Role of carbon and hydrogen in limiting $n$-type doping of monoclinic (Al$_x$Ga$_{1-x}$)$_2$O$_3$

Abstract: We use hybrid density functional calculations to assess n-type doping in monoclinic (Al$x$Ga${1-x}$)$2$O$_3$ alloys. We focus on Si, the most promising donor dopant, and study the structural properties, formation energies and charge-state transition levels of its various configurations. We also explore the impact of C and H, which are common impurities in metal-organic chemical vapor deposition (MOCVD). In Ga$_2$O$_3$, Si${Ga}$ is an effective shallow donor, but in Al$2O_3$ Si${Al}$ acts as a DX center with a (+/-) transition level in the band gap. Interstitial H acts as a shallow donor in Ga$2$O$_3$, but behaves as a compensating acceptor in n-type Al$_2O_3$. Interpolation indicates that Si is an effective donor in (Al$_x$Ga${1-x}$)$2$O$_3$ up to 70% Al, but it can be compensated by H already at 1% Al. We also assess the diffusivity of H and study complex formation. Si${cation}$-H complexes have relatively low binding energies. Substitutional C on a cation site acts as a shallow donor in Ga$2$O$_3$, but can be stable in a negative charge state in (Al$_x$Ga${1-x}$)$2$O$_3$ when x>5%. Substitutional C on an O site (C$_O$) always acts as an acceptor in n-type (Al$_x$Ga${1-x}$)$2$O$_3$, but will incorporate only under relatively O-poor conditions. C$_O$-H complexes can actually incorporate more easily, explaining observations of C-related compensation in Ga$_2$O$_3$ grown by MOCVD. We also investigate C${cation}$-H complexes, finding they have high binding energies and act as compensating acceptors when x>56%; otherwise the H just passivates the unintentional C donors. C-H complex formation explains why MOCVD grown Ga$_2$O$_3$ can exhibit record-low free-carrier concentrations, in spite of the unavoidable incorporation of C. Our study highlights that, while Si is a suitable shallow donor in ALGO alloys, control of unintentional impurities is essential to avoid compensation.