Capturing Metastable Oxide Semiconductors for Applications in Solar Energy Conversion

Many small bandgap semiconductors have been discovered or predicted to exist beyond the edges of stability, that is, accessible only as metastable solids that are thermodynamically unstable. In many cases, these metastable semiconductors have been revealed to have technologically promising properties for solar energy conversion, such as in photocatalysis or in photovoltaics. This Account presents a review of research results selected from my group and others in recent years on these semiconductors. Notably, these include the chemical systems of mixed-metal oxides (i.e., M'MOx; M = Ti(IV) Nb(V), or Ta(V) cation; M' = Ag(I), Cu(I), Sn(II), Pb(II), or Bi(III) cation), which have diverse structure types and compositions. High photocatalytic activities have been found for the light-driven reduction or oxidation of water as p- or n-type photoelectrodes, respectively, or as suspended powders in aqueous solutions. These have exhibited new combinations of favorable semiconductor properties, such as deep visible-light absorption, near-optimal band edge energies, defect tolerance, and functional carrier mobilities and charge separation. As described herein, this set of properties is inextricably linked to their metastable nature, that is, the crystalline structures and compositions needed for these characteristics lead naturally to thermodynamic instabilities. This Account focuses on current research efforts that have begun unlocking the potential of these semiconductors via new recent advances in (1) synthetic approaches that enable their preparation and (2) the understanding of structure-property relationships discovered at the precipices of stability that lead to the improved semiconductor properties. For example, low-temperature reactions have been developed to facilitate greater kinetic control, such as with the use of molten salts, and have been a key factor in preparing many of these semiconductors. As a result, a plethora of promising new mixed-metal oxide systems have been uncovered that exhibit band gaps spanning the range of photon energies from similar to 1.3 to >3.0 eV. Especially relevant for visible-light applications are the Cu(I)- and Sn(II)-containing semiconductors. For example, n-type Sn(II)-titanates and p-type Cu(I)-niobates can be synthesized by flux methods and exhibit some of the smallest known visible-light band gaps that also maintain suitable conduction and valence band edges for driving the water-splitting half reactions. Kinetic stabilization of these metastable semiconductors against thermally driven phase segregation is increased with the formation of solid solutions for both the M and M' cation sites, leading to effective strategies to more finely tune their band gaps, band edge energies, and photoelectrochemical properties. Many unique and useful relationships are emerging between the synthesis and structures of metastable semiconductors and their physical properties, leading to more efficient solar energy conversion.

Automated summary

Many small bandgap semiconductors with promising properties for solar energy conversion have been discovered as metastable solids, showing high photocatalytic activities and suitable semiconductor properties. Current research efforts are focused on unlocking the potential of these semiconductors through new advances in synthetic approaches and understanding of structure-property relationships.