Stacked white organic light-emitting devices (WOLEDs) comprising of blue fluorescent and orange phosphorescent emissive units employing tri(8-hydroxyquinoline) aluminum (Alq3):Mg/MoO3 as charge generation layer are fabricated. The working mechanism of Alq3:Mg/MoO3 is also discussed using a simple method. We demonstrate charge-carrier separation takes place only in MoO3 layer. Stacked WOLED with better performance was obtained by adjusting the thickness of MoO3. The stacked WOLED with efficiency of 39.2 cd/A has excellent color stability with the Commission Internationale de l’Eclairage coordinates only changing from (0.407, 0.405) to (0.398, 0.397) when luminance increases from 22 to 10000cd/m2.

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