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$CuGa_3Se_5$ is a promising candidate material with wide band gap for topcells in tandem photovoltaic (PV) and photoelectrochemical (PEC) devices.However, traditional CdS contact layers used with other chalcopyrite absorbersare not suitable for $CuGa_3Se_5$ due to the higher position of its conductionband minimum. $Mg_xZn_{1-x}O$ is a transparent oxide with adjustable band gapand conduction band position as a function of magnesium composition, but itsdirect application is hindered by $CuGa_3Se_5$ surface oxidation. Here,$Mg_xZn_{1-x}O$ is investigated as a contact (n-type buffer or window) materialto $CuGa_3Se_5$ absorbers pretreated in $Cd^{2+}$ solution, and an onsetpotential close to 1 V vs RHE in 10 mM hexaammineruthenium (III) chlorideelectrolyte is demonstrated. The $Cd^{2+}$ surface treatment changes thechemical composition and electronic structure of the $CuGa_3Se_5$ surface, asdemonstrated by photoelectron spectroscopy measurements. The performance of$CuGa_3Se_5$ absorber with $Cd^{2+}$ treated surface in the solid-state teststructure depends on the Zn/Mg ratio in the $Mg_xZn_{1-x}O$ layer. The measuredopen circuit voltage close to 1 V is promising for tandem PEC water splittingwith $CuGa_3Se_5$/$Mg_xZn_{1-x}O$ top cells.

$Mg_xZn_{1-x}O$ contact to $CuGa_3Se_5$ absorber for photovoltaic and photoelectrochemical devices