Solar-Powered Gram-Scale Ammonia Production from Nitrate.

The photoelectrochemical (PEC) method has the potential to be an attractive route for converting and storing solar energy as chemical bonds. In this study, a maximum NH3 production yield of 1.01 g L-1 with a solar-to-ammonia conversion efficiency of 8.17% through the photovoltaic electrocatalytic (PV-EC) nitrate (NO3 -) reduction reaction (NO3 -RR) is achieved, using silicon heterojunction solar cell technology. Additionally, the effect of tuning the operation potential of the PV-EC system and its influence on product selectivity are systematically investigated. By using this unique external resistance tuning approach in the PV-EC system, ammonia production through nitrate reduction performance from 96 to 360 mg L-1 is enhanced, a four-fold increase. Furthermore, the NH3 is extracted as NH4Cl powder using acid stripping, which is essential for storing chemical energy. This work demonstrates the possibility of tuning product selectivity in PV-EC systems, with prospects toward pilot scale on value-added product synthesis.

Moisture-Resilient Perovskite Solar Cells for Enhanced Stability.

With the rapid rise in device performance of perovskite solar cells (PSCs), overcoming instabilities under outdoor operating conditions has become the most crucial obstacle toward their commercialization. Among stressors such as light, heat, voltage bias, and moisture, the latter is arguably the most critical, as it can decompose metal-halide perovskite (MHP) photoactive absorbers instantly through its hygroscopic components (organic cations and metal halides). In addition, most charge transport layers (CTLs) commonly employed in PSCs also degrade in the presence of water. Furthermore, photovoltaic module fabrication encompasses several steps, such as laser processing, subcell interconnection, and encapsulation, during which the device layers are exposed to the ambient atmosphere. Therefore, as a first step toward long-term stable perovskite photovoltaics, it is vital to engineer device materials toward maximizing moisture resilience, which can be accomplished by passivating the bulk of the MHP film, introducing passivation interlayers at the top contact, exploiting hydrophobic CTLs, and encapsulating finished devices with hydrophobic barrier layers, without jeopardizing device performance. Here, existing strategies for enhancing the performance stability of PSCs are reviewed and pathways toward moisture-resilient commercial perovskite devices are formulated.

Efficient and stable perovskite-silicon tandem solar cells through contact displacement by MgFx.

The performance of perovskite solar cells with inverted polarity (p-i-n) is still limited by recombination at their electron extraction interface, which also lowers the power conversion efficiency (PCE) of p-i-n perovskite-silicon tandem solar cells. A MgFx interlayer with thickness of ~1 nanometer at the perovskite/C60 interface favorably adjusts the surface energy of the perovskite layer through thermal evaporation, which facilitates efficient electron extraction and displaces C60 from the perovskite surface to mitigate nonradiative recombination. These effects enable a champion open-circuit voltage of 1.92 volts, an improved fill factor of 80.7%, and an independently certified stabilized PCE of 29.3% for a monolithic perovskite-silicon tandem solar cell ~1 square centimeter in area. The tandem retained ~95% of its initial performance after damp-heat testing (85°C at 85% relative humidity) for >1000 hours.

Damp heat-stable perovskite solar cells with tailored-dimensionality 2D/3D heterojunctions.

If perovskite solar cells (PSCs) with high power conversion efficiencies (PCEs) are to be commercialized, they must achieve long-term stability, which is usually assessed with accelerated degradation tests. One of the persistent obstacles for PSCs has been successfully passing the damp-heat test (85°C and 85% relative humidity), which is the standard for verifying the stability of commercial photovoltaic (PV) modules. We fabricated damp heat-stable PSCs by tailoring the dimensional fragments of two-dimensional perovskite layers formed at room temperature with oleylammonium iodide molecules; these layers passivate the perovskite surface at the electron-selective contact. The resulting inverted PSCs deliver a 24.3% PCE and retain >95% of their initial value after >1000 hours at damp-heat test conditions, thereby meeting one of the critical industrial stability standards for PV modules.

Tin Oxide Electron-Selective Layers for Efficient, Stable, and Scalable Perovskite Solar Cells.

Perovskite solar cells (PSCs) have become a promising photovoltaic (PV) technology, where the evolution of the electron-selective layers (ESLs), an integral part of any PV device, has played a distinctive role to their progress. To date, the mesoporous titanium dioxide (TiO2 )/compact TiO2 stack has been among the most used ESLs in state-of-the-art PSCs. However, this material requires high-temperature sintering and may induce hysteresis under operational conditions, raising concerns about its use toward commercialization. Recently, tin oxide (SnO2 ) has emerged as an attractive alternative ESL, thanks to its wide bandgap, high optical transmission, high carrier mobility, suitable band alignment with perovskites, and decent chemical stability. Additionally, its low-temperature processability enables compatibility with temperature-sensitive substrates, and thus flexible devices and tandem solar cells. Here, the notable developments of SnO2 as a perovskite-relevant ESL are reviewed with emphasis placed on the various fabrication methods and interfacial passivation routes toward champion solar cells with high stability. Further, a techno-economic analysis of SnO2 materials for large-scale deployment, together with a processing-toxicology assessment, is presented. Finally, a perspective on how SnO2 materials can be instrumental in successful large-scale module and perovskite-based tandem solar cell manufacturing is provided.

