Low-Temperature Plasma-Assisted Atomic-Layer-Deposited SnO2 as an Electron Transport Layer in Planar Perovskite Solar Cells.

In this work, we present an extensive characterization of plasma-assisted atomic-layer-deposited SnO2 layers, with the aim of identifying key material properties of SnO2 to serve as an efficient electron transport layer in perovskite solar cells (PSCs). Electrically resistive SnO2 films are fabricated at 50 °C, while a SnO2 film with a low electrical resistivity of 1.8 × 10-3 Ω cm, a carrier density of 9.6 × 1019 cm-3, and a high mobility of 36.0 cm2/V s is deposited at 200 °C. Ultraviolet photoelectron spectroscopy indicates a conduction band offset of ∼0.69 eV at the 50 °C SnO2/Cs0.05(MA0.17FA0.83)0.95Pb(I2.7Br0.3) interface. In contrast, a negligible conduction band offset is found between the 200 °C SnO2 and the perovskite. Surprisingly, comparable initial power conversion efficiencies (PCEs) of 17.5 and 17.8% are demonstrated for the champion cells using 15 nm thick SnO2 deposited at 50 and 200 °C, respectively. The latter gains in fill factor but loses in open-circuit voltage. Markedly, PSCs using the 200 °C compact SnO2 retain their initial performance at the maximum power point over 16 h under continuous one-sun illumination in inert atmosphere. Instead, the cell with the 50 °C SnO2 shows a decrease in PCE of approximately 50%.

Highly Efficient and Stable Flexible Perovskite Solar Cells with Metal Oxides Nanoparticle Charge Extraction Layers.

In this study, the fabrication of highly efficient and durable flexible inverted perovskite solar cells (PSCs) is reported. Presynthesized, solution-derived NiOx and ZnO nanoparticles films are employed at room temperature as a hole transport layer (HTL) and electron transport layer (ETL), respectively. The triple cation perovskite films are produced in a single step and for the sake of comparison, ultrasmooth and pinhole-free absorbing layers are also fabricated using MAPbI3 perovskite. The triple cation perovskite cells exhibit champion power conversion efficiencies (PCEs) of 18.6% with high stabilized power conversion efficiency of 17.7% on rigid glass/indium tin oxide (ITO) substrates (comparing with 16.6% PCE with 16.1% stabilized output efficiency for the flexible polyethylene naphthalate (PEN)/thin film barrier/ITO substrates). More interestingly, the durability of flexible PSC under simulation of operative condition is proved. Over 85% of the maximum stabilized output efficiency is retained after 1000 h aging employing a thin MAPbI3 perovskite (over 90% after 500 h with a thick triple cation perovskite). This result is comparable to a similar state of the art rigid PSC and represents a breakthrough in the stability of flexible PSC using ETLs and HTLs compatible with roll to roll production speed, thanks to their room temperature processing.

Photonic Flash Sintering of Ink-Jet-Printed Back Electrodes for Organic Photovoltaic Applications.

A study of the photonic flash sintering of a silver nanoparticle ink printed as the back electrode for organic solar cells is presented. A number of sintering settings with different intensities and pulse durations have been tested on both full-area and grid-based silver electrodes, using the complete emission spectrum of the flash lamps from UV-A to NIR. However, none of these settings was able to produce functional devices with performances comparable to those of reference cells prepared using thermally sintered ink. Different degradation mechanisms were detected in the devices with a flash-sintered back electrode. The P3HT:PCBM photoactive layer appears to be highly heat-sensitive and turned out to be severely damaged by the high temperatures generated in the silver layer during the sintering. In addition, UV-induced photochemical degradation of the functional materials was identified as another possible source of performance deterioration in the devices with grid-based electrodes. Reducing the light intensity does not provide a proper solution because in this case the Ag electrode is not sintered sufficiently. For both types of devices, with full-area and grid-based electrodes, these problems could be solved by excluding the short wavelength contribution from the flash light spectrum using a filter. Optimized sintering parameters allowed manufacture of OPV devices with performance equal to those of the reference devices. Photonic flash sintering of the top electrode in organic solar cells was demonstrated for the first time. It reveals the great potential of this sintering method for the future roll-to-roll manufacturing of organic solar cells from solution.

Reversible degradation in ITO-containing organic photovoltaics under concentrated sunlight.

Stabilities of ITO-containing and ITO-free organic solar cells were investigated under simulated AM 1.5G illumination and under concentrated natural sunlight. In both cases ITO-free devices exhibit high stability, while devices containing ITO show degradation of their photovoltaic performance. The accelerated degradation under concentrated sunlight (of up to 20 suns) in ITO-containing devices was found to be reversible. Dark exposure of degraded samples can partly restore performance. A possible underlying mechanism for such a phenomenon is discussed.

Comparative Indoor and Outdoor Degradation of Organic Photovoltaic Cells via Inter-laboratory Collaboration.

