Czochralski-grown bulk β-Ga2O3 single crystals doped with mono-, di-, tri-, and tetravalent ions

The present report relates to a systematic study of dopant incorporation into bulk β-Ga2O3 single crystals grown by the Czochralski method, and their impact on growth stability, crystal appearance (growth habit), electrical properties, and transmittance of the obtained crystals. At very similar growth conditions, the dopant incorporation is driven mainly by ionic radii difference between dopant and Ga3+ ion and by thermal stability of the dopant during crystal growth. Good growth stability was achieved with Li1+, Mg2+, Co2+, Ni2+, Ce3+, Al3+, and Ge4+ doping, as that resulted in lowering or entirely compensating the free electron concentration (ne), and, in some cases, presence of additional oxygen through a dopant oxide/carbonate decomposition that is added to the starting material. Undoped crystals had the ne of 2.5 × 1016–2 × 1018 cm−3 with the Hall mobility of 80–152 cm2 V−1 s−1. The ne within that range was also achieved by doping the melt with Li1+, Cu1+, Cr3+, Ce3+, and Ge4+. The two former (Li, Cu) and the latter (Ge) dopants entirely evaporate during or even before growth due to very high partial pressures, but at the same time they leave in the melt extra oxygen that affect to some extent (depending on its initial concentration) the ne. Therefore, we provide a new tool to control the free electron concentration at low levels (ne = 1016–1017 cm−3) by doping a Ga2O3 starting material with thermally unstable oxides or carbonates (such as GeO2 or Li2CO3) that undergo thermal decomposition at high temperatures with entirely evaporated cations and released in the melt an extra oxygen (dopant acting as an additional oxygen source). Si4+ and Sn4+ increase the ne to 2.5 × 1018–1019 cm−3, consistent with previous studies. At such high ne, the Hall mobility drops to values of 50–84 cm2 V−1 s−1. Divalent ions (Mg2+, Co2+, Ni2+) and trivalent Al3+ made the crystals electrically insulating. We also empirically showed that the underlying conductivity of undoped β-Ga2O3 crystals is caused by residual solid impurities, mainly by Si4+ and hydrogen, the latter could be easily removed by annealing. The transmittance near the absorption edge is not affected by the dopants at studied concentrations, except Cr3+, Co2+, and Ni2+ that introduce an extra absorption in the UV and blue spectral regions, and Al3+ that slightly shifts the absorption edge towards shorter wavelengths.