To investigate the origin of the Na effect on photovoltaic (PV) devices, Cu(In,Ga)Se 2 (CIGS) and CdS/ CIGS layers were grown on borosilicate (BS) and soda-lime glass (SLG), respectively. The defect states and nonequilibrium carrier dynamics of the samples were measured using photoluminescence (PL) and optical pump-THz probe (OPTP) spectroscopy. From the PL results, we discovered that different shallow donor−acceptor levels were formed in the CIGS layer grown on BS and SLG, respectively. In the OPTP results, relaxation times of photocarriers excited from the CdS/CIGS layer were clearly distinguishable, and are explained by the formation of different defect states depending on substrates. In BS, deep defect level 'DX states' were formed in the E g near the p−n junction, which induce trapping photocarriers, resulting in shortening relaxation time. In SLG, there was no "DX state", which clearly demonstrates the positive effect of Na atoms at the p−n junction on performance of PV devices.

We fabricated Cu(In,Ga)Se2 (CIGS) solar cells with a chemical bath deposition (CBD)-ZnS buffer layer grown with varying ammonia concentrations in aqueous solution. The solar cell performance was degraded with increasing ammonia concentration, due to actively dissolved Zn atoms during CBD-ZnS precipitation. These formed interfacial defect states, such as hydroxide species in the CBD-ZnS film, and interstitial and antisite Zn defects at the p-n heterojunction. After light/UV soaking, the CIGS solar cell performance drastically improved, with a rise in fill factor. With the Zn-based buffer layer, the light soaking treatment containing blue photons induced a metastable state and enhanced the CIGS solar cell performance. To interpret this effect, we suggest a band structure model of the p-n heterojunction to explain the flow of photocarriers under white light at the initial state, and then after light/UV soaking. The determining factor is a p+ defect layer, containing an amount of deep acceptor traps, located near the CIGS surface. The p+ defect layer easily captures photoexcited electrons, and then when it becomes quasi-neutral, attracts photoexcited holes. This alters the barrier height and controls the photocurrent at the p-n junction, and fill factor values, determining the solar cell performance.

The proposed safe and cheap method for enhanced sulfur reaction enables the formation of high-quality chalcogenide thin films.

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