Adharsh Rajagopal

Stable Low-Bandgap Pb–Sn Binary Perovskites for Tandem Solar Cells

A low-bandgap (1.33 eV) Sn-based MA0.5 FA0.5 Pb0.75 Sn0.25 I3 perovskite is developed via combined compositional, process, and interfacial engineering. It can deliver a high power conversion efficiency (PCE) of 14.19%. Finally, a four-terminal all-perovskite tandem solar cell is demonstrated by combining this low-bandgap cell with a semitransparent MAPbI3 cell to achieve a high efficiency of 19.08%.

Current Challenges and Prospective Research for Upscaling Hybrid Perovskite Photovoltaics

Organic-inorganic hybrid perovskite photovoltaics (PSCs) are poised to push toward technology translation, but significant challenges complicating commercialization remain. Though J-V hysteresis and ecotoxicity are uniquely imposing issues at scale, CH3NH3PbI3 degradation is by far the sharpest limitation to the technologys potential market contribution. Herein, we offer a perspective on the practical market potential of PSCs, the nature of fundamental PSC challenges at scale, and an outline of prospective solutions for achieving module scale PSC production tailored to intrinsic advantages of CH3NH3PbI3. Although integrating PSCs into the energy grid is complicated by CH3NH3PbI3 degradation, the ability of PSCs to contribute to consumer electronics and other niche markets like those organic photovoltaics have sought footing in rests primarily upon the technologys price point. Thus, slot die, roll-to-roll processing has the greatest potential to enable PSC scale-up, and herein, we present a perspective on the research necessary to realize fully printable PSCs at scale.

Highly Efficient Perovskite–Perovskite Tandem Solar Cells Reaching 80% of the Theoretical Limit in Photovoltage

Organic-inorganic hybrid perovskite multijunction solar cells have immense potential to realize power conversion efficiencies (PCEs) beyond the Shockley-Queisser limit of single-junction solar cells; however, they are limited by large nonideal photovoltage loss (V oc,loss ) in small- and large-bandgap subcells. Here, an integrated approach is utilized to improve the V oc of subcells with optimized bandgaps and fabricate perovskite-perovskite tandem solar cells with small V oc,loss . A fullerene variant, Indene-C60 bis-adduct, is used to achieve optimized interfacial contact in a small-bandgap (≈1.2 eV) subcell, which facilitates higher quasi-Fermi level splitting, reduces nonradiative recombination, alleviates hysteresis instabilities, and improves V oc to 0.84 V. Compositional engineering of large-bandgap (≈1.8 eV) perovskite is employed to realize a subcell with a transparent top electrode and photostabilized V oc of 1.22 V. The resultant monolithic perovskite-perovskite tandem solar cell shows a high V oc of 1.98 V (approaching 80% of the theoretical limit) and a stabilized PCE of 18.5%. The significantly minimized nonideal V oc,loss is better than state-of-the-art silicon-perovskite tandem solar cells, which highlights the prospects of using perovskite-perovskite tandems for solar-energy generation. It also unlocks opportunities for solar water splitting using hybrid perovskites with solar-to-hydrogen efficiencies beyond 15%.

Improved efficiency and stability of Pb–Sn binary perovskite solar cells by Cs substitution

Partially replacing Pb with Sn in organic–inorganic lead halide perovskites has been proven as a promising approach to reduce environmental toxicity and develop low bandgap (as low as 1.20 eV) perovskite solar cells (PVSCs) beneficial for constructing perovskite-based tandem solar cells. In this work, we demonstrated that partially replacing MA+ or FA+ with Cs+ in a Pb–Sn binary perovskite system can effectively retard the associated crystallization rate to facilitate homogenous film formation, subsequently resulting in enhanced device performance and stability, especially for high Sn-containing compositions. The representative MA0.9Cs0.1Pb0.5Sn0.5I3 PVSC with a low Eg of 1.28 eV not only achieves an improved efficiency up to 10.07% but also possesses much improved thermal and ambient stability as compared to the pristine MAPb0.5Sn0.5I3 PVSC showing poorer efficiency (6.36%) and stability. Similarly, when Cs was introduced into FAPb1−xSnxI3 perovskite, enhanced performance was observed, affirming its general applicability and beneficial role in mediating the crystal growth and film formation of Pb–Sn binary perovskites.

Ag-Incorporated Organic–Inorganic Perovskite Films and Planar Heterojunction Solar Cells

Controlled doping for adjustable material polarity and charge carrier concentration is the basis of semiconductor materials and devices, and it is much more difficult to achieve in ionic semiconductors (e.g., ZnO and GaN) than in covalent semiconductors (e.g., Si and Ge), due to the high intrinsic defect density in ionic semiconductors. The organic-inorganic perovskite material, which is frenetically being researched for applications in solar cells and beyond, is also an ionic semiconductor. Here we present the Ag-incorporated organic-inorganic perovskite films and planar heterojunction solar cells. Partial substitution of Pb2+ by Ag+ leads to improved film morphology, crystallinity, and carrier dynamics as well as shifted Fermi level and reduced electron concentration. Consequently, in planar heterojunction photovoltaic devices with inverted stacking structure, Ag incorporation results in an enhancement of the power conversion efficiency from 16.0% to 18.4% in MAPbI3 based devices and from 11.2% to 15.4% in MAPbI3-xClx based devices. Our work implies that Ag incorporation is a feasible route to adjust carrier concentrations in solution-processed perovskite materials in spite of the high concentration of intrinsic defects.

Abnormal Current-Voltage Hysteresis Induced by Reverse Bias in Organic-Inorganic Hybrid Perovskite Photovoltaics

In this study, reverse bias (RB)-induced abnormal hysteresis is investigated in perovskite solar cells (PVSCs) with nickel oxide (NiOx)/methylammonium lead iodide (CH3NH3PbI3) interfaces. Through comprehensive current-voltage (I-V) characterization and bias-dependent external quantum efficiency (EQE) measurements, we demonstrate that this phenomenon is caused by the interfacial ion accumulation intrinsic to CH3NH3PbI3. Subsequently, via systematic analysis we discover that the abnormal I-V behavior is remarkably similar to tunnel diode I-V characteristics and is due to the formation of a transient tunnel junction at NiOx/CH3NH3PbI3 interfaces under RB. The detailed analysis navigating the complexities of I-V behavior in CH3NH3PbI3-based solar cells provided here ultimately illuminates possibilities in modulating ion motion and hysteresis via interfacial engineering in PVSCs. Furthermore, this work shows that RB can alter how CH3NH3PbI3 contributes to the functional nature of devices and provides the first steps toward approaching functional perovskite interfaces in new ways for metrology and analysis of complex transient processes.

Ideal Bandgap Organic–Inorganic Hybrid Perovskite Solar Cells

Extremely high power conversion efficiencies (PCEs) of ≈20-22% are realized through intensive research and development of 1.5-1.6 eV bandgap perovskite absorbers. However, development of ideal bandgap (1.3-1.4 eV) absorbers is pivotal to further improve PCE of single junction perovskite solar cells (PVSCs) because of a better balance between absorption loss of sub-bandgap photons and thermalization loss of above-bandgap photons as demonstrated by the Shockley-Queisser detailed balanced calculation. Ideal bandgap PVSCs are currently hindered by the poor optoelectronic quality of perovskite absorbers and their PCEs have stagnated at <15%. In this work, through systematic photoluminescence and photovoltaic analysis, a new ideal bandgap (1.35 eV) absorber composition (MAPb0.5 Sn0.5 (I0.8 Br0.2 )3 ) is rationally designed and developed, which possesses lower nonradiative recombination states, band edge disorder, and Urbach energy coupled with a higher absorption coefficient, which yields a reduced Voc,loss (0.45 V) and improved PCE (as high as 17.63%) for the derived PVSCs. This work provides a promising platform for unleashing the complete potential of ideal bandgap PVSCs and prospects for further improvement.

Realizing a new class of hybrid organic–inorganic multifunctional perovskite

Modification of CH3NH3PbI3 and related hybrid organic–inorganic semiconductors has become an increasingly important effort because of the need to control fundamental material properties. Herein, we closely study material growth to identify the most significant controlling variables determining morphological evolution in a new class of hybrid perovskite alloy. Specifically, drop-casting based perovskite analysis shows that CH3NH3Pb(Mn)yI3, CH3NH3Pb(Fe)yI3, CH3NH3Pb(Co)yI3, and CH3NH3Pb(Ni)yI3 constitute a unique class of hybrid organic–inorganic perovskite in which growth route most strongly determines morphology. Mn, Fe, Co, and Ni consistently modify CH3NH3PbI3 growth, enabling direct perovskite nucleation to compete with growth through solvent induced intermediate states. We show unambiguously that solvent-perovskite co-crystal formation is responsible for the rod-like thin-film morphology that a great deal of work optimizing perovskite growth in planar heterojunction solar cells endeavors to circumvent. In addition to providing insight into the role of growth route in morphological evolution, we also identity the impact of CH3NH3I stoichiometry and the impact of magnetic properties on growth as secondary variables that significantly affect optoelectronic properties. Leveraging this understanding to minimize the impact of morphological phenomena on performance, we closely analyze the compositional impact of these transition metals on optoelectronic quality using CH3NH3Pb(Fe)yI3 as a model system showing that transition metal inclusion of this type leads to trap-assisted recombination within the perovskite bulk that both sharply limits Jsc and causes significant hysteresis. By comparing device performance of Mn, Fe, Co, and Ni based systems, we show that Mn relieves this sharp limitation on Jsc and almost completely eliminates hysteresis. CH3NH3Pb(Mn)yI3 thus allows the implementation of direct perovskite nucleation while minimizing the deleterious impact of transition metal inclusion. PL analysis shows that this material is also more emissive than CH3NH3PbI3, making it ideal for light production as well. Methodology and insights developed herein outline a generalizable approach for navigating complexity of perovskite compositional modification.

Overcoming the Photovoltage Plateau in Large Bandgap Perovskite Photovoltaics

Development of large bandgap (1.80-1.85 eV Eg) perovskite is crucial for perovskite-perovskite tandem solar cells. However, the performance of 1.80-1.85 eV Eg perovskite solar cells (PVKSCs) are significantly lagging their counterparts in the 1.60-1.75 eV Eg range. This is because the photovoltage ( Voc) does not proportionally increase with Eg due to lower optoelectronic quality of conventional (MA,FA,Cs)Pb(I,Br)3 and results in a photovoltage plateau ( Voc limited to 80% of the theoretical limit for ∼1.8 eV Eg). Here, we incorporate phenylethylammonium (PEA) in a mixed-halide perovskite composition to solve the inherent material-level challenges in 1.80-1.85 eV Eg perovskites. The amount of PEA incorporation governs the topography and optoelectronic properties of resultant films. Detailed structural and spectroscopic characterization reveal the characteristic trends in crystalline size, orientation, and charge carrier recombination dynamics and rationalize the origin of improved material quality with higher luminescence. With careful interface optimization, the improved material characteristics were translated to devices and Voc values of 1.30-1.35 V were achieved, which correspond to 85-87% of the theoretical limit. Using an optimal amount of PEA incorporation to balance the increase in Voc and the decrease in charge collection, a highest power conversion efficiency of 12.2% was realized. Our results clearly overcome the photovoltage plateau in the 1.80-1.85 eV Eg range and represent the highest Voc achieved for mixed-halide PVKSCs. This study provides widely translatable insights, an important breakthrough, and a promising platform for next-generation perovskite tandems.

Photoluminescence and Photoconductivity to Assess Maximum Open-Circuit Voltage and Carrier Transport in Hybrid Perovskites and Other Photovoltaic Materials

Photovoltaic (PV) device development is much more expensive and time-consuming than the development of the absorber layer alone. This Perspective focuses on two methods that can be used to rapidly assess and develop PV absorber materials independent of device development. The absorber material properties of quasi-Fermi level splitting and carrier diffusion length under steady effective 1 Sun illumination are indicators of a materials ability to achieve high VOC and JSC. These two material properties can be rapidly and simultaneously assessed with steady-state absolute intensity photoluminescence and photoconductivity measurements. As a result, these methods are extremely useful for predicting the quality and stability of PV materials prior to PV device development. Here, we summarize the methods, discuss their strengths and weaknesses, and compare photoluminescence and photoconductivity results with device performance for four hybrid perovskite compositions of various bandgaps (1.35-1.82 eV), CISe, CIGSe, and CZTSe.