A multilayered structure including a first barrier layer adjacent to a substrate, a barrier bi-layer adjacent to the first barrier layer, the barrier bi-layer comprising a second barrier layer and a third barrier layer, a transparent conductive oxide layer adjacent to the barrier bi-layer, and a buffer layer adjacent to the transparent conductive oxide layer and method of forming the same. A multilayered substrate including a barrier layer structure having a plurality of barrier layers being alternating layers of low refractive index material and high refractive index material, a transparent conductive oxide layer adjacent to the barrier bi-layer and a buffer layer adjacent to the transparent conductive oxide layer. The multilayered structure may serve as a front contact for photovoltaic devices.