Today's best perovskite solar cells use a mixture of formamidinium and methylammonium as the monovalent cations. With the addition of inorganic cesium, the resulting triple cation perovskite compositions are thermally more stable, contain less phase impurities and are less sensitive to processing conditions. This enables more reproducible device performances to reach a stabilized power output of 21.1% and ∼18% after 250 hours under operational conditions. These properties are key for the industrialization of perovskite photovoltaics.

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Cesium-containing triple cation perovskite solar cells: improved stability, reproducibility and high efficiency

In recent years, the power conversion efficiency of perovskite solar cells has increased to reach over 20%. Finding an effective means of defect passivation is thought to be a promising route for bringing further increases in the power conversion efficiency and the open-circuit voltage (VOC) of perovskite solar cells. Here, we report the use of an organic halide salt phenethylammonium iodide (PEAI) on HC(NH2)2–CH3NH3 mixed perovskite films for surface defect passivation. We find that PEAI can form on the perovskite surface and results in higher-efficiency cells by reducing the defects and suppressing non-radiative recombination. As a result, planar perovskite solar cells with a certificated efficiency of 23.32% (quasi-steady state) are obtained. In addition, a VOC as high as 1.18 V is achieved at the absorption threshold of 1.53 eV, which is 94.4% of the Shockley–Queisser limit VOC (1.25 V). Planar perovskite solar cells that have been passivated using the organic halide salt phenethylammonium iodide are shown to have suppressed non-radiative recombination and operate with a certified power conversion efficiency of 23.3%.

Surface passivation of perovskite film for efficient solar cells

Metal-halide perovskites are crystalline materials originally developed out of scientific curiosity. Unexpectedly, solar cells incorporating these perovskites are rapidly emerging as serious contenders to rival the leading photovoltaic technologies. Power conversion efficiencies have jumped from 3% to over 20% in just four years of academic research. Here, we review the rapid progress in perovskite solar cells, as well as their promising use in light-emitting devices. In particular, we describe the broad tunability and fabrication methods of these materials, the current understanding of the operation of state-of-the-art solar cells and we highlight the properties that have delivered light-emitting diodes and lasers. We discuss key thermal and operational stability challenges facing perovskites, and give an outlook of future research avenues that might bring perovskite technology to commercialization.

Metal-halide perovskites for photovoltaic and light-emitting devices

The recent dramatic rise in power conversion efficiencies (PCEs) of perovskite solar cells (PSCs) has triggered intense research worldwide. However, high PCE values have often been reached with poor stability at an illuminated area of typically less than 0.1 square centimeter. We used heavily doped inorganic charge extraction layers in planar PSCs to achieve very rapid carrier extraction, even with 10- to 20-nanometer-thick layers, avoiding pinholes and eliminating local structural defects over large areas. The robust inorganic nature of the layers allowed for the fabrication of PSCs with an aperture area >1 square centimeter that have a PCE >15%, as certified by an accredited photovoltaic calibration laboratory. Hysteresis in the current-voltage characteristics was eliminated; the PSCs were stable, with >90% of the initial PCE remaining after 1000 hours of light soaking.

http://science.sciencemag.org/content/sci/350/6263/944.full.pdf

Efficient and stable large-area perovskite solar cells with inorganic charge extraction layers

The remarkable performance of hybrid perovskite photovoltaics is attributed to their long carrier lifetimes and high photoluminescence (PL) efficiencies. High-quality films are associated with slower PL decays, and it has been claimed that grain boundaries have a negligible impact on performance. We used confocal fluorescence microscopy correlated with scanning electron microscopy to spatially resolve the PL decay dynamics from films of nonstoichiometric organic-inorganic perovskites, CH3NH3PbI3(Cl). The PL intensities and lifetimes varied between different grains in the same film, even for films that exhibited long bulk lifetimes. The grain boundaries were dimmer and exhibited faster nonradiative decay. Energy-dispersive x-ray spectroscopy showed a positive correlation between chlorine concentration and regions of brighter PL, whereas PL imaging revealed that chemical treatment with pyridine could activate previously dark grains.

