Wide Band Gap Chalcopyrite Photoelectrodes for Direct Water Splitting (Final Technical Report)

Abstract

The chalcopyrite material class, typically identified by its most popular alloy CuInGaSe2, provides exceptionally good candidates for photoelectrochemical (PEC) water splitting and has the potential to meet DoE EERE’s targets in terms of hydrogen production costs (less than $2/gge). Some key advantages of this class include remarkable photon-to-electron conversion efficiency and a high Faradaic efficiency for the hydrogen evolution reaction, two characteristics essential for efficient PEC water splitting. However, the band gaps of commonly used chalcopyrites in the photovoltaic field (1.0-1.6 eV) are too narrow to be compatible with the multi-junction approach for efficient PEC hydrogen production, in which a stack of solar absorbers generates the bias required for water splitting. Nonetheless, previous studies performed by our team demonstrated that chalcopyrites’ narrow band gaps could be effectively widened using simple conversion steps, leading to functional chalcopyrite-based PEC electrodes with optical band gap in the 1.8-2.4 eV range, making this class highly suitable for renewable hydrogen production via water splitting. This multi-disciplinary research program lead by the University of Hawai’i/Hawai’i Natural Energy Institute combined unique analytical techniques (UNLV), state-of-the-art theoretical modeling (LLNL) with advanced thin film materials synthesis (HNEI, NREL and Stanford) to provide deeper understanding of wide band gap chalcopyrite-based PEC materials and engineer high performance/corrosion-resistant photocathodes with tunable energetics and compatible with the multi-junction approach. The goals of this project were to demonstrate photoelectrochemical (PEC) solar-hydrogen production using a dual absorber system with a solar-to-hydrogen conversion efficiency of at least 15% with an operational life up to 2,000 hours and capable of generating at least 3 liters of hydrogen in 8 hours. After a brief introduction (Section 1) and description of our work plan (Section 2), we present in Section 3 our results on the development of new wide bandgap copper chalcopyrites absorbers for PEC waters splitting. We first show through modeling how alloying can be used to tailor the optical properties and/or surface energetics of various material candidates. We also present how specific defects (e.g., GaCu) can lead to recombination centers within the forbidden gap of copper-poor chalcopyrites. Then, we present our efforts to synthesize high efficiency wide band gap CuGa3Se5, CuGa(S,Se)2 and Cu(In,Ga)S2 photocathodes capable of generating photocurrent density over 10 mA/cm2. We also demonstrate that Cu-rich absorbers should be avoided as they lead to poor sub-band gap optical transmission. In Section 4, we first report on our efforts to tune the energetics of chalcopyrites toward the hydrogen evolution reaction. First, we quantified the energetics of wide band gap chalcopyrites interfaced with conventional CdS buffer layer, as measured with X-ray photoelectron spectroscopy techniques, and evidence the presence of a large (and undesirable) conduction band offset at this interface. Then, we highlight some of the work performed with alternative buffer layers, including In2S3. Durability improvements with various ultra-thin protective layers are presented in Section 5. Our data show that TiO2 combined with MoS2 can significantly improve chalcopyrites lifetime up to 350 hours under continuous operation at 8 mA/cm2. Finally, in Section 6 we report strategies to integrate chalcopyrite photocathodes into standalone tandem PEC devices. Although promising methods were proposed for both mechanical and monolithic stacking with narrow band gap PV drivers, no functional device was fabricated on time to fulfill the program end goals.