• Zywitzki, D.; Mitoraj, D.; Vilk, Y.; Mendoza Reyes, O.; Schleuning, M.; Friedrich, D.; Sadlo, A.; Rogalla, D.; Eichberger, R.; Beranek, R.; Devi, A.: CVD grown GaSbxN1-x films as visible-light active photoanodes. Dalton Transactions 50 (2021), p. 14832-14841


The III–V semiconductor GaN is a promising material for photoelectrochemical (PEC) cells, however the large bandgap of 3.45 eV is a considerable hindrance for the absorption of visible light. Therefore, the substitution of small amounts of N anions by isovalent Sb is a promising route to lower the bandgap and thus increase the PEC activity under visible light. Herein we report a new chemical vapor deposition (CVD) process utilizing the precursors bis(N,N′-diisopropyl-2-methyl-amidinato)-methyl gallium (III) and triphenyl antimony (TPSb) for the growth of GaSbxN1−x alloys. X-ray diffraction (XRD) and scanning electron microscopy (SEM) measurements show crystalline and homogeneous thin films at deposition temperatures in the range of 500–800 °C. Rutherford backscattering spectrometry (RBS) combined with nuclear reaction analysis (NRA) shows an incorporation of 0.2–0.7 at% antimony into the alloy, which results in a slight bandgap decrease (up to 0.2 eV) accompanied by enhanced sub-bandgap optical response. While the resulting photoanodes are active under visible light, the external quantum efficiencies remained low. Intriguingly, the best performing films exhibits the lowest charge carrier mobility according to time resolved THz spectroscopy (TRTS) and microwave conductivity (TRMC) measurements, which showed mobilities of up to 1.75 cm2 V−1 s−1 and 1.2 × 10–2 cm2 V−1 s−1, for each timescale, respectively.