Enhanced visible light absorption in layered Cs3Bi2Br9 through mixed-valence Sn (ii)/Sn (iv) doping
Chemical Science 12, 14686-14699 (2021)
Abstract:
Lead-free halides with perovskite-related structures, such as the vacancy-ordered perovskite Cs3Bi2Br9, are of interest for photovoltaic and optoelectronic applications. We find that addition of SnBr2 to the solution-phase synthesis of Cs3Bi2Br9 leads to substitution of up to 7% of the Bi(III) ions by equal quantities of Sn(II) and Sn(IV). The nature of the substitutional defects was studied by X-ray diffraction, 133Cs and 119Sn solid state NMR, X-ray photoelectron spectroscopy and density functional theory calculations. The resulting mixed-valence compounds show intense visible and near infrared absorption due to intervalence charge transfer, as well as electronic transitions to and from localised Sn-based states within the band gap. Sn(II) and Sn(IV) defects preferentially occupy neighbouring B-cation sites, forming a double-substitution complex. Unusually for a Sn(II) compound, the material shows minimal changes in optical and structural properties after 12 months storage in air. Our calculations suggest the stabilisation of Sn(II) within the double substitution complex contributes to this unusual stability. These results expand upon research on inorganic mixed-valent halides to a new, layered structure, and offer insights into the tuning, doping mechanisms, and structure–property relationships of lead-free vacancy-ordered perovskite structures.
Optoelectronic Properties of Low-Bandgap Halide Perovskites for Solar Cell Applications
Advanced Materials 33, 2102300 (2021)
Abstract:
Riding on the coat tails of rapid developments in single-junction halide perovskite solar cells, all-perovskite multijunction solar cells have recently garnered significant attention, with the highest power-conversion efficiency already reaching 25.6%. Much of this progress has been fueled by the rapid rise in the photovoltaic performance of low-bandgap halide perovskite absorbers, materials, which, to date, have only been achievable by the partial or complete substitution of lead with tin. However, much room still exists to develop a more critical understanding of key material properties in these low-bandgap perovskites. Herein, the key optoelectronic properties of absorption, carrier generation, recombination, and transport in these tin-containing perovskites are discussed, showing that intrinsic doping distinctively impacts many of these properties, thereby rendering this class of halide perovskites unique within the family. Current understanding of the mechanisms that degrade optoelectronic performance in these materials and the corresponding devices are also summarized. These collective results highlight an important interplay between doping, defects, and degradation that will need to be controlled. Finally, the current gaps in understanding of these low-bandgap perovskites are outlined, thereby providing guidelines for further research, which will unlock their full potential for realizing a plethora of high-performance optoelectronic devices.
Superior optoelectrical properties of magnetron sputter-deposited cerium-doped indium oxide thin films for solar cell applications
Ceramics International 47, 1798-1806 (2021)
Abstract:
Indium tin oxide (ITO) is the most commonly used front contact material for a variety of photovoltaic technologies. However, the presence of a high free carrier concentration in ITO thin films results in the well-known phenomenon of free carrier absorption in the near-infrared (NIR) region of the solar spectrum. This causes optical losses especially in those solar cells where the active layer is designed to preferentially absorb NIR photons. Therefore, a combination of high carrier mobility and high NIR transparency is desired for advanced transparent conductive oxides for substituting ITO in solar cells. In this work, cerium-doped indium oxide (ICeO) thin films are deposited by pulsed DC magnetron sputtering, giving a remarkable 137% improvement of the mobility (71 cm2−1s−1) compared to the previous record value of 30 cm2V−1s−1 for DC magnetron sputtered cerium-doped ITO films on glass. When compared to conventional ITO films prepared in this work, the highest mobility of ICeO is found to be almost four times higher and also the NIR transmission is substantially enhanced. Theoretical modelling of the experimental results indicates that neutral impurity scattering limits the carrier mobility in our films. With the recent advancements in single and multi-junction organic and perovskite solar cells, the development of ICeO/glass substrates (as possible replacements for the commonly used ITO/glass substrates) demonstrates significant potential in minimizing optical losses in the NIR region.
Critical Assessment of the Use of Excess Lead Iodide in Lead Halide Perovskite Solar Cells
Journal of Physical Chemistry Letters 11, 6505–6512 (2020)
Abstract:
It is common practice in the lead halide perovskite solar cell field to add a small molar excess of lead iodide (PbI2) to the precursor solution to increase the device performance. However, recent reports have shown that an excess of PbI2 can accelerate performance loss. In addition, PbI2 is photoactive (band gap ∼2.3 eV), which may lead to parasitic absorption losses in a solar cell. Here we show that devices using small quantities of excess PbI2 exhibit better device performance as compared with stoichiometric devices, both initially and for the duration of a stability test under operating conditions, primarily by enhancing the charge extraction. However, the photolysis of PbI2 negates the beneficial effect on charge extraction by leaving voids in the perovskite film and introduces trap states that are detrimental for device performance. We propose that although excess PbI2 provides a good template for enhanced performance, the community must continue to seek other additives or synthesis routes that fulfill the same beneficial role as excess PbI2, but without the photolysis that negates these beneficial effects under long-term device operation.
Numerical analysis of high-efficiency lead-free perovskite solar cell with NiO as hole transport material and PCBM as electron transport material
CSI Transactions on ICT 8, 111–116 (2020)
Abstract:
In this work a lead free perovskite solar cell structure is proposed with NiO as the hole transport material (HTM), CH3NH3SnI3 as the perovskite absorber material and PCBM (phenyl C61 butyric acid methyl ester) as the electron transport material (ETM). Numerical analysis of the designed solar cell is performed using Solar Cell Capacitance Simulator (SCAPS-1D) program. The power conversion efficiency (PCE) of the optimized device stack is found to be above 29% with Voc = 0.98 V, Jsc = 34.86 mA/cm2, FF = 85.64%. The lead free perovskite solar cell with different HTM and ETM may be investigated for high PCE.