We report on the degradation of organic photovoltaic (OPV) cells in both indoor and outdoor environments. Eight different research groups contributed state of the art OPV cells to be studied at Pomona College. Power conversion efficiency and fill factor were determined from IV curves collected at regular intervals over six to eight months. Similarly prepared devices were measured indoors, outdoors, and after dark storage. Device architectures are compared. Cells kept indoors performed better than outdoors due to the lack of temperature and humidity extremes. Encapsulated cells performed better due to the minimal oxidation. Some devices showed steady aging but many failed catastrophically due to corrosion of electrodes not active device layers. Degradation of cells kept in dark storage was minimal over periods up to one year.

TOF-SIMS investigation of degradation pathways occurring in a variety of organic photovoltaic devices--the ISOS-3 inter-laboratory collaboration.

The present work is the fourth (and final) contribution to an inter-laboratory collaboration that was planned at the 3rd International Summit on Organic Photovoltaic Stability (ISOS-3). The collaboration involved six laboratories capable of producing seven distinct sets of OPV devices that were degraded under well-defined conditions in accordance with the ISOS-3 protocols. The degradation experiments lasted up to 1830 hours and involved more than 300 cells on more than 100 devices. The devices were analyzed and characterized at different points of their lifetimes by a large number of non-destructive and destructive techniques in order to identify specific degradation mechanisms responsible for the deterioration of the photovoltaic response. Work presented herein involves time-of-flight secondary ion mass spectrometry (TOF-SIMS) in order to study chemical degradation in-plane as well as in-depth in the organic solar cells. Various degradation mechanisms were investigated and correlated with cell performance. For example, photo-oxidation of the active material was quantitatively studied as a function of cell performance. The large variety of cell architectures used (some with and some without encapsulation) enabled valuable comparisons and important conclusions to be drawn on degradation behaviour. This comprehensive investigation of OPV stability has significantly advanced the understanding of degradation behaviour in OPV devices, which is an important step towards large scale application of organic solar cells.

On the stability of a variety of organic photovoltaic devices by IPCE and in situ IPCE analyses--the ISOS-3 inter-laboratory collaboration.

This work is part of the inter-laboratory collaboration to study the stability of seven distinct sets of state-of-the-art organic photovoltaic (OPV) devices prepared by leading research laboratories. All devices have been shipped to and degraded at RISØ-DTU up to 1830 hours in accordance with established ISOS-3 protocols under defined illumination conditions. In this work, we apply the Incident Photon-to-Electron Conversion Efficiency (IPCE) and the in situ IPCE techniques to determine the relation between solar cell performance and solar cell stability. Different ageing conditions were considered: accelerated full sun simulation, low level indoor fluorescent lighting and dark storage. The devices were also monitored under conditions of ambient and inert (N(2)) atmospheres, which allows for the identification of the solar cell materials more susceptible to degradation by ambient air (oxygen and moisture). The different OPVs configurations permitted the study of the intrinsic stability of the devices depending on: two different ITO-replacement alternatives, two different hole extraction layers (PEDOT:PSS and MoO(3)), and two different P3HT-based polymers. The response of un-encapsulated devices to ambient atmosphere offered insight into the importance of moisture in solar cell performance. Our results demonstrate that the IPCE and the in situ IPCE techniques are valuable analytical methods to understand device degradation and solar cell lifetime.

Defects in divided zinc-copper aluminate spinels: structural features and optical absorption properties.

Zn1-xCuxAl2O4 (0 < or = x < 0.30) compounds have been synthesized by polyesterification using metallic salts and annealing at low temperatures as well as by conventional solid state. XRD-powder data refinements (Rietveld method) have demonstrated that both compound series crystallize in the spinel structure (Fd3m) and exhibit similar inversion rates. This low-temperature route lead to metastable phases with crystallite sizes around 40 nm whereas particle sizes are larger than 1 moicrom in the case of solid-state route. This preparative method largely described in the literature allows stabilizing reduced copper states thanks to the presence of reductive organic species, which are decomposed below T = 700 degrees C. The absorption spectra of the x = 0.15 composition exhibit strong differences depending on the synthesis route. These differences can be explained by the occurrence of Cu2+/Cu+ mixed valencies in compounds prepared by the low-temperature route; 33% of monovalent copper has been identified in the x = 0.15 composition prepared by low-temperature process, whereas the solid-state compound contains only divalent copper. Reductive properties of polyesterification reaction implying citric acid and low annealing temperature (T = 700 degrees C) are mainly responsible of the occurrence of the Cu2+/Cu+ mixed valencies. Actually, the annealing under air at T = 1000 degrees C of divided zinc-copper aluminates prepared at low temperatures (T = 700 degrees C) leads to the oxidation reaction Cu+ --> Cu2+ + e- confirmed by the evolution of magnetic measurements, ESR spectra, and optical absorption properties. Defects such as oxygen vacancies in the anionic network leading to reduction in the cations coordination number could also explain the strong evolution of optical absorption spectra especially around lambda = 700 nm where intervalencies transfer (Cu+/Cu2+) as well as intra-atomic d-d transitions (Cu2+ in a 5-fold coordination) can occur. Finally the occurrence of monovalent and divalent copper at the surface of such divided oxides, probably in tetrahedral sites, has been demonstrated by FTIR spectroscopy using the co-adsorption of CO and NO as probe molecules.