Lewis-Acid Doping of Triphenylamine-Based Hole Transport Materials Improves the Performance and Stability of Perovskite Solar Cells.

Highly efficient perovskite solar cells (PSCs) fabricated in the classic n-i-p configuration generally employ triphenylamine-based hole-transport layers (HTLs) such as spiro-OMeTAD, PTAA, and poly-TPD. Controllable doping of such layers has been critical to achieve increased conductivity and high device performance. To this end, LiTFSI/tBP doping and subsequent air exposure is widely utilized. However, this approach often leads to low device stability and reproducibility. Departing from this point, we introduce the Lewis acid tris(pentafluorophenyl)borane (TPFB) as an effective dopant, resulting in a significantly improved conductivity and lowered surface potential for triphenylamine-based HTLs. Here, we specifically investigated spiro-OMeTAD, which is the most widely used HTL for n-i-p devices, and revealed improved power conversion efficiency (PCE) and stability of the PSCs. Further, we demonstrated the applicability of TPFB doping to other triphenylamine-based HTLs. Spectroscopic characterizations reveal that TPFB doping results in significantly improved charge transport and reduced recombination losses. Importantly, the TPFB-doped perovskite devices retained near 85% of the initial PCE after 1000 h of storage in the air, while the conventional LiTFSI-doped device dropped to 75%. Finally, we give insight into utilizing other similar molecular dopants such as fluorine-free triphenylborane and phosphorus-centered tris(pentafluorophenyl)phosphine (TPFP) by density functional theory analysis underscoring the significance of the central boron atom and fluorination in TPFB for the formation of Lewis acid-base adducts.

Pseudohalide (SCN(-))-Doped MAPbI3 Perovskites: A Few Surprises.

Pseudohalide thiocyanate anion (SCN(-)) has been used as a dopant in a methylammonium lead tri-iodide (MAPbI3) framework, aiming for its use as an absorber layer for photovoltaic applications. The substitution of SCN(-) pseudohalide anion, as verified using Fourier transform infrared (FT-IR) spectroscopy, results in a comprehensive effect on the optical properties of the original material. Photoluminescence measurements at room temperature reveal a significant enhancement in the emission quantum yield of MAPbI3-x(SCN)x as compared to MAPbI3, suggestive of suppression of nonradiative channels. This increased intensity is attributed to a highly edge specific emission from MAPbI3-x(SCN)x microcrystals as revealed by photoluminescence microscopy. Fluoresence lifetime imaging measurements further established contrasting carrier recombination dynamics for grain boundaries and the bulk of the doped material. Spatially resolved emission spectroscopy on individual microcrystals of MAPbI3-x(SCN)x reveals that the optical bandgap and density of states at various (local) nanodomains are also nonuniform. Surprisingly, several (local) emissive regions within MAPbI3-x(SCN)x microcrystals are found to be optically unstable under photoirradiation, and display unambiguous temporal intermittency in emission (blinking), which is extremely unusual and intriguing. We find diverse blinking behaviors for the undoped MAPbI3 crystals as well, which leads us to speculate that blinking may be a common phenomenon for most hybrid perovskite materials.

Inorganic Hole Conducting Layers for Perovskite-Based Solar Cells.

Hybrid organic-inorganic semiconducting perovskite photovoltaic cells are usually coupled with organic hole conductors. Here, we report planar, inverse CH3NH3PbI3-xClx-based cells with inorganic hole conductors. Using electrodeposited NiO as hole conductor, we have achieved a power conversion efficiency of 7.3%. The maximum VOC obtained was 935 mV with an average VOC value being 785 mV. Preliminary results for similar cells using electrodeposited CuSCN as hole conductor resulted in devices up to 3.8% in efficiency. The ability to obtain promising cells using NiO and CuSCN expands the presently rather limited range of available hole conductors for perovskite cells.

On the Uniqueness of Ideality Factor and Voltage Exponent of Perovskite-Based Solar Cells.

Perovskite-based solar cells have attracted much recent research interest with efficiency approaching 20%. While various combinations of material parameters and processing conditions are attempted for improved performance, there is still a lack of understanding in terms of the basic device physics and functional parameters that control the efficiency. Here we show that perovskite-based solar cells have two universal features: an ideality factor close to two and a space-charge-limited current regime. Through detailed numerical modeling, we identify the mechanisms that lead to these universal features. Our model predictions are supported by experimental results on solar cells fabricated at five different laboratories using different materials and processing conditions. Indeed, this work unravels the fundamental operation principle of perovskite-based solar cells, suggests ways to improve the eventual performance, and serves as a benchmark to which experimental results from various laboratories can be compared.