DOE OSTI2017
The first monolithic perovskite/silicon tandem was made with a diffused silicon p-n junction, a tunnel junction made of n ++ hydrogenated amorphous silicon, a titania electron transport layer, a methylammonium lead iodide absorber, and a Spiro-OMeTAD hole transport layer (HTL). The power conversion efficiency (PCE) was only 13.7% due to excessive parasitic absorption of light in the HTL, limiting the matched current density to 11.5 mA/cm 2 . Werner et al. 15 raised the PCE to a record 21.2% by switching to a silicon heterojunction bottom cell and carefully tuning layer thicknesses to achieve lower optical loss and a higher current density of 15.9 mA/cm 2 . It is clear from these reports that minimizing parasitic absorption in the window layers is crucial to achieving higher current densities and efficiencies in monolithic tandems. To this end, the window layers through which light first passes before entering the perovskite and silicon absorber materials must be highly transparent. The front electrode must also be conductive to carry current laterally across the top of the device. Indium tin oxide (ITO) is widely utilized as a transparent electrode in optoelectronic devices such as flat-panel displays, smart windows, organic light-emitting diodes, and solar cells due to its high conductivity and broadband transparency. ITO is typically deposited through magnetron sputtering; however, the high kinetic energy of sputtered particles can damage underlying layers. In perovskite solar cells, a sputter buffer layer is required to protect the perovskite and organic carrier extraction layers from damage during sputter deposition. The ideal buffer layer should also be energetically well aligned so as to act as a carrier-selective contact, have a wide bandgap to enable high optical transmission, and have no reaction with the halides in the perovskite. Additionally, this buffer layer should act as a diffusion barrier layer to prevent both organic cation evolution and moisture penetration to overcome the often-reported thermal and environmental instability of metal halide perovskites. Previous perovskite-containing tandems utilized molybdenum oxide (MoO x ) as a sputter buffer layer, but this has raised concerns over long-term stability, as the iodide in the perovskite can chemically react with MoO x . Mixed-cation perovskite solar cells have consistently outperformed their single-cation counterparts. The first perovskite device to exceed 20% PCE was fabricated with a mixture of methylammonium (MA) and formamidinium (FA). Recent reports have shown promising results with the introduction of cesium mixtures, enabling high efficiencies with improved photo-, moisture, and thermal stability. The increased moisture and thermal stability are especially important as they broaden the parameter space for processing on top of the perovskite, enabling the deposition of metal oxide contacts through atomic layer deposition (ALD) or chemical vapor deposition (CVD) that may require elevated temperatures or water as a counter reagent. Both titanium dioxide (TiO 2 ) and tin oxide (SnO 2 ) have consistently proven to be effective electron-selective contacts for perovskite solar cells and both can be deposited via ALD at temperatures below 150 °C. We introduced a bilayer of SnO 2 and zinc tin oxide (ZTO) that can be deposited by either low-temperature ALD or pulsed-CVD as a window layer with minimal parasitic absorption, efficient electron extraction, and sufficient buffer properties to prevent the organic and perovskite layers from damage during the subsequent sputter deposition of a transparent ITO electrode. We explored pulsed-CVD as a modified ALD process with a continual, rather than purely step-wise, growth component in order to considerably reduce the process time of the SnO 2 deposition process and minimize potential perovskite degradation. These layers, when used in an excellent mixed-cation perovskite solar cell atop a silicon solar cell tuned to the infrared spectrum, enable highly efficient perovskite-silicon tandem solar cells with enhanced thermal and environmental stability.