https://science.sciencemag.org/content/sci/early/2015/04/29/science.aaa5333.full.pdf

Impact of microstructure on local carrier lifetime in perovskite solar cells

Long, balanced electron and hole diffusion lengths greater than 100 nanometers in the polycrystalline organolead trihalide compound CH3NH3PbI3 are critical for highly efficient perovskite solar cells. We found that the diffusion lengths in CH3NH3PbI3 single crystals grown by a solution-growth method can exceed 175 micrometers under 1 sun (100 mW cm(-2)) illumination and exceed 3 millimeters under weak light for both electrons and holes. The internal quantum efficiencies approach 100% in 3-millimeter-thick single-crystal perovskite solar cells under weak light. These long diffusion lengths result from greater carrier mobility, longer lifetime, and much smaller trap densities in the single crystals than in polycrystalline thin films. The long carrier diffusion lengths enabled the use of CH3NH3PbI3 in radiation sensing and energy harvesting through the gammavoltaic effect, with an efficiency of 3.9% measured with an intense cesium-137 source.

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Electron-hole diffusion lengths > 175 μm in solution-grown CH3NH3PbI3 single crystals

A real-time quantification of Li transport using a nondestructive neutron method to measure the Li distribution upon charge and discharge in a Li-ion cell is reported. By using in situ neutron depth profiling (NDP), we probed the onset of lithiation in a high-capacity Sn anode and visualized the enrichment of Li atoms on the surface followed by their propagation into the bulk. The delithiation process shows the removal of Li near the surface, which leads to a decreased coulombic efficiency, likely because of trapped Li within the intermetallic material. The developed in situ NDP provides exceptional sensitivity in the temporal and spatial measurement of Li transport within the battery material. This diagnostic tool opens up possibilities to understand rates of Li transport and their distribution to guide materials development for efficient storage mechanisms. Our observations provide important mechanistic insights for the design of advanced battery materials.

https://nars.osu.edu/sites/nars.osu.edu/files/uploads/In%20Situ%20Quantification%20and%20Visualization%20of%20Lithium%20Transport%20with%20Neutrons**.pdf

In Situ Quantification and Visualization of Lithium Transport with Neutrons

Hydrogen and helium ion beams delivering different doses are used in the ion implantation, at room temperature, of China Low Activation Martensitic (CLAM) steel and the induced defects studied by Doppler broadening of gamma-rays generated in positron annihilation. Defect profiles are analysed in terms of conventional S and W parameters, measures of relative contributions of low and high-momentum electrons in the annihilation peak, as functions of incident positron energies E up to 30 keV. The behaviours of the S – E , W – E and S – W plots under different implantation doses indicate clearly that the induced defect size has obvious variation with depth, taking values that interpolate between surface and bulk values, and depend mainly on helium ion fluences. The S – W plot indicates that two types of defects have formed after ion implantation.

Investigation by slow positron beam of defects in CLAM steel induced by helium and hydrogen implantation

He and H-implanted CLAM steel investigated by positron-annihilation spectroscopy

Depth-resolved cathodoluminescence spectroscopy (DRCLS), time-resolved surface photovoltage spectroscopy, X-ray photoemission spectroscopy (XPS), and current-voltage measurements together show that fast versus thermal neutrons differ strongly in their electronic and morphological effects on metal-GaN Schottky diodes. Fast and thermal neutrons introduce GaN displacement damage and native point defects, while thermal neutrons also drive metallurgical reactions at metal/GaN interfaces. Defect densities exhibit a threshold neutron fluence below which thermal neutrons preferentially heal versus create new native point defects. Scanning XPS and DRCLS reveal strong fluence- and metal-dependent electronic and chemical changes near the free surface and metal interfaces that impact diode properties.

Jie Qiu

Papers

Electron-hole diffusion lengths > 175 μm in solution-grown CH3NH3PbI3 single crystals

In Situ Quantification and Visualization of Lithium Transport with Neutrons

Investigation by slow positron beam of defects in CLAM steel induced by helium and hydrogen implantation

He and H-implanted CLAM steel investigated by positron-annihilation spectroscopy

Neutron irradiation effects on gallium nitride-based Schottky diodes