), are strongly influenced by the latter. The absorption and photoluminescence excitation spectra of Cu 2 O-AAs blue-shift with growing AA content, indicating band gap widening. This is attributed to the void-induced quantum confinement effects. Surprisingly, no such shift occurs in the emission spectra. The theoretical model, assuming an inhomogeneous AA distribution within Cu 2 O-AAs due to compositional disorder, explains the deviating behavior of the photoluminescence. The model predicts that the potential causing the confinement effects becomes a function of the local AA density. It results in a Gaussian band gap distribution that shapes the optical properties of Cu 2 O-AAs. Imitating and harnessing the process of biomineralization can pave the way toward new functional materials.