Systems and methods are provided for nonvolatile memory devices that incorporate a band-gap engineered gate stack with asymmetric tunnel barriers. One embodiment of a memory device includes first and second source / drain regions separated by a channel region in a substrate, a control gate, and a gate stack between the control gate and the channel region. The gate stack includes a first insulator region in contact with the channel region, a floating charge-storage region in contact with the first insulator region, and a second insulator region in contact with the floating charge-storage region and the control gate. The gate stack includes selected material, in conjunction with control gate metallurgy, for providing desired asymmetric energy barriers that are adapted to primarily restrict carrier flow during programming to a selected carrier between the control gate and the floating charge-storage region, and to retain a programmed charge in the floating charge-storage region. Other aspects are provided herein.