Dowon Bae

Iron-Treated NiO as a Highly Transparent p-Type Protection Layer for Efficient Si-Based Photoanodes

Sputter deposition of 50 nm thick NiO films on p(+)-n-Si and subsequent treatment in an Fe-containing electrolyte yielded highly transparent photoanodes capable of water oxidation (OER) in alkaline media (1 M KOH) with high efficiency and stability. The Fe treatment of NiO thin films enabled Si-based photoanode assemblies to obtain a current density of 10 mA/cm(2) (requirement for >10% efficient devices) at 1.15 V versus RHE (reversible hydrogen electrode) under red-light (38.6 mW/cm(2)) irradiation. Thus, the photoanodes were harvesting ∼80 mV of free energy (voltage), which places them among the best-performing Si-based photoanodes in alkaline media. The stability was proven by chronoamperometry at 1.3 V versus RHE for 300 h. Furthermore, measurements with electrochemical quartz crystal microbalances coupled with ICP-MS showed minor corrosion under dark operation. Extrapolation of the corrosion rate showed stability for more than 2000 days of continuous operation. Therefore, protection by Fe-treated NiO films is a promising strategy to achieve highly efficient and stable photoanodes.

Back-illuminated Si photocathode: a combined experimental and theoretical study for photocatalytic hydrogen evolution

Si is an excellent absorber material for use in 2-photon photoelectrochemical hydrogen production. So far nearly all studies of silicon photoelectrodes have employed frontal illumination despite the fact that in most water-splitting 2-photon device concepts the silicon is the “bottom” cell in the tandem stack and therefore illuminated from the back with respect to the electrolyte. In the present work, we investigate back-illuminated Si photoelectrodes experimentally, as well as by modelling, the dependence of induced photocurrent on various parameters, such as carrier diffusion length (Le) and surface recombination velocity (vs) to quantify their relative importance. A bifacial light absorbing structure (p+pn+ Si) is tested under back-illumination conditions which mimic the actual working environment in a tandem water splitting device. The thickness of the absorbing Si layer is varied from 30 to 350 μm to assess the impact of the diffusion length/thickness ratio (Le/L) on photocatalytic performance. It is shown how the induced photocurrent (JL) of a back-illuminated sample increases as wafer thickness decreases. Compared to the 350 μm thick sample, a thinned 50 μm thick sample shows a 2.7-fold increase in JL, and consequently also a higher open circuit voltage. An analytical model is developed to quantify how the relative Le/L-ratio affects the maximum JL under back-illumination, and the result agrees well with experimental results. JL increases with the Le/L-ratio only up to a certain point, beyond which the surface recombination velocity becomes the dominant loss mechanism. This implies that further efforts should to be focused on reduction of surface recombination. The present study is the first experimental demonstration of a Si wafer based photocathode under back-illumination. Moreover, the comparative experimental and theoretical treatment also highlights which photoabsorber properties merit the most attention in the further development towards full tandem water splitting devices.

Tailoring Mixed-Halide, Wide-Gap Perovskites via Multistep Conversion Process

Wide-band-gap mixed-halide CH3NH3PbI3-XBrX-based solar cells have been prepared by means of a sequential spin-coating process. The spin-rate for PbI2 as well as its repetitive deposition are important in determining the cross-sectional shape and surface morphology of perovskite, and, consequently, J-V performance. A perovskite solar cell converted from PbI2 with a dense bottom layer and porous top layer achieved higher device performance than those of analogue cells with a dense PbI2 top layer. This work demonstrates a facile way to control PbI2 film configuration and morphology simply by modification of spin-coating parameters without any additional chemical or thermal post-treatment.

Unbiased, complete solar charging of a neutral flow battery by a single Si photocathode

Solar redox flow batteries have attracted attention as a possible integrated technology for simultaneous conversion and storage of solar energy. In this work, we review current efforts to design aqueous solar flow batteries in terms of battery electrolyte capacity, solar conversion efficiency and depth of solar charge. From a materials cost and design perspective, a simple, cost-efficient, aqueous solar redox flow battery will most likely incorporate only one semiconductor, and we demonstrate here a system where a single photocathode is accurately matched to the redox couples to allow for a complete solar charge. The single TiO2 protected Si photocathode with a catalytic Pt layer can fully solar charge a neutral TEMPO-sulfate/ferricyanide battery with a cell voltage of 0.35 V. An unbiased solar conversion efficiency of 1.6% is obtained and this system represents a new strategy in solar RFBs where a single silicon photocathode is paired with energetically suitable redox couples to build an integrated solar energy conversion and storage device with full realization of the energy storage capacity.

Protected, back-illuminated silicon photocathodes or photoanodes for water splitting tandem stacks(Conference Presentation)

Silicon is a promising contender in the race for low-bandgap absorbers for use in a solar driven monolithic water splitting cell (PEC). However, given its role as the low-bandgap material the silicon must sit behind the corresponding high-bandgap material and as such, it will be exposed to (red) light from the dry back-side – not from the wet front side, where the electrochemistry takes place.[1,2] Depending on the configuration of the selective contacts (junctions) this may lead to compromises between high absorption and low recombination.[2,3] We discuss the tradeoffs and compare modeling results to measurements. Regardless of configuration, the wet surface of the silicon is prone to passivation or corrosion and must therefore be carefully protected in service in order to remain active. We demonstrate the use of TiO2 as an effective protection layer for both photoanodes and photocathodes in acid electrolyte [4] and NiCoOx for photoanodes in alkaline electrolyte. [3] References: [1]: B. Seger et alia, Energ. Environ. Sci., 7 (8), 2397-2413 (2014), DOI:10.1039/c4ee01335b [2]: D. Bae et alia, Energ. Environ. Sci., 8 (2), 650-660 (2015), DOI: 10.1039/c4ee03723e [3]: D. Bae et alia, submitted, (2016) [4]: B. Mei et alia, J. Phys. Chem. C., 119 (27), 15019-15027 (2015), DOI: 10.1021/acs.jpcc.5b04407