The valence band offsets of chalcopyrite ZnSnP2 (ZSP), CdSnP2 (CSP), CuInSe2 (CIS), and CuGaSe2 (CGS) against zincblende CdS and ZnS are obtained using first-principles calculations based on hybrid density functional theory. The ZSP-CSP (ZCSP) alloy is isostructural to the CIS-CGS (CIGS) alloy and is known for its potential usage in photovoltaic applications. Therefore, the band offsets with other semiconductors, such as CdS and ZnS, are important. The calculated valence band offsets are ∼1.0 eV for ZSP/CdS and CSP/CdS, ∼1.2 eV for ZSP/ZnS and CSP/ZnS, ∼1.2 eV for CIS/CdS and CGS/CdS, and ∼1.3 eV for CIS/ZnS and CGS/ZnS. The CdS/ZnS valence band offset is within 0.1 eV. Transitivity of natural valence band offsets in the investigated semiconductors holds within ∼0.1 eV, which is smaller than the error in band alignment of ∼0.2 eV when ionization potential differences are used. The ZSP-CSP and CIS-CGS systems have similar valence and conduction band positions, which is an important piece of information for band offset engineering in the development of photovoltaics using ZCSP alloys.

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