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Grading of bandgap by alloying CdTe with selenium to form a CdSexTe1–x/CdTe‐graded bilayer device has led to a device efficiency over 19%. A CdSexTe1–xabsorber would increase the short‐circuit current due to its lower bandgap but at the expense of open‐circuit voltage. It has been demonstrated that adding a CdTe layer at the back of such a CdSexTe1–xfilm reduces the voltage deficit caused by the lower bandgap of absorber from selenium alloying while maintaining the higher short‐circuit current. This leads to a photovoltaic device that draws advantage from both materials with an efficiency greater than either of them. Herein, a detailed account using device data, ultraviolet photoelectron spectroscopy, electron microscopy, and first‐principles density functional theory modeling is provided, which shows that CdTe acts as an electron reflector for CdSexTe1–x.more » « less
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