Impact of Monovalent Metal Halides on the Structural and Photophysical Properties of Halide Perovskite

This chapter discusses the importance and impact of metal halide additives into perovskite to enhance its semiconductor quality and realize highly efficient and stable perovskite photovoltaic devices. Monovalent metal halides have been introduced as the most promising candidates due to their loading capacity and chemical compatibility with the perovskite materials, as well as ease of incorporation and their remarkable positive impact on the crystal growth, optoelectronic properties, and subsequently the performance of perovskite solar cells (PSCs). Among all the monovalent metal cations, Cs is the only one that could fit in the perovskite structure and forms photoactive perovskite. The other monovalent cations are located at the interstitials sites, grain boundaries, and crystalline surfaces. We also discuss the key roles of monovalent metal halide additives that include modulating morphology of perovskite films, modification of structural and optoelectronic properties, adjusting energy level alignment in PSCs, inhibiting non-radiative recombination in perovskites, eliminating hysteresis, and enhancing operational stability of PSCs

Advances in All-Inorganic Perovskite Nanocrystal-Based White Light Emitting Devices

Metal halide perovskites (MHPs) are exceptional semiconductors best known for their intriguing properties, such as high absorption coefficients, tunable bandgaps, excellent charge transport, and high luminescence yields. Among various MHPs, all-inorganic perovskites exhibit benefits over hybrid compositions. Notably, critical properties, including chemical and structural stability, could be improved by employing organic-cation-free MHPs in optoelectronic devices such as solar cells and light-emitting devices (LEDs). Due to their enticing features, including spectral tunability over the entire visible spectrum with high color purity, all-inorganic perovskites have become a focus of intense research for LEDs. This Review explores and discusses the application of all-inorganic CsPbX3 nanocrystals (NCs) in developing blue and white LEDs. We discuss the challenges perovskite-based LEDs (PLEDs) face and the potential strategies adopted to establish state-of-the-art synthetic routes to obtain rational control over dimensions and shape symmetry without compromising the optoelectronic properties. Finally, we emphasize the significance of matching the driving currents of different LED chips and balancing the aging and temperature of individual chips to realize efficient, uniform, and stable white electroluminescence

Interface engineering of mesoscopic hybrid organic-inorganic perovskite solar cells

We report on the optimization of the interfacial properties of titania in mesoscopic CH3NH3PbI3 perovskite solar cells (PSCs). Modification of the mesoporous titania (mp-TiO2) film by TiCl4 treatment substantially reduced the surface traps, as is evident from the sharpness of the absorption edge with a significant reduction in Urbach energy (from 320 to 140 meV) determined from photothermal deflection spectroscopy, and led to an order of magnitude enhancement in the bulk electron mobility and corresponding decrease in the transport activation energy (from 170 to 90 meV) within a device. After optimization of the photoanode–perovskite interface using various sizes of TiO2 nanoparticles, the best photovoltaic efficiency of 16.3% was achieved with the mesoporous TiO2 composed of 36 nm sized nanoparticles. The improvement in device performance can be attributed to the enhanced charge collection efficiency that is driven by improved charge transport in the mesoporous TiO2 layer. Also, the decreased recombination at the TiO2–perovskite interface and better perovskite coverage play important roles

Champion Device Architectures for Low-Cost and Stable Single-Junction Perovskite Solar Cells

High power conversion efficiencies (PCE), low energy payback time (EPBT), and low manufacturing costs render perovskite solar cells (PSCs) competitive; however, a relatively low operational stability impedes their large-scale deployment. In addition, state-of-the-art PSCs are made of expensive materials, including the organic hole transport materials (HTMs) and the noble metals used as the charge collection electrode, which induce degradation in PSCs. Thus, developing inexpensive alternatives is crucial to fostering the transition from academic research to industrial development. Combining a carbon-based electrode with an inorganic HTM has shown the highest potential and should replace noble metals and organic HTMs. In this review, we illustrate the incorporation of a carbon layer as a back contact instead of noble metals and inorganic HTMs instead of organic ones as two cornerstones for achieving optimal stability and economic viability for PSCs. We discuss the primary considerations for the selection of the absorbing layer as well as the electron-transporting layer to be compatible with the champion designs and ultimate architecture for single-junction PSCs. More studies regarding the long-term stability are still required. Using the recommended device architecture presented in this work would pave the way toward constructing low-cost and stable PSCs.Copyright © 2022 The Authors. Published by American Chemical Society. This publication is licensed under CC-BY 4.0

Charge extraction via graded doping of hole transport layers gives highly luminescent and stable metal halide perovskite devices.

One source of instability in perovskite solar cells (PSCs) is interfacial defects, particularly those that exist between the perovskite and the hole transport layer (HTL). We demonstrate that thermally evaporated dopant-free tetracene (120 nm) on top of the perovskite layer, capped with a lithium-doped Spiro-OMeTAD layer (200 nm) and top gold electrode, offers an excellent hole-extracting stack with minimal interfacial defect levels. For a perovskite layer interfaced between these graded HTLs and a mesoporous TiO2 electron-extracting layer, its photoluminescence yield reaches 15% compared to 5% for the perovskite layer interfaced between TiO2 and Spiro-OMeTAD alone. For PSCs with graded HTL structure, we demonstrate efficiency of up to 21.6% and an extended power output of over 550 hours of continuous illumination at AM1.5G, retaining more than 90% of the initial performance and thus validating our approach. Our findings represent a breakthrough in the construction of stable PSCs with minimized nonradiative losses.Cambridge Materials Limite

Monovalent Cation Doping of CH3NH3PbI3 for Efficient Perovskite Solar Cells.

Here, we demonstrate the incorporation of monovalent cation additives into CH3NH3PbI3 perovskite in order to adjust the optical, excitonic, and electrical properties. The possibility of doping was investigated by adding monovalent cation halides with similar ionic radii to Pb2+, including Cu+, Na+, and Ag+. A shift in the Fermi level and a remarkable decrease of sub-bandgap optical absorption, along with a lower energetic disorder in the perovskite, was achieved. An order-of-magnitude enhancement in the bulk hole mobility and a significant reduction of transport activation energy within an additive-based perovskite device was attained. The confluence of the aforementioned improved properties in the presence of these cations led to an enhancement in the photovoltaic parameters of the perovskite solar cell. An increase of 70 mV in open circuit voltage for AgI and a 2 mA/cm2 improvement in photocurrent density for NaI- and CuBr-based solar cells were achieved compared to the pristine device. Our work paves the way for further improvements in the optoelectronic quality of CH3NH3PbI3 perovskite and subsequent devices. It highlights a new avenue for investigations on the role of dopant impurities in crystallization and controls the electronic defect density in perovskite structures.M. Abdi-Jalebi thanks Nava Technology Limited for a PhD scholarship. M.I. Dar and M.Grätzel thank the King Abdulaziz City for Science and Technology (KACST) and the Swiss National Science Foundation (SNSF) for financial support

Perovskite solar cells with CuSCN hole extraction layers yield stabilized efficiencies greater than 20%

Perovskite solar cells (PSCs) with efficiencies greater than 20% have been realized only with expensive organic hole-transporting materials. We demonstrate PSCs that achieve stabilized efficiencies exceeding 20% with copper(I) thiocyanate (CuSCN) as the hole extraction layer. A fast solvent removal method enabled the creation of compact, highly conformal CuSCN layers that facilitate rapid carrier extraction and collection. The PSCs showed high thermal stability under long-term heating, although their operational stability was poor. This instability originated from potential-induced degradation of the CuSCN/Au contact. The addition of a conductive reduced graphene oxide spacer layer between CuSCN and gold allowed PSCs to retain >95% of their initial efficiency after aging at a maximum power point for 1000 hours under full solar intensity at 60 degrees C. Under both continuous full-sun illumination and thermal stress, CuSCN-based devices surpassed the stability of spiro-OMeTAD-based PSCs

Hill climbing hysteresis of perovskite-based solar cells: a maximum power point tracking investigation

The surge of the power conversion efficiency of metal halide lead perovskite solar cells comes with concerns, such as the long-term ecotoxicity of lead compounds, their sensitivity toward moisture and oxygen, or the scarcity of some of their components. Most perovskite solar cells still suffer from serious stability problems when measured under real working conditions (maximum power point tracking at 60 degrees C). In the long run, stability will certainly decide on the fate of CH3NH3PbI3 and related lead perovskites for their use in photovoltaic modules. Herein, we show an effective and inexpensive strategy to perform ageing of perovskite solar cells under maximum power point tracking. For the first time, we analyze the issue of power extraction from solar cells exhibiting hysteresis. We show that a standard tracking algorithm such as perturb and observe fails to converge to the maximum power point of the solar cell if it exhibits j(V) hysteresis, and we present an effective strategy to stabilize the algorithm. We show that enforcing oscillations in forward bias can boost the mean power output of some perovskite solar cells by more than 10%, in contrast to a reference crystalline silicon solar cell. Copyright (c) 2017 John Wiley & Sons, Ltd

The Role of Rubidium in Multiple-Cation-Based High-Efficiency Perovskite Solar Cells

Perovskite solar cells (PSCs) based on cesium (Cs)- and rubidium (Rb)-containing perovskite films show highly reproducible performance; however, a fundamental understanding of these systems is still emerging. Herein, this study has systematically investigated the role of Cs and Rb cations in complete devices by examining the transport and recombination processes using current-voltage characteristics and impedance spectroscopy in the dark. As the credibility of these measurements depends on the performance of devices, this study has chosen two different PSCs, (MAFACs) Pb(IIBr)(3) (MA = CH3NH3+, FA = CH(NH2)(2)(+)) and (MAFACsRb) Pb(IIBr)(3), yielding impressive performances of 19.5% and 21.1%, respectively. From detailed studies, this study surmises that the confluence of the low trap-assisted charge-carrier recombination, low resistance offered to holes at the perovskite/2,2', 7,7'-tetrakis(N, N-di-p-methoxyphenylamine)- 9,9-spirobifluorene interface with a low series resistance (R-s), and low capacitance leads to the realization of higher performance when an extra Rb cation is incorporated into the absorber films. This study provides a thorough understanding of the impact of inorganic cations on the properties and performance of highly efficient devices, and also highlights new strategies to fabricate efficient multiple-cation-based PSCs

High photovoltage in perovskite solar cells: New physical insights from the ultrafast transient absorption spectroscopy

To understand the cause of the high open circuit photovoltage (VOC) achieved by todays' state of the art perovskite solar cells (PSCs), we examine formamidinium lead bromide CH(NH2)(2)PbBr3 films by ultrafast transient absorption spectroscopy (TAS). By using TiO2 and spiro-OMeTAD as charge extraction layers, the devices based on the CH(NH2)(2)PbBr3 films yield VOC as high as 1.5 V ascertaining their high quality. TAS establish that the presence of charge extraction layers has very little influences on the nature of a negative band at 535 nm corresponding to the bleaching of the absorption band edge and two positive bands in the CH(NH2)(2)PbBr3 films. Therefore, we contend that the V-OC in PSC is predominantly determined by the quasi Fermi level splitting within the perovskite layer. (C) 2017 Published by Elsevier